Abstract:
A topical skin protectant formulation containing a barrier cream and an active moiety for protecting warfighters and civilians against all types of harmful chemicals, specifically chemical warfare agents (CWA). The active moiety is an amine, polyalkenimines and/or derivatives. The topical skin protectant offers a barrier property and an active moiety that serves to neutralize chemical warfare agents into less toxic agents.

Description:
This application claims priority of provisional application No. 60/378,443 filed May 6, 2003. 
    
    
     The invention described herein may be manufactured, used and licensed by or for the U.S. Government. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to active topical skin protectants. More specifically, the invention relates to an active barrier cream for protection against all types of harmful chemicals, specifically chemical warfare agents (CWAs). The active barrier cream is applied prior to exposure on the skin of persons at risk of exposure to harmful chemicals to provide a protective barrier for the skin. The active barrier cream chemically or physically reacts with harmful chemicals such as CWAs (vesicants and nerve agents) to neutralize these harmful chemicals while the barrier properties of the cream prevent penetration of harmful chemicals through the cream to the skin. 
     2. Description of Related Art 
     The concept of applying a topical protectant to vulnerable skin surfaces before entry into a chemical combat arena has been proposed as a protective measure against percutaneous CWA toxicity since the first use of CWA in World War I. The protectant was applied to vulnerable skin surfaces prior to entry into a chemical combat area. Topical protectants should augment the protection afforded by the protective over garments and/or redefine the circumstances requiring mission oriented protective posture (MOPP) levels. The rapid action of vesicating agents, also known as blistering agents, such as sulfur mustard (HD) and lewisite (L), require a pre-exposure skin protection system or a contamination avoidance approach that may preclude the percutaneous toxicity of these agents. These approaches also reduce the risk of exposure to organophosphorus (OP) chemical agents (nerve agents), which unlike the vesicating agents are lethal in droplet amounts. 
     An organic molecule, S-330, that reacts with CWA was incorporated into a product and fielded as the M-5 ointment kit at the end of World War II (Formula 1). 
                                
However, the unacceptable barrier properties and the undesirable cosmetic properties (specifically foul odor and sticky texture) caused a recall of this product.
 
     Two non-active topical skin protectant (TSP) formulations were developed at the United States Army Medical Research Institute of Chemical Defense (USAMRICD) and were transferred to advanced development following a Milestone Zero (MS 0 ) Review in October 1990. The timeline of the approval of the TSP continued with MSI in 1993, a Investigational New Drug (IND) filed with the FDA in 1994, MSII in 1995, and culminated with New Drug Application (NDA) approval in February, 2000. Upon approval by the FDA, the TSP was designated Skin Exposure Reduction Paste Against Chemical Warfare Agents (SERPACWA). SERPACWA is a 50:50 (wt/wt) mixture of perfluoropolyether oil (Fomblin® Y25 from Ausimont) and poly(tetrafluoroethylene) (Polymist® F5a powder from Ausimont). The formulation described in McCreery U.S. Pat. No. 5,607,979 is directed to a topical skin protectant cream that acts as a barrier to CWA. 
     Although SERPACWA extends the protection afforded by MOPP and allows a longer window for decontamination, it does not completely remove the possibility for contamination because the CWA is not neutralized. To avoid contamination of other areas of the battlefield and to preclude the future percutaneous absorption of the CWA, decontamination is still required. Furthermore, although the McCreery formulation provides excellent protection against soman (GD) and sulfur mustard (HD) liquid, its protection against GD and HD vapor is minimal. 
     To overcome these deficiencies, there is a need for a new TSP that contains an active component. This active Topical Skin Protectant (active TSP, aTSP) was developed within the following criteria. First, the active TSP should neutralize CWA including but not limited to HD, GD, and VX. Second, the barrier properties of the TSP should be maintained or increased. Third, the protection against GD and HD vapor should increase. And fourth, the cosmetic characteristics (i. e. odor, texture) of the TSP should be maintained. 
     This invention meets the above criteria and solves the problems associated with the past TSPs by providing an active topical skin protectant that increases effectiveness of the TSP barrier quality and neutralizes CWA into less harmful products. 
     It is therefore, an objective of the present invention to provide an active topical skin protectant that prevents the percutaneous absorption of CWA and converts these toxic materials into less harmful products. 
     It is a further objective of the present invention to provide an active topical skin protectant that maintains desirable cosmetic properties making it acceptable to the user. Specifically, the active TSP should not be sticky, should be without offensive odor, and should be nonirritating to the skin. 
     It is still a further object of the invention to provide an active topical skin protectant that is practical for field operations. Specifically, the active TSP should have a stable shelf life, not be easily washed off with water, and should not react with insecticides or camouflage paint. 
     SUMMARY OF THE INVENTION 
     A topical skin protectant formulation for neutralizing chemical warfare agents into less toxic products comprising: a barrier base cream and one or more active moieties. The base cream comprises poly(tetrafluoroethylene) resins dispersed in perfluorinated polyether oils. A chemical family of active moieties that has been found to be very effective with the base cream is the polyalkenimines. Effective formulations containing polyalkenimines and other active materials in the base cream are listed in Table 1. The active barrier cream is applied to the skin prior to exposure of persons at risk of exposure to harmful chemicals to provide an active barrier to protect the skin. The active barrier cream chemically or physically reacts with harmful chemicals such as CWA to neutralize these harmful chemicals while the barrier properties of the cream prevent penetration of harmful chemicals through the cream to the skin. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a flow diagram of the active TSP Decision Tree Network for efficacy evaluation; 
         FIG. 2  is series of  31 P NMR Spectra that measures the hydrolysis of Phosphorofluoridic acid diisopropyl ester (DFP) in D 2 O with 2.5 wt % Lupasol WF (ICD 3732); 
         FIG. 3  is the  1 H NMR spectrum of 2-chloroethylethylsulfide (CEES) in d 6 -DMSO; 
         FIG. 4  is the  1 H NMR spectrum of 2-chloroethylethylsulfide (CEES) in d 6 -DMSO+100 eq D 2 O after 18 h; 
         FIG. 5  is the  1 H NMR spectrum of CEES+2.5 wt % Lupasol WF (ICD 3732) in 100 eq D 2 O in d 6 -DMSO after 12 h; 
         FIG. 6  is a graph showing GD vapor penetration cell data of a 0.15 mm thick aTSP barrier in 20 hours; 
         FIG. 7  is a graph showing HD vapor penetration cell data for the cumulative amount of HD vapor through active TSP over 20 hours; 
         FIG. 8  is a graph showing a M8 paper test of the time to GD and HD liquid breakthrough for active TSPs containing polyalkenimines; 
         FIG. 9  is a graph showing HD liquid and GD liquid penetration cell data of the cumulative amount of HD and GD liquid through active TSP” over 20 hours; 
         FIG. 10  is a graph showing HS-SPME/GC-MS; 
         FIG. 11  is a graph comparing polyalkenimines at 2.5wt % in D 2 O solution against DFP challenge; 
         FIG. 12  is a graph showing results of active TSPs containing polyalkenimines; 
         FIG. 13  is a graph showing GD vapor rabbit lethality test giving results of active TSPs containing polyalkenimines; 
         FIG. 14  is a graph showing VX liquid rabbit lethality test giving results of active TSPs containing polyalkenimines. 
     
    
    
     DETAILED DESCRIPTION 
     Candidate Active Moieties 
     The types of materials that neutralize harmful agents use three main modes of action: oxidation, reduction or hydrolysis. 
     Operating criteria, however, restricts the selection of the active materials. Thus, the active moiety must not irritate the skin, react with insecticides or camouflage paints or be lack thermal or temporal stability. This restriction eliminates many of the most active species. Furthermore, the active moiety must be incorporated into a highly fluorinated environment that is not amenable to many reaction pathways. 
     Table 1 is a list of formulations containing amines, polyalkenimines and/or its derivatives and other active materials that are acceptable for use in the present invention: 
     
       
         
               
             
               
               
               
               
               
               
             
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 LIST OF AMINES, POLYALKENIMINES AND/OR DERIVATIVES FOR 
               
               
                 ACTIVE TOPICAL SKIN PROTECTANTS 
               
             
          
           
               
                 ICD # 
                 Active Moiety 
                 % Active 
                 % Other 
                 % PFPE 
                 % PTFE 
               
               
                   
               
               
                 3470 
                 Lupasol P (ICD3720) 
                 10 
                 Fluorolink 7004 
                 38 
                 43 
               
               
                   
                   
                   
                 (ICD3719) 2% 
                   
                   
               
               
                   
                   
                   
                 Water 7% 
                   
                   
               
               
                 3471 
                 Lupasol P (ICD3720) 
                 15 
                 Fluorolink 7004 
                 27 
                 49 
               
               
                   
                   
                   
                 (ICD3719) 3% 
                   
                   
               
               
                   
                   
                   
                 Water 6% 
                   
                   
               
               
                 3630 
                 DEAM (ICD3604) 
                  2 
                 Light Surfactant 
                 49 
                 46 
               
               
                   
                   
                   
                 (ICD 2853) 1% 
                   
                   
               
               
                   
                   
                   
                 Water 1% 
                   
                   
               
               
                 3631 
                 DEAM (ICD3605) 
                  2 
                 Light Surfactant 
                 48 
                 48 
               
               
                   
                   
                   
                 (ICD 2853) 1% 
                   
                   
               
               
                   
                   
                   
                 Water 1% 
                   
                   
               
               
                 3632 
                 DEAM (ICD3606) 
                  2 
                 Light Surfactant 
                 49 
                 47 
               
               
                   
                   
                   
                 (ICD 2853) 1% 
                   
                   
               
               
                   
                   
                   
                 Water 1% 
                   
                   
               
               
                 3712 
                 Lupasol P (ICD# 3720) 
                  9 
                 Fluorolink 7004 
                 48 
                 32 
               
               
                   
                   
                   
                 (ICD3719, 3%), 
                   
                   
               
               
                   
                   
                   
                 water (8%) 
                   
                   
               
               
                 3713 
                 Lupasol P (ICD# 3720) 
                  7 
                 Fluorolink 7004 
                 48 
                 32 
               
               
                   
                   
                   
                 (ICD3719, 3%), 
                   
                   
               
               
                   
                   
                   
                 water (10%) 
                   
                   
               
               
                 3714 
                 Lupasol P (ICD# 3720) 
                 20 
                 Fluorolink 7004 
                 60 
                 15 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (3%) 
                   
                   
               
               
                 3715 
                 Lupasol P (ICD# 3720) 
                 25 
                 Fluorolink 7004 
                 45 
                 21 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (7%) 
                   
                   
               
               
                 3716 
                 Lupasol P (ICD# 3720) 
                 25 
                 Fluorolink 7004 
                 43 
                 25 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3717 
                 Lupasol P (ICD# 3720) 
                 25 
                 Fluorolink 7004 
                 40 
                 30 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (3%) 
                   
                   
               
               
                 3718 
                 Lupasol P (ICD# 3720) 
                 25 
                 Fluorolink 7004 
                 35 
                 30 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (8%) 
                   
                   
               
               
                 3728 
                 Lupasol P (ICD# 3720) 
                 20 
                   
                 55 
                 25 
               
               
                 3729 
                 Lupasol P (ICD# 3720) 
                 20 
                   
                 40 
                 40 
               
               
                 3742 
                 Lupasol P (ICD# 3720) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD#3719, 3%) 
                   
                   
               
               
                 3743 
                 Lupasol P (ICD# 3720) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD#3730, 3%) 
                   
                   
               
               
                 3746 
                 Lupasol SC (ICD# 3731) 
                 10 
                 Fluorolink 7004 
                 40 
                 45 
               
               
                   
                   
                   
                 (ICD3719, 2%); 
                   
                   
               
               
                   
                   
                   
                 water (3%) 
                   
                   
               
               
                 3747 
                 Lupasol SC (ICD# 3731) 
                 10 
                 Fluorolink 7004 
                 40 
                 40 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (8%) 
                   
                   
               
               
                 3748 
                 Lupasol SC (ICD# 3731) 
                 10 
                 Fluorolink 7005 
                 40 
                 40 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (9%) 
                   
                   
               
               
                 3749 
                 Lupasol SC (ICD# 3731) 
                 15 
                 Fluorolink 7005 
                 35 
                 44 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3750 
                 Lupasol SC (ICD# 3731) 
                 15 
                 Fluorolink 7004 
                 34 
                 44 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3751 
                 Lupasol G20 (ICD# 3733) 
                 10 
                 Fluorolink 7004 
                 40 
                 40 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (8%) 
                   
                   
               
               
                 3752 
                 Lupasol G20 (ICD# 3733) 
                 10 
                 Fluorolink 7004 
                 40 
                 43 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3753 
                 Lupasol G20 (ICD# 3733) 
                 10 
                 Fluorolink 7005 
                 40 
                 43 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (6%) 
                   
                   
               
               
                 3754 
                 Lupasol G20(ICD# 3733) 
                 15 
                 Fluorolink 7005 
                 36 
                 43 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3755 
                 Lupasol WF (ICD# 3732) 
                 10 
                 Fluorolink 7004 
                 40 
                 40 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (8%) 
                   
                   
               
               
                 3756 
                 Lupasol WF (ICD# 3732) 
                 10 
                 Fluorolink 7004 
                 40 
                 35 
               
               
                   
                   
                   
                 (ICD3719, 2%), 
                   
                   
               
               
                   
                   
                   
                 water (13%) 
                   
                   
               
               
                 3757 
                 Lupasol WF (ICD# 3732) 
                 10 
                 Fluorolink 7005 
                 40 
                 35 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (14%) 
                   
                   
               
               
                 3758 
                 Lupasol WF (ICD# 3732) 
                 15 
                 Fluorolink 7005 
                 44 
                 35 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3759 
                 Lupasol P (ICD# 3720) 
                 15 
                 Fluorolink 7005 
                 44 
                 36 
               
               
                   
                   
                   
                 (ICD3730, 1%), 
                   
                   
               
               
                   
                   
                   
                 water (5%) 
                   
                   
               
               
                 3760 
                 Lupasol P (ICD# 3720) 
                 19 
                 Fluorolink 7005 
                 44 
                 36 
               
               
                   
                   
                   
                 (ICD3730, 1%) 
                   
                   
               
               
                 3771 
                 Lupasol P (ICD# 3720) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3772 
                 Lupasol G20 (ICD# 3733) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3773 
                 Lupasol G20 (ICD# 3733) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3774 
                 Lupasol SC (ICD# 3731) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3775 
                 Lupasol SC (ICD# 3731) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%); 
                   
                   
               
               
                 3778 
                 Lupasol WF (ICD# 3732) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3779 
                 Lupasol WF (ICD# 3732) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3780 
                 Lupasol FG (ICD# 3766) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3781 
                 Lupasol FG (ICD# 3766) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3782 
                 Lupasol FG (ICD# 3766); 
                 13 and 13 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3719, 1.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7005 
                   
                   
               
               
                   
                   
                   
                 (ICD3730, 1.5%) 
                   
                   
               
               
                 3786 
                 Lupasol WF (ICD# 3732) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3787 
                 Lupasol WE (ICD# 3732) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3790 
                 Lupasol G20 (ICD# 3733) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3791 
                 Lupasol WF (ICD# 3732) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3792 
                 Lupasol FG (ICD# 3766) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3793 
                 Lupasol P (ICD# 3720) 
                 24 
                 Fluorolink 7005 
                 35 
                 30 
               
               
                   
                   
                   
                 (ICD3730, 3%); 
                   
                   
               
               
                   
                   
                   
                 water (9%) 
                   
                   
               
               
                 3808 
                 Dytek EP (ICD# 3863) 
                  5 
                 Fluorolink 7005 
                 49 
                 45 
               
               
                   
                   
                   
                 (ICD3730, 1%) 
                   
                   
               
               
                 3809 
                 Lupasol WF (ICD# 3732); 
                 21 and 5 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Dytek EP 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3810 
                 Dytek EP (ICD# 3863) 
                  5 
                 Fluorolink 7004 
                 49 
                 45 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3811 
                 Lupasol FG (ICD# 3766); 
                 21 and 5 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Dytek EP )ICD #3863) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3829 
                 Lupasol P (ICD# 3720) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3830 
                 Lupasol G20 (ICD# 3733) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3831 
                 Lupasol SC (ICD# 3731) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3832 
                 Lupasol WF (ICD# 3732) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3833 
                 Lupasol FG (ICD# 3766) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3834 
                 Lupasol FG (ICD# 3766); 
                 13 and 13 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3719, 1.5%) 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7005 
                   
                   
               
               
                   
                   
                   
                 (ICD3730, 1.5%) 
                   
                   
               
               
                 3835 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3836 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (lCD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3837 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3838 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol P (ICD# 3720) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3839 
                 Lupasol P (ICD# 3720); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3840 
                 Lupasol P (ICD# 3720); 
                 14 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3841 
                 Lupasol P (ICD# 3720); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3842 
                 Lupasol FG (ICD# 3766); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3843 
                 Lupasol SC (ICD# 3731); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3844 
                 Lupasol G20 (ICD# 3733); 
                 11 and 12 
                 Fluorolink 7005 
                 34 
                 40 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3853 
                 Lupasol LU (ICD# 3852) 
                 17 
                 Fluorolink 7005 
                 31 
                 46 
               
               
                   
                   
                   
                 (ICD3730, 2%); 
                   
                   
               
               
                   
                   
                   
                 water (4%) 
                   
                   
               
               
                 3854 
                 Lupasol LU (ICD# 3852) 
                 23 
                 Fluorolink 7005 
                 35 
                 40 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3855 
                 Lupasol LU (ICD# 3852) 
                 20 
                 Fluorolink 7004 
                 38 
                 35 
               
               
                   
                   
                   
                 (ICD3719, 1%); 
                   
                   
               
               
                   
                   
                   
                 water (4%) 
                   
                   
               
               
                 3856 
                 Lupasol LU (ICD# 3852) 
                 25 
                 Fluorolink 7004 
                 38 
                 35 
               
               
                   
                   
                   
                 (ICD3719, 2%) 
                   
                   
               
               
                 3857 
                 Lupasol LU (ICD# 3852); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3858 
                 Lupasol LU (ICD# 3852); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3859 
                 Lupasol LU (ICD# 3852); 
                 11 and 12 
                 Fluorolink 7005 
                 34 
                 41 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3860 
                 Lupasol LU (ICD# 3852); 
                 12 and 12 
                 Fluorolink 7005 
                 35 
                 38 
               
               
                   
                 Lupasol P (ICD# 3720) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3861 
                 Lupasol LU (ICD# 3852); 
                 12 and 12 
                 Fluorolink 7005 
                 36 
                 37 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3871 
                 PAA-HCL-3L (ICD#3867) 
                 23 
                 Fluorolink 7004 
                 34 
                 41 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3872 
                 PAA-HCL-3L (ICD#3867) 
                 26 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3873 
                 PAA-10C (ICD#3868) 
                 19 
                 Fluorolink 7004 
                 28 
                 52 
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 3874 
                 PAA-10C (ICD#3868) 
                 18 
                 Fluorolink 7005 
                 25 
                 55 
               
               
                   
                   
                   
                 (ICD3730, 2%) 
                   
                   
               
               
                 3875 
                 PAA-HCL-3L (ICD#3867) and 
                 12 and 12 
                 Fluorolink 7005 
                 34 
                 40 
               
               
                   
                 PAA-10C (ICD#3868) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3884 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3885 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3886 
                 Lupasol P (ICD# 3720); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3887 
                 Lupasol P (ICD# 3720); 
                 14 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3900 
                 Lupasol P (ICD# 3720); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3901 
                 Lupasol FG (ICD# 3766); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol SC (ICD# 3731) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3902 
                 Lupasol SC (ICD# 373); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3903 
                 Lupasol G20 (ICD# 3733 
                 11 and 12 
                 Fluorolink 7005 
                 34 
                 40 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3970 
                 Lupasol WF (ICD# 3732) 
                 26 
                 Fluorolink 7004 
                 38 
                 33 
               
               
                   
                   
                   
                 (ICD3719 3%) 
                   
                   
               
               
                 3971 
                 Lupasol LU 321 (ICD# 3852) 
                 25 
                 Fluorolink 7004 
                 38 
                 35 
               
               
                   
                   
                   
                 (ICD3719, 2%) 
                   
                   
               
               
                 3972 
                 Lupasol LU 321 (ICD# 3852) 
                 23 
                 Fluorolink 7005 
                 35 
                 40 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3994 
                 Lupasol WF (ICD# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol P (ICD# 3720) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3997 
                 PAA-HCL-3L (ICD#3867) 
                 23 
                 Fluorolink 7004 
                 34 
                 41 
               
               
                   
                   
                   
                 (ICD3719, 3%) 
                   
                   
               
               
                 3998 
                 PAA-HCL-3L (ICD#3867) 
                 26 
                 Fluorolink 7005 
                 37 
                 34 
               
               
                   
                   
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 3999 
                 PAA-10C (ICD#3868) 
                 19 
                 Fluorolink 7005 
                 28 
                 52 
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 4000 
                 PAA-10C (ICD#3868) 
                 18 
                 Fluorolonk 7005 
                 25 
                 55 
               
               
                   
                   
                   
                 (ICD3730, 2%) 
                   
                   
               
               
                 4020 
                 Lupasol P (ICD# 3720); 
                 14 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol G20 (ICD# 3733) 
                   
                 (ICD3730, 1.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 1.5%) 
                   
                   
               
               
                 4021 
                 Lupasol P (ICD# 3720); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 4022 
                 Lupasol WF (IDC# 3732); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 3%) 
                   
                   
               
               
                 4029 
                 Lupasol P (ICD# 3720) 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3730, 1.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 1.5%) 
                   
                   
               
               
                 4032 
                 Lupasol G20 (ICD# 3733) 
                 13 
                 Fluorolink 7005 
                 44 
                 42 
               
               
                   
                   
                   
                 (ICD3730, 2%) 
                   
                   
               
               
                 4033 
                 Lupasol G20 (ICD# 3733) 
                  6 
                 Fluorolink 7005 
                 47 
                 46 
               
               
                   
                   
                   
                 (ICD3730, 1%) 
                   
                   
               
               
                 4034 
                 Lupasol WF (ICD# 3732) 
                 13 
                 Fluorolink 7005 
                 44 
                 42 
               
               
                   
                   
                   
                 (ICD3730, 2%) 
                   
                   
               
               
                 4035 
                 Lupasol WF (ICD# 3732) 
                  6 
                 Fluorolink 7005 
                 47 
                 46 
               
               
                   
                   
                   
                 (ICD3730, 1%) 
                   
                   
               
               
                 4036 
                 Lupasol G20 (ICD# 3733) 
                 14 
                 Fluorolink 7004 
                 43 
                 41 
               
               
                   
                   
                   
                 (ICD3719, 2%) 
                   
                   
               
               
                 4037 
                 Lupasol G20 (ICD# 3733) 
                  7 
                 Fluorolink 7004 
                 47 
                 45 
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 4038 
                 Lupasol FG (ICD# 3766) 
                 13 
                 Fluorolink 7004 
                 44 
                 42 
               
               
                   
                   
                   
                 (ICD3719, 2%) 
                   
                   
               
               
                 4039 
                 Lupasol FG (ICD# 3766) 
                  7 
                 Fluorolink 7004 
                 47 
                 46 
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 4040 
                 Lupasol FG (ICD# 3766) 
                 13 
                 Fluorolink 7005 
                 44 
                 41 
               
               
                   
                   
                   
                 (ICD3730, 2%) 
                   
                   
               
               
                 4041 
                 Lupasol FG (ICD# 3766) 
                  7 
                 Fluorolink 7005 
                 47 
                 46 
               
               
                   
                   
                   
                 (ICD3730, 1%) 
                   
                   
               
               
                 4042 
                 Lupasol FG (ICD# 3766); 
                 7 and 7 
                 Fluorolink 7005 
                 44 
                 42 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3730, 1%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 4043 
                 Lupasol FG (ICD# 3766); 
                 3 and 3 
                 Fluorolink 7005 
                 49 
                 47 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3730, 0.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 0.5%) 
                   
                   
               
               
                 4044 
                 Lupasol P (ICD# 3720) 
                 13 
                 Fluorolink 7005 
                 45 
                 41 
               
               
                   
                   
                   
                 (ICD3730, 1.5%) 
                   
                   
               
               
                 4045 
                 Lupasol P (ICD# 3720) 
                  6 
                 Fluorolink 7005 
                 48 
                 45 
               
               
                   
                   
                   
                 (ICD3730, 1%) 
                   
                   
               
               
                 4046 
                 Lupasol WF (ICD# 3732) 
                 15 
                 Fluorolink 7004 
                 51 
                 33 
               
               
                   
                   
                   
                 (ICD3719, 2%) 
                   
                   
               
               
                 4047 
                 Lupasol P (ICD# 3720) 
                 14 
                 Fluorolink 7004 
                 48 
                 36 
               
               
                   
                   
                   
                 (ICD3719, 2%) 
                   
                   
               
               
                 4048 
                 Lupasol WF (ICD# 3732) 
                  7 
                 Fluorolink 7004 
                 50 
                 41 
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 4049 
                 Lupasol P (ICD# 3720) 
                  7 
                 Fluorolink 7004 
                 49 
                 43 
               
               
                   
                   
                   
                 (ICD3719, 1%) 
                   
                   
               
               
                 4050 
                 Lupasol P (ICD# 3720); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3730, 1.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 1.5%) 
                   
                   
               
               
                 4051 
                 Lupasol G20 (ICD# 3733); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol FG (ICD# 3766) 
                   
                 (ICD3719, 1.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 1.5%) 
                   
                   
               
               
                 4052 
                 Lupasol G20 (ICD# 3733); 
                 13 and 13 
                 Fluorolink 7005 
                 38 
                 33 
               
               
                   
                 Lupasol WF (ICD# 3732) 
                   
                 (ICD3730, 1.5%); 
                   
                   
               
               
                   
                   
                   
                 Fluorolink 7004 
                   
                   
               
               
                   
                   
                   
                 (ICD3719, 1.5%) 
               
               
                   
               
             
          
           
               
                 Abbreviations for Table 1: 
               
               
                 PTFE: poly(tetrafluoroethylene) available as F5A powder from Ausimont, Morristown, NJ. 
               
               
                 PFPE: perfluoropolyether available as FOMBLIM ™ Y25 oil from Ausimont, Morristown, NJ. 
               
               
                 ICD 3719 (Fluorolink 7004 ®), available from Ausimont USA, Inc.; 1, Propene, 1,1,2,3,3,3- 
               
               
                 hexafluoro-, telomers with chlorotrifluoroethene, oxidized, reduced, ethyl ester, hydrolyzed, 
               
               
                 CAS # 220182-27-4. 
               
               
                 LCD 3720 (Lupasol P ®), available from BASE Corp., a 50:50 wt % mixture of water and aziridine, 
               
               
                 homopolymer, CAS # 9002-98-6. 
               
               
                 LCD 3730 (Fluorolink 7005 ®), available from Ausimont USA, Inc.; a perfluoropolyether derivative 
               
               
                 (PFPE-CONH—(CH 2 ) 3 —(OCH 2 CH 3 ) 18 —CH 3 ) from Ausimont, CAS # not assigned. 
               
               
                 ICD2853 Light PFPE Surfactant, Dupont, Wilmington, DE 
               
               
                 ICD3731 (Lupasol SC 61B ®), available from BASE Corp., hydroxyethylated polyethylenimine, 
               
               
                 Product ID # NLE 555415. CAS #26658-46-8 
               
               
                 ICD3732 (Lupasol WF ®) (water free), available from BASE Corp., polyethylenimine, 
               
               
                 (CH 2 —CH 2 —NH—) x  Product ID # NLE 187702, CAS # 9002-98-6. 
               
               
                 ICD3733 (Lupasol G20 ®) water free, available from BASE Corp., polyethylenimine, Product 
               
               
                 ID # NLE 555415, CAS # 25987-06-8. 
               
               
                 ICD3852 (Lupasol LU 321 ®), available from BASE Corp., a 15:80:5 wt % mixture of formamide 
               
               
                 polymer (Product ID # NLE 073991) water, and sodium formate. 
               
               
                 ICD3863 (Dytek EP ®), 1,3-pentanediamine, CAS # 589-37-7. 
               
               
                 ICD3766 (Lupasol FG ®), available from BASE Corp., ethylenediamine-ethylenimine copolymer, 
               
               
                 (C 2 H 8 N 2 .C 2 H 5 N) x  Product # NCS 971991, CAS # 25987-06-8. 
               
               
                 ICD3867 PAA-HCL-3L, 50.4 wt % aqueous solution of homopolymer of 2-propen-1-amine 
               
               
                 hydrochloride, CAS # 71550-12-4. 
               
               
                 ICD3868 PAA-10C, 10.3 wt % aqueous solution of homopolymer of 2-propen-1-amine, 
               
               
                 CAS # 30551-89-4. 
               
               
                 ICD3604 Diethanolamine modified (DEAM). Cross-linked polystyrene/divinylbenzene 
               
               
                 copolymer modified with 1.2 mmol/g diethanolamine. 
               
               
                 ICD3605 Diethanolamine modified (DEAM). Cross-linked polystyrene/divinylbenzene 
               
               
                 copolymer modified with 1.5 mmol/g diethanolamine. 
               
               
                 ICD 3606 Diethanolamine modified (DEAM). Cross-linked polystyrene/divinylbenzene 
               
               
                 copolymer modified with 1.0 mmol/g diethanolamine. 
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                 DEAM Structure (J. H. Hartley, and T. D. James, Tetrahedron Lett. 1999, 40, 2597-2600). 
               
               
                   
               
             
          
         
       
     
     Examples of polyalkenimines are the polyethylenimines. These materials are available from BASF Corporation (4330 Chesapeake Dr., Charlotte, N.C.) under the trade name Lupasols.™ Lupasols (polyethylenimines, PEI) are multi-functional branched or spherical non-toxic cationic and neutral polymers. They are synthesized by the ring-opening polymerization of aziridine (ethylenimine). Depending on polymerization conditions, Lupasols contain various ratios of primary, secondary, and tertiary amines along the polymer backbone. Molecular weights also range from 800 to 2,000,000. 
     
       
                 
         
             
             
         
      
     
     Polyethylenimines are synthesized from the ring opening polymerization of the nitrogen homologue of ethylene oxide. The resulting product is a highly branched, spherical polymer, which is easily protonated to form the most highly charged cationic polymer. As a result of their spherical shape and high cationic charge density, polyethylenimines are able to strongly bind onto anionic and polar surfaces. In addition, non-protonated amino groups are available to form hydrogen bonds or undergo further chemical reactions. Examples are given below: 
     
       
                 
         
             
             
         
      
     
     The percent values assigned to the above listed components of the example skin protectant formulations in Table 1 are given for example only. These values may be adjusted up or down and still embody the spirit of the invention if the herein described qualities of efficacy and composition of the present invention are met. 
     All active moieties listed above are useful for both liquid and vapor challenges. The amount of each varies with each formulation. The object is to optimize the quantity of active moiety in the base cream without losing the barrier properties of the base cream. The amount of active moiety can vary from about 1-30%. The amount of perfluorinated polyether oil can vary from about 30 to 60%. The amount of poly(tetrafluoroethylene) can vary from about 20 to 50%. One criterion for selection of the active materials is increased efficacy against HD and/or GD vapor. Most the listed formulations have significantly (P=0.05) increased protection compared to SERPACWA (ICD 3004) in the penetration cell model against HD and/or GD and are listed in the Results sections. 
     The polyalkenimines must also be incorporated into the TSP matrix without degradation of the barrier properties. These materials were incorporated into the cream either as solids or aqueous suspensions. Typically they are dispersed into the perfluorinated oil followed by sequential addition of the appropriate amount of F5A poly(tetrafluoroethylene). The TSP can contain individual polyalkenimines or mixtures of two or more polyalkenimines. 
     SERPACWA (ICD3004) consists of fine particles of poly(tetrafluoroethylene) resin dispersed in perfluorinated polyether oil. The excellent barrier properties of this high molecular weight polymer formulation are related to the low solubility of most materials in it. Only highly fluorinated solvents like Freon® have been observed to show appreciable solubility. This aprotic non-polar polymer mixture provides a unique medium for active moieties of the invention. Reaction mechanisms that do not involve charged transition states should be favored in this chemical environment. 
     Base creams formed from about 20-50% fine particulates of certain poly(tetrafluoroethylene) PTFE resins dispersed in perfluorinated polyether oils (PFPE) having viscosities from about 20 cSt to about 500 cSt afford good protection against chemical warfare agents such as HD, Lewisite (L), sulfur mustard/Lewisite mixtures (HL), pinacolyl methylphosphonofluoridate (soman or GD), thickened soman (TGD) and O-ethyl S-(2-diisopropylaminoethyl)methylphosphonothiolate (VX). PTFE and PFPE are available commercially from Ausimont (Morristown, N.J.) and Dupont (Wilmington, Del.). 
     The base creams used in the invention are suspensions of 20-50% finely divided PTFE having a surface area below about 6 m 2 /g in a perfluorinated polyether base oil prepared from poly(perfluoropropylene oxide), which has a viscosity between about 20 and about 500 cSt. More preferred compositions comprise from about 20% to about 50% of finely divided PTFE having an average particle size from about 0.1 μm to about 10 μm and a surface area below about 4 m 2 /g in a perfluorinated polyether base oil from 30% to 60% having a viscosity between about 20 and about 500 cSt. 
     Suitable perfluorinated polyether oils are Fomblin® HC- and Y-oils (Ausimont) and Krytox® oils (Dupont). The Fomblin® oils are mixtures of linear polymers based on poly(perfluoropropylene oxide) having the following chain structure: CF 3 -[(OCF(CF 3 )CF 2 ) n -(OCF 2 CF 2 ) m ]OCF 3 . The Krytox® oils are mixtures of linear polymers also based on perfluoropropylene oxide and have the chemical structure F-[(CF(CF 3 )CF 2 O)] m CF 2 CF 3 . Fomblin® Z oils having the formula: CF 3 -[(OCF 2 CF 2 ) n -(OCF 2 ) m ]-OCF 3 , may also be useful in the practice of the invention. The indices n and m indicate the average number of repeating polymeric subunits in the oil molecules. The oils may have a viscosity of about 20 cSt to about 500 cSt or more. The creams were generally prepared according to U.S. Pat. No. 5,607,979, incorporated herein in its entirety. 
     Other additives to the base cream are water and surfactant and other chemicals necessary to maintain activity. The surfactant facilitates the mixing of the water with the base cream. Examples of typical surfactants are perfluoropolyalkylether (Krytox® CAS #60164-51-4 from Dupont), Fluorolink® 7004 (1,Propene, 1,1,2,3,3,3-hexafluoro-, telomers with chlorotrifluoroethene, oxidized, reduced, ethyl ester, hydrolyzed, CAS #220182-27-4 from Ausimont), and Fluorolink® 7005 (a perfluoropolyether derivative from Ausimont, CAS # not assigned). Additional materials may also be incorporated as long as they do not reduce effectiveness of the topical protectant, such as stabilizers, camouflage paints, and sunscreens. 
     A further understanding of the composition of the topical protectant of the invention can be obtained by reference to certain specific example formulations set forth in Table 1. These examples are provided herein for purposes of illustration only and are not intended to be limiting. Many active moieties require the presence of water as a reagent for the hydrolysis of HD and GD. The active moieties that react by a hydrolysis mechanism require the presence of water. When the topical protectant is applied to the skin of a user, moisture in the form of perspiration may also aid in the hydrolysis of HD and GD. The addition of perfluorinated polyether surfactants to the base cream facilitates the addition of water. 
     Temperature and mixing sheer should be monitored to maintain the base cream at the desired consistency and quality. The active TSPs are typically prepared at ambient temperature using mechanical mixing or at controlled temperatures using either a single screw or dual screw commercial extruder (Haake® Rheomix extruder). Mixing times of 10-20 minutes are usually sufficient for dispersal of polyalkenimines into the PFPE/PTFE matrix. A typical procedure for the preparation of an active TSP with a polyalkenimine is presented below: 
     In a polypropylene container is added the appropriate amount of polyalkenimine (1-30% by weight) and Y25 (30-60% by weight) perfluorinated oil. The suspension is mixed with a mechanical stirrer at ambient temperature for 5 to 15 minutes or with a magnetic stirrer for 10 to 20 hours. To the suspension is added F5A poly(tetrafluoroethylene) in three portions with vigorous mechanical stirring for 5 to 10 minutes between each addition. After final addition the container is tightly capped and sealed with Parafilm®. Commercial extruders or other high-shear mixing techniques can improve the quality of the final product. 
     Multilayer Approach 
     Although an active TSP can be applied directly to the skin, the application of a powder (or liquid) that is a polyalkenimine sprinkled on the skin, or an active moiety in a base cream wherein the cream is spread on the skin, a multilayering approach can also be used. The multilayer approach would be to use the active TSP as the first layer and a solid active moiety powder (or liquid or other reactive matrix) as the second layer. The second layer would be a thin coating of the active moiety sprinkled over the active TSP cream. This approach would provide a concentrated decontamination material at the surface of the barrier cream, which would accelerate the neutralization process of CWAs coming in contact with the surface. Alternatively, the first layer can be a thin coating of the active moiety followed by a second layer of the active TSP. 
     Testing 
     Evaluation of formulations was conducted with a decision tree network (DTN) that describes the path that active TSPs follow during evaluation ( FIG. 1 ). 
     The DTN is divided into two pathways: one for vesicants and the other for nerve agents. Within these pathways there are three blocks each with a decision point. The first block consists of a series of three mechanical (in vitro) modules used to determine the initial efficacy of candidate formulations and to eliminate non-effective candidates before animal testing, the second block consists of in vivo modules and the third block consists of an advanced animal module to determine the influence of time, water, sweat, and interactions with other products. 
     The M8 paper test is used to evaluate the barrier resistance of liquid CWA challenges, including HD, pinacolyl methylphosphonofluoridate (soman, GD), and O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothioate (VX). In this test a 0.15 mm layer of active TSP is placed over a well-defined area of M8 chemical detection paper and challenged with an 8 μl droplet of CWA. When agent penetrates the active TSP barrier and reaches the M8 paper, a colored spot develops on the paper. The test assemblies are observed for 6 hr and the breakthrough time is reported for each sample. A total of nine replicates are run for each test, and a standard reference compound is included each day for quality control. 
     The penetration cell test is used to evaluate the barrier properties against both liquid and vapor CWA challenges (Braue, E. H. Jr.  Journal of Applied Toxicology , 1999, 19(S), S47-S53). In this test the lower half of a Reifenrath diffusion cell (Reifenrath Consulting and Research, Richmond, Calif.) is used. A 0.15 mm thick layer of active TSP is supported by nitrocellulose paper on top of the cell. The active TSP layer is challenged with a 10-μl liquid droplet of HD or an 8 μl droplet of GD, or a saturated vapor cup of HD or GD. Breakthrough of CWA into the lower chamber of the diffusion cell is monitored using a miniature continuous air monitoring system (MINICAMS, CMS Research, Birmingham, Ala.). This system has been automated to allow continuous monitoring of five cells in a 40-min cycle. The test runs for 20 hr and the accumulated amounts of agent that break through the active TSP barrier are calculated. From these data, we obtained two values: the cumulative amount of CWA that penetrates through the active TSP, and the time at which a “breakthrough” occurs. We defined “breakthrough” values at the minimum amount of HD (1000 ng) and GD (1000 ng) that results in a physiological response. Minimal amount of HD for vesication is 1000 ng. See F. R. Sidell, J. S. Urbanetti, W. J. Smith, and C. G. Hurst in  Textbook of Military Medicine, Medical Aspects of Chemical and Biological Warfare , edited by F. R. Sidell, E. T. Takafuji, and D. R. Franz (Office of the Surgeon General at TMM Publications, Washington, D. C. 1997) p 201. The LD 50  for soman (GD) is 350 mg/70 kg man. See F. R. Sidell in  Textbook of Military Medicine, Medical Aspects of Chemical and Biological Warfare , edited by F. R. Sidell, E. T. Takafuji, and D. R. Franz (Office of the Surgeon General at TMM Publications, Washington, D. C. 1997) p 141. These two values allow us to rank the active TSP formulations and to select the appropriate component for advanced development. 
     The proof-of-neutralization test is used to verify that active TSP formulations actually neutralize CWAs into less toxic materials. This test uses the headspace solid phase microextraction (HS-SPME) technique for the collection of CWAs. Samples collected on the extraction filament are analyzed by gas chromatography/mass spectroscopy. 100 mg of active TSP formulation are challenged with 0.1 μl of neat CWA (HD, GD, or VX) in a small vial. The headspace above the mixture is sampled periodically to determine the amount of CWA remaining in the flask. Efficacy is determined by the % loss of CWA. Other analytical techniques such as Nuclear Magnetic Resonance (NMR) and Fourier-Transform Infrared Spectrometry (FTIR) have also been used in this module. 
     Formulations that pass this initial set of screens are moved into the second phase of testing using animal models. The weakling pig test for HD vapor evaluates a 0.15 mm thick layer of active TSP spread on the depilated dorsa. The standard saturated vapor cup is used for a 30 min challenge. The effectiveness of the active TSP is determined by measuring the degree of erythema that developed on the skin exposure site. Erythema is measured objectively using a reflectance calorimeter (see Braue, E. H. Jr.  Journal of Applied Toxicology , 1999, 19(S), S47-S53). 
     The rabbit lesion area ratio (LAR) test is used to evaluate a challenge by HD liquid. In this test, a 0.15 mm layer of active TSP spread on the clipped dorsa is challenged with 1.0 μl of liquid HD spread by a 12 mm disk. The effectiveness of the active TSP is determined by measuring the lesion areas of protected and non-protected sites. 
     The rabbit lethality test is used to evaluate a challenge by GD vapor. In this test, a 0.15 mm layer of active TSP spread on the clipped dorsa is challenged with two vapor cups (7 cm 2  each) containing 28 mg GD per kg of body weight. The liquid GD is saturated onto filter paper fitted into the top of the cap so that liquid can not run down. The caps are left in place for 4 hours. After the exposure period the caps are removed and the exposure sites decontaminated. This exposure dose is lethal to all animals not protected with active TSP. The effectiveness of the active TSP is determined by lethality 1, 2, 3, 4 and 24 hr following exposure. 
     The guinea pig lethality test is performed by applying a 0.15 mm thick layer of active TSP on the clipped dorsa of guinea pig followed by a fixed dose of GD, TGD or VX. The effectiveness of the active TSP is determined by lethality 1, 2, 3, 4 and 24 hr following exposure. 
     Candidate formulations that pass the in vivo test modules move into advanced animal testing. These tests are similar to the initial animal tests with the addition of stresses for wear-time and washing with a simulated sweat solution. Interactions with other products that a warfighter might use are also evaluated. These products include camouflage paints, sunscreens and insecticides. 
     Results 
     The polyalkenimines are effective active moieties reducing the amount of HD vapor by &gt;99% relative to the TSP alone. Although the exact mechanisms for HD neutralization are not clear, they may react by hydrolysis, direct alkylation of the polyalkenimine, or dehydrohalogenation (Scheme 1). 
     
       
                 
         
             
             
         
      
     
     Against GD vapor the polyalkenimines reduced the amount of GD by &gt;99% compared to TSP alone. In this case, it is likely that the polyalkenimines are active as nucleophiles or else accelerate hydrolysis through general base catalysis (Scheme 2). 
                                
Many of the listed active TSPs contain water, and the in model reactions with a GD simulant, diisopropylfluorophosphate, (DFP), the products have FT-IR and  31 p NMR spectra that are consistent with hydrolysis. Another possibility is that adventitious adsorbed water in formulations that did not have water added directly act as a reagent for this hydrolysis.
 
     The increase in protection for the polyalkenimines was impressive against GD vapor as seen by the decrease in total ng that breakthrough the active TSP as compared to SERPACWA (ICD3004) ( FIG. 6 ).  FIG. 6  shows a total amount of GD vapor that penetrates a 0.15 mm thick aTSP barrier in 20 hr. ICD3004 (SERPACWA) is off scale with a value of 6672 ng. 
     Many of the formulations reduce the amount of GD vapor by &gt;99%. Most samples display significantly (P=0.05) increased protection compared to SERPACWA (ICD 3004) in the penetration cell model against GD vapor. 
     The increase in protection for aTSPs formulations containing polyalkenimines was also remarkable against HD vapor as demonstrated by the decrease in total ng that break through the active TSP in 20 hours as compared to SERPACWA (ICD3004) ( FIG. 7 ). 
     As clearly seen in  FIG. 7 , most of the formulations containing polyalkenimines have shown outstanding protection against HD vapor in the penetration cell model. Many offer significantly better (P=0.05) protection against HD vapor compared to SERPACWA (ICD 3004). 
     To roughly determine the resistance of aTSPs containing polyalkenimines, the M8 paper test was performed. All formulations tested against HD liquid proved impervious over the duration of the test (360 min) but showed variable resistance against GD liquid ( FIG. 8 ). 
     Limited penetration cell testing has also been accomplished against HD and GD liquid. In this module, the aforementioned a TSPs performed well against GD but were ineffective against HD ( FIG. 9 ). 
     In addition to the penetration cell model, certain active TSP containing polyalkenimines were tested in the headspace solid phase micro-extraction gas chromatography/mass spectrometry (HS-SPME/GC-MS) test against HD. In this module significant efficacy was seen against HD, GD, and VX ( FIG. 10 ). For  FIG. 10 , evaluation of active TSPs containing polyalkenimines against HD, GD, and VX liquid using headspace solid phase micro-extraction gas chromatography/mass spectrometry (HS-SPME-GC/MS). Percent of Control is the ratio (expressed as %) of the headspace concentration of the CWA determined for each formulation divided by the headspace concentration determined for SERPACWA. 
     Possible neutralization pathways of these amines, polyalkenimines, and derivatives were probed using NMR with diisopropylfluorophosphate (DFP) as a GD simulant and CEES as an HD simulant. To determine the relative activity of different polyalkenimines towards organophosphates, the first experiments monitored the hydrolysis of DFP in deuterated water (D 2 O).  31 P NMR spectra were obtained displaying both the native DFP (d, −11.6 ppm) and it hydrolysis product (s, −2.5 ppm). These spectra were obtained at regular intervals over 14 hours ( FIG. 2 ). The extent of hydrolysis was determined by taking the ratio of the integrations of the signals for DFP and its hydrolysis product. By plotting the percent hydrolysis versus time, we were able to perform an initial ranking of the polyalkenimines ( FIG. 11 ). 
     To determine the possible reaction pathways for the neutralization of HD by polyalkenimines, we performed a series of experiments measuring the degree of hydrolysis in an HD simulant, 2-chloroethylethylsulfide (CEES). First, we obtained the  1 H NMR spectra of CEES in d 6 -DMSO ( FIG. 3 ). Next, we added 100 equivalents of D 2 O to the NMR tube and obtained  1 H spectra after 18 hours giving us a baseline extent of hydrolysis ( FIG. 4 ). Finally, we prepared a standard solution of CEES in d 6 -DMSO and added a 2.5 wt % solution of polyalkenimine in D 2 O (still 100 eq D 2 O). Peak at ˜4.1 ppm is from D 2 O, broad peak from 2.5 to 3.0 ppm is from the Lupasol WF ( FIG. 5 ). By comparing the spectra of CEES, CEES/D 2 O and CEES/polyalkenimine/D 2 O, it is evident that significant hydrolysis occurs by the disappearance of CEES signals (3.75, 2.85, 2.55, 1.17 ppm). 
     Most of the active TSPs containing polyalkenimines also show excellent efficacy in the weanling pig HD vapor model (Table 2). The best active TSPs containing polyalkenimines almost completely eliminated erythema in this test. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Weanling pig test results for HD vapor. Erythema as percentage 
               
               
                 of positive control (% of PC). Positive control has no aTSP applied. 
               
               
                 SEM is the standard error of the mean. Formulations pass the test if 
               
               
                 they offer significantly (p &lt; 0.05) better protection than 
               
               
                 un-protected skin. 
               
             
          
           
               
                 Formulations 
                 Formulations 
               
               
                 Passing Test 
                 Failing Test 
               
             
          
           
               
                 ICD No. 
                 % of PC 
                 SEM 
                 ICD No. 
                 % of PC 
                 SEM 
               
               
                   
               
             
          
           
               
                 3470 
                 56.4 
                 10.5 
                 3004 
                 102 
                 1.8 
               
               
                 3718 
                 −9.6 
                 17.5 
                 3471 
                 61.5 
                 11.9 
               
               
                 3742 
                 39 
                 10.6 
                 3630 
                 110.6 
                 5.9 
               
               
                 3743 
                 41.7 
                 10 
                 3631 
                 103.5 
                 5.4 
               
               
                 3771 
                 25.1 
                 7.6 
                 3724 
                 100.4 
                 3.1 
               
               
                 3772 
                 30.8 
                 7.2 
                 3725 
                 86.3 
                 7.1 
               
               
                 3773 
                 16.3 
                 3.3 
                 3728 
                 93.9 
                 9.5 
               
               
                 3778 
                 29 
                 3.2 
                 3729 
                 95.7 
                 7.3 
               
               
                 3779 
                 43.3 
                 8.5 
                 3744 
                 117.3 
                 8.2 
               
               
                 3780 
                 28.1 
                 3.8 
                 3745 
                 117.2 
                 10.2 
               
               
                 3781 
                 39.4 
                 7.3 
                 3809 
                 87.9 
                 8.6 
               
               
                 3782 
                 16 
                 3.8 
                 3831 
                 82.7 
                 5.9 
               
               
                 3829 
                 61.7 
                 9.4 
                 3900 
                 80.5 
                 10.4 
               
               
                 3830 
                 38.9 
                 7.1 
                 4033 
                 104.3 
                 13 
               
               
                 3832 
                 26.1 
                 5.7 
                 4037 
                 90.9 
                 12.9 
               
               
                 3833 
                 15.7 
                 7.3 
                 4039 
                 91.5 
                 4 
               
               
                 3834 
                 11.6 
                 5.9 
                 4040 
                 77.4 
                 11 
               
               
                 3884 
                 23.5 
                 10.7 
                 4041 
                 114.7 
                 15.3 
               
               
                 3885 
                 70.7 
                 13.1 
                 4043 
                 90.6 
                 6.5 
               
               
                 3886 
                 46.9 
                 11.8 
               
               
                 3887 
                 48.3 
                 9.1 
               
               
                 3901 
                 73.6 
                 7.4 
               
               
                 3902 
                 68.5 
                 5.3 
               
               
                 3903 
                 50.5 
                 9.5 
               
               
                 4020 
                 12.4 
                 11.6 
               
               
                 4021 
                 35.9 
                 16.7 
               
               
                 4022 
                 43.4 
                 13.5 
               
               
                 4029 
                 25.5 
                 5 
               
               
                 4032 
                 54.6 
                 7.7 
               
               
                 4034 
                 59.7 
                 7.1 
               
               
                 4036 
                 46.3 
                 7.6 
               
               
                 4038 
                 55.5 
                 6.4 
               
               
                 4042 
                 59.6 
                 10.9 
               
               
                 4044 
                 69.6 
                 7.7 
               
               
                 4046 
                 13.2 
                 4.6 
               
               
                 4047 
                 44.3 
                 6.1 
               
               
                 4048 
                 66.1 
                 7.2 
               
               
                 4049 
                 82.8 
                 6.2 
               
               
                 4050 
                 13.4 
                 5.4 
               
               
                 4051 
                 18.6 
                 7.9 
               
               
                 4052 
                 10.2 
                 8 
               
               
                   
               
             
          
         
       
     
     All of the active TSPs containing polyalkenimines tested against HD liquid in the Lesion Area Ratio (LAR) test showed significant (p&lt;0.05) protection compared to un-protected skin ( FIG. 12 ). Lesion Area Ratio is the measure of the protection given by the aTSP and compares the lesion size between sites protected by aTSP with sites not protected by aTSP. Several of the formulations also demonstrate significantly improved protection compared to SERPACWA (ICD3004). 
     A limited number of the active TSPs containing polyalkenimines were also tested in the rabbit lethality test for GD vapor. Many show excellent efficacy. Lethality at 1, 2, 3, 4 and 24 hours post exposure from 2 vapor caps each containing 28 mg GD/kg for 4 hrs. ( FIG. 13 ). 
     A limited number of the active TSPs containing polyalkenimines were also tested in the rabbit lethality test for VX liquid. Lethality at 1, 2, 3, 4 and 24 hr. post exposure to 0.5 mg VX/kg for 4 hrs. All were significantly (p &lt;0.05) better than no protection ( FIG. 14 ). 
     Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.