bluuebunny/crossref_metadata_2025 huggingface dataset:
The Metalation Reaction with Organolithium Compounds
Authors: Gilman Henry , Morton John W.
Published: March 2011

The term metalation denotes the replacement of hydrogen by metal to yield a true organometallic compound. The replacement of hydrogen by metal in a compound such as acetoacetic acid is not generally classed as a metalation reaction in this sense because the resulting salt is not a typical organometallic compound. This distinction is matter of degree. The ability to yield ortho priducts, usually unmixed with para or other isomers, distinguishes the metalation reaction from the more familiar types of substitutions and makes possible the preparation of many products not readily available by other routes. The derivative most commonly prepared from a metalation product has been the carboxylic acid, made by the reaction of the lithium compound with carbon dioxide. This reaction is useful in the study of metalation products because the usual metalating agents, the alkyllithium compounds, yield volatile acids which are easily separated from the acids of higher molecular weight obtained from the metalated products themselves.
The Cleavage of Non‐Enolizable Ketones with Sodium Amide. TheHaller‐Bauer Reaction
Authors: Hamlin K. E. , Weston Arthur W.
Published: March 2011

In this chapter the Haller‐Bauer is defined as the action of sodium amide on a non‐enolizable ketone causing cleavage of a carbon‐to‐carbon bond and resulting in the formation of an amide and a hydrocarbon. Textbook definitions have limited the reaction to the alkylation of ketones in which sodium amide acts a condensing agent or have considered it a combination of the alkylation and cleavage reactions. Haller and Bauer reported the isolation of benzamide after the treatment of benzophenone with sodium amide in boiling benzene or toluene and followed this observation with an extended study of the reaction. A modification of the Haller‐Bauer reaction involving the use of a fused eutectic mixture of sodium an potassium amides has been applied to certain alicyclic and bicyclic terpenoid ketones as well as to some amides.
The Alkylation of Esters and Nitriles
Authors: Cope Arthur C , Holmes H. L , House Herbert O
Published: March 2011

This chapter is concerned with the reactions of metal salts (enolates) of active methylene compounds with alkylating agents such as alkyl halides to produce allyl derivatives. The first example of this reaction is found in the literature when Geuther prepared ethyl alpha‐ethyl acetoacetate by the reaction of the sodium enolate of ethyl acetoacetate with ethyl iodide. The active methylene compounds considered in the chapter include malonic esters, cyanoacetic esters, malonitriles, monocarboxylic esters and mononitriles. These classes of compounds are characterized by the presence of one or more acidic hydrogen atoms attached to carbon. Only C‐alkylation has been observed with active methylene compounds and are discussed here. Several alternative methods for the preparation of alkyl and aryl derivatives of carboxylic esters and nitriles have been included.
The Synthesis of β‐Lactams
Authors: Sheehan John C. , Corey Ellas J.
Published: March 2011

The four‐membered ring appears to be the smallest cyclic system that is capable of accommodating the amide function as a constituent. Such four‐membered cyclic amides are commonly referred to as beta‐lactams. The reluctance with which beta‐lactams are formed using conventional methods of lactam synthesis has necessitated unique approaches to the problem. After 1943, interest in beta‐lactams was stimulated by the importance of natural penicillins. Although there are at present several useful approaches to the beta‐lactam ring systems, the synthesis of beta‐lactams by a single general method is not possible. In principle, the synthesis of the beta‐lactam ring might be accomplished by the formation of one, two, three, or all four bonds of the ring during the cyclization step. Of these four possibilities, only the last has been realized.
TheBeckmann Rearrangement
Authors: Guy Donaruma L. , Heldt Walter Z.
Published: March 2011

The rearrangement of a ketoxime to the corresponding amide was discovered in 1886 by E. Beckmann and is known as the Beckmann rearrangement. The rearrangement is brought about by acids, including Lewis acids. The more common rearranging agents are concentrated sulfuric acid, phosphorus pentachloride in ether, and Beckmann's mixture, hydrogen chloride in a mixture of acetic acid and acetic anhydride. The Beckmann rearrangement is used frequently to determine the structure of ketones, by identification of the acid and amine obtained by hydrolysis of the amide formed by the rearrangement. There is no uniform convention for the designation of the stereochemistry of oximes in the literature. The conventions used in this chapter for the configurations of ketoximes and aldoximes are explained.
The
D
emjanov and
T
iffeneau‐
D
emjanov Ring Expansions
Authors: Smith Peter A. S , Baer Donald R
Published: March 2011

The reaction of aminomethylcycloalkanes with nitrous acid to produce cycloalkanols in which the ring is larger by one carbon atom is known as the Demjanov rearrangement. The first example of this type of ring expansion was encountered in 1901, but was not recognized until 1903 when cyclopentanol was identified as one of the products formed from cyclobutanemethylamine. Since that time the reaction has extended to rings of many sizes. Olefins almost invariably accompany the alcohols that are formed. The Demjanov rearrangement includes within its scope the rearrangements that occur when acyclic amines are treated with nitrous acid as well as other ring expansion detailed in this chapter. The Tiffeneau‐Demjanov ring expansion is used here to designate ring enlargements by pinacolic deamination. This ring expansion can be made the key step in the conversion of a cyclic alcohol or ketone into its next ring homolog.
Olefins from Amines: TheHofmann Elimination Reaction and Amine Oxide Pyrolysis
Authors: Cope Arthur C. , Trumbull Elmer R.
Published: March 2011

The conversion of an amine to an olefin by elimination of the nitrogen atom and an adjoining hydrogen atom is a useful procedure for degradation and synthesis. The Hofmann exhaustive methylation method has been used most often to bring about change, but other methods as the thermal decomposition of amine oxides and the pyrolysis of amine phosphates or acetyl or benzoyl derivative have often been employed to advantage. This chapter reviews the Hofmann elimination because of its extensive history. Alternative methods are considered.
The Preparation of Olefins by the Pyrolysis of Xanthates. TheChugaev Reaction
Authors: Nace Harold R.
Published: March 2011

In this chapter the Chugaev reaction is defined as the thermal decomposition of the xanthate ester of an alcohol that contains at least one beta‐hydrogen atom to produce one or more olefins, carbon oxysulfide and a mercaptan. The formation of olefins by the pyrolysis of xanthates was discovered in 1899 by Chugaev in connection with his studies on the optical properties of xanthates and other compounds. He subsequently employed the reaction in his investigation of terpenes and demonstrated both its utility as an olefin‐forming reaction and its usefulness in structural determination. The reaction, which is particularly valuable for the conversion of sensitive alcohols to the corresponding olefins without the rearrangement of the carbon skeleton is analogous to the thermal decomposition of carboxylic esters of alcohols and other derivatives such as carbamates and carbonates, to yield olefins.
Halocyclopropanes from Halocarbenes
Authors: Parham William E. , Schweizer Edward E.
Published: March 2011

This chapter reviews methods for the generation of halocarbenes and the reaction of the latter with unsaturated substrates. Chemical transformations of the derived halocyclopropanes are discussed in sufficient detail to demonstrate the synthetic utility of this class. The formation of dihalocyclopropanes from dihalocarbenes was first accomplished in 1954 by Doering and Hoffmann who used chloroform t‐ butoxide to generate the dichlorocarbene. Since that time a variety of other methods have been developed for the generation of halocarbenes. The various methods are discussed.
Free Radical Additions to Olefins to Form Carbon‐Carbon Bonds
Authors: Walling Cheves , Huyser Earl S.
Published: March 2011

Some of the most useful reactions in synthetic organic chemistry involve the addition of reagents across the double bonds of olefins. These reactions, which can occur by a variety of mechanisms involving electrophilic, nucleophilic or radical intermediates, have been the subject of numerous mechanistic studies. Electrophilic additions involve polar reagents, and in general the direction of addition follows Markownikoff's rule. Nucleophilic additions require rather special and drastic conditions unless the olefin contains strong electron‐withdrawing substituents. Radical reactions are very general in scope, but are markedly influenced by light, oxygen, peroxides, and various inhibitors. The direction of addition in free‐radical reaction is commonly the opposite of that encountered in the electrophilic ionic (Markownikoff) additions. Hence these free‐radical additions have been referred to as Anti‐Markownikoff, abnormal or Karasch addition reactions. This chapter is concerned with the synthetic aspects of Kharasch addition reactions that result in the formation of a new carbon‐carbon bond.
The
C
hapman Rearrangement
Authors: Schulenberg J. W. , Archer S.
Published: March 2011

The thermal conversion of aryl N‐arylbenzimidates to N‐aroyldiphenylamines is known as the Chapman rearrangement. The starting materials for the Chapman rearrangement have been referred to as imino ethers, imido esters, imidates, and by miscellaneous other names. Roger and Neilson have named all the compounds as imidates. This chapter does not name the rearrangement products according to Chemical Abstracts, which lists the compounds as derivatives of benzanilide or benzamide. Here the products are called aroyldiarylamines. All of the compounds obtained by amide hydrolysis are named diarylamines. The Chapmann rearrangement has been shown to be an intramolecular reaction in which a 1,3 shift of an aryl group from oxygen to nitrogen occurs.
α‐Amidoalkylations at Carbon
Authors: Zaugg Harold E. , Martin William B.
Published: March 2011

This chapter is concerned with reactions that lead to the formation of a new carbon‐carbon bond by the replacement of X (eg, halogen, ‐OH, ‐OR, ‐OCOR, ‐NHCOR ‐NR 2 or NR3) from an electrophilic reagent, RCON(R')CH(R”)X. The R' group may be hydrogen or alkyl or an acyl group. In a few cases a sulfonyl group may replace the acyl group of the electrophilic reagent. The nucleophiles that react with these reagents fall into two broad groups: aromatic compounds and aliphatic compounds containing reactive methylene or methane groups. Methods for preparing the electrophilic reagents are included in this chapter.
The Wittig Reaction
Authors: Maercker Adalbert
Published: March 2011

In 1953 Wittig and Geissler found that reaction of benzophenone with methylenetriphenylphosphorane gave 1,1‐diphenylethylene and triphenylphosphine oxide in almost quantitative yield; the phosphine had been prepared from triphenylmethylphosphonium bromide and phenyl lithium. The discovery led to the development of a new method for the synthesis of olefins, under the name Wittig reaction. One advantage of this new method is that the carbonyl group is replaced specifically by a carbon‐carbon double bond without the formation of isomeric olefins. In contrast, the older method of converting carbonyl compounds to olefins using the Grignard reaction usually give a mixture of isomeric olefins. Another advantage is the Wittig reaction is carried out under mild conditions. Discussions of modern techniques for the preparation of methylene phosphoranes are included in this review.
TheKnoevenagel Condensation
Authors: Jones G.
Published: March 2011

Knoevenagel's first papers in this field were concerned with the condensation of formaldehyde with diethyl malonate and with ethyl benzoylacetate. The catalyst was ethylamine. A number of other aldehydes were reported to condense similarly with diethyl malonate, ethyl benzoylacetate, ethyl benzoylpyruvate, and acetylacetone under the influence of various primary and secondary amines. In 1896, Knoevenagel reported benzaldehyde with ethyl aceoacetate condensed at room temperature in the presence of piperdine to give a bis compound, but that when the reaction was run in a freezing mixture, the product was acetoacetate. For the purposes of this chapter, the Knoevenagel condensation is defined as the reaction between an aldehyde or ketone or any compound having an active methylene group, brought about by an organic base or ammonia and their salts.
Preparation of Ketones from the Reaction of Organolithium Reagents with Carboxylic Acids
Authors: Jorgenson Margaret J.
Published: March 2011

The reaction of organolithium reagents and carboxylic acids constitutes a simple general method for the synthesis of ketones. This preparative route is the method of choice for direct conversion of carboxylic acid to ketones. It is the purpose of this chapter to evaluate critically the scope and limitations of this reaction and to recommend optimal conditions for its applications. The reaction of organolithium reagents with carboxylic acid is limited to the preparation of acyclic ketones. Although the objective of this reaction, the formation of unsymmetrical ketones, the method is clearly applicable to the synthesis of symmetrical ketones. Two different routes are possible and are discussed. To date, the reaction has been applied only to the preparation of monoketones.
The Smiles and Related Rearrangements of Aromatic Systems
Authors: Truce William E. , Kreider Eunice M. , Brand William W.
Published: March 2011

In 1894, Henriques reported that bis(2‐hydroxy‐1‐naphthyl) sulfide was converted to an isomeric dibasic substance by treatment with alkaline ferricyanide and a subsequent reduction of the intermediate obtained. Hinsberg carried out a similar sequence of reactions with bis(2‐hydroxy 1 naphthyl) sulfone. The structures of the isomeric products of the two series were established by Smiles who recognized the occurrence of a novel intramolecular nucleophilic rearrangement.

This chapter surveys the reactions, which because of the extensive work of Smiles, have been called Smiles rearrangements. They may be characterized as intramolecular displacements at aromatic rings initiated by nucleophilic centers located two or three atoms distant from the functional group which is displaced.
The Reactions of Diazoacetic Esters with Alkenes, Alkynes, Heterocyclic and Aromatic Compounds
Authors: Dave Vinod , Warnhoff E. W.
Published: March 2011

After the first unsuccessful attempt of Curtius in 1884 to affect the reaction of ethyl diazoacetate with toluene other researchers studied the reaction. Later, Buchner and Curtius treated several aromatic, olefinic, and acetylenic compounds with diazoacetic esters to form cyclopropanes. Since then the reactions of diazoacetates with various unsaturated compounds have been studied. The carbalkoxy carbenes are of interest since they are believed to be intermediates in higher temperature thermal and photochemical reactions of diazoacetates.
The Base‐Promoted Rearrangements of Quaternary Ammonium Salts
Authors: Pine Stanley H.
Published: March 2011

The based‐promoted rearrangements of quaternary ammonium salts can be divided into two categories. In the Stevens rearrangement one‐alkyl group migrates from the quaternary nitrogen group to the alpha carbon atom of a second alkyl group. The Somelet‐Hayser rearrangement involves migration to the ortho position of a benzyl quaternary ammonium salt. When structurally feasible, both rearrangements may occur simultaneously although experimental conditions markedly affect the competing pathways.
Conjugate Addition Reactions of Organocopper Reagents
Authors: Posner Gary H.
Published: March 2011

Addition of an organometallic reagent to alpha,beta‐usaturated carbonyl compounds occurs in one or both of two modes: attack at the carbonyl function produces a 1,2 adduct, whereas reaction with the entire system gives a 1,4 adduct. Organoalkali metal reagents derived from unstabilized carbanions generally add across the carbonyl group, where as enolate and other stabilized anions usually undergo a Michael addition, introducing a carboalkyl group at the beta carbon. Grignard reagents normally give 1,2 adducts. The wide scope of these reagents has made conjugate addition of alkyl and aryl groups a useful reaction in organic synthesis. Copper‐promoted conjugate additions were generally effected by allowing an organomagnesium reagent and a alpha, beta‐ unsaturated carbonyl compound to react in the presence of a catalytic amount of copper salt. Studies since 1966 have shown that stoichiometric organocopper reagents in addition to their broad utility in coupling reactions with organic halides and in reaction with other substrates undergo unusually effective conjugate addition to a wide variety alpha,beta‐ unsaturated carbonyl substrates. Emphasis in this chapter is on stoichiometric organic copper reagents. Mechanism, scope, limitations, synthetic utility, and optimal conditions are considered.
TheThiele‐Winter Acetoxylation of Quinones
Authors: McOmie J. F. W. , Blatchly J. M.
Published: March 2011

In 1898, Johannes Thiele described the reaction of p‐benzoquinone with acetic acid in the presence of a small quantity of sulfuric acid to give 1,2,4‐triacetoxybenzene in 80% yield. Later Thiele and Winter described further experiments that showed both 1,2‐ and 1,4‐naphthoquinone gave 1,2,4‐triacetoxynaphthalene and that the same product was obtained when sulfuric acid was replaced by zinc chloride. Thiele‐Winter acetoxylation can be defined as the acid‐catalyzed reactions of quinones with acetic acid to give triacetoxy aromatic compounds. This reaction has been carried out on a large number of quinones and to this point there has been no review. Very little work has been done on the reaction of quinones with anhydrides other than acetic anhydride. Results of these studies are summarized. Reactions with other anhydrides are discussed.
Cyclopropanes from Unsaturated Compounds, Methylene Iodide, and Zinc‐Copper Couple
Authors: Simmons Howard E. , Cairns Theodore L. , Vladuchick Susan A. , Hoiness Connie M.
Published: March 2011

The reaction of the organozinc reagent prepared from methylene iodide and zinc‐copper couple with substituted unsaturated compounds has proved to be a versatile and convenient method for the synthesis of cyclopropanes. The synthesis is stereospecific with regard to the stereochemistry of the unsaturated compound and is usually free from serious side reactions; it can be carried out under mild conditions in diethyl and affords cyclopropanes often in good yields. This method can be easily adapted to large‐scale preparations. Two useful variations of the cyclopropanation reaction have appeared which involve the same or a similar organozinc intermediate: (1) diazomethane reacts with iodide in ether to form a reagent which converts unsaturated compounds to cyclopropanes; (2) methlyene iodide and diethyl zinc react in ether in the presence of unsaturated compounds to cyclopropanes. Processes are known in which a divalent carbon fragment adds to carbon‐carbon double bonds either as a free carbene or as an organometallic complex.
The Zinin Reduction of Nitroarenes
Authors: Porter H. K.
Published: March 2011

The Zinin reduction is a method for the reduction of nitroarenes by negative divalent sulfur. This versatile reaction can be carried out in the laboratory and for plant‐scale manufacture of aromatic amines when other reduction media are destructive to sensitive compounds or result in undesired side reactions. The first reaction, used by Zinin, was to prepare aniline from nitrobenzene. It has been of great importance in the preparation of aromatic amines. Refinements in technique and a better understanding of the reaction mechanism should make this method attractive for the preparation of a variety of amines.
Fluorination by Sulfur Tetrafluoride
Authors: Boswell G. A. , Ripka W. C. , Scribner R. M. , Tullock C. W.
Published: March 2011

Although sulfur tetrafluoride is a remarkably versatile agent for selectively introducing fluorine atoms into organic compounds, its existence was doubted as late as 1950. A colorless gas boiling at ‐38o C, sulfur tetrafluoride was probably first made by treatment of sulfur with uranium hexafluoride and subsequently by the reaction of sulfur with cobalt(III) fluoride. Both products were of questionable purity. In 1950 sulfur tetrafluoride was unequivocally synthesized by electrical decomposition of trifluormethylsulfur pentafluoride. It was not until 1955 that gram amounts were prepared and thus making sulfur tetrafluoride a viable compound. This led the way for the discovery of its remarkable fluorinating ability. The ability of sulfur tetrafluoride to replace carbonyl oxygen selectively is probably the most useful synthetic application.
Modern Methods to Prepare Monofluoroaliphatic Compounds
Authors: Sharts Clay M. , Sheppard William A.
Published: March 2011

Organic fluorine chemistry has been important since the 1930s. The development of fluorine chemistry during World War II is well documented. Fluorine chemistry emerged in the 1950s because of three events:

Large‐scale research designed to synthesize fluorine‐containing rockets was initiated.

A fluorine atom at a specific site in a steroid molecule was found to enhance beneficial pharmacological effects

New analytical techniques evolved (e.g., GC and NMR).

There are eight reactions important for preparation of monofluoroaliphatic compounds.

Halogen addition to alkenes and alkynes

Fluoroalkylamine reagent for replacement of a hydoxy group.

Nitrosyl fluoride addition to an activated double bond

Hypofluorites for electrophilic fluorination.

Inorganic and heteroatom fluorides for replacement of halogen, hydroxyl, or ester groups

Hydrogen fluoride for addition

Perchloryl fluoride for hydrogen replacement

Condensation of a monolfluorinated organic compound.
Clemmensen Reduction of Ketones in Anhydrous Organic Solvents
Authors: Vedejs E.
Published: March 2011

The Clemmensen reduction of ketones and aldehydes using zinc and hydrochloric acid is the simplest direct method for converting the carbonyl group into a methylene group. Typically the carbonyl is refluxed for several hours with 40% hydrochloric acid, amalgamated zinc, and a water‐immiscible organic solvent such as tolurene. Because of these harsh conditions, reports of successful Clemmensen reduction of polyfunctional ketones have been rare. A milder procedure using dry hydrogen chloride in organic solvent extends the potential of this reaction. Other developments that define scope of both aqueous and anhydrous reduction conditions are discussed and an effort is made to compare the properties of possible reduction intermediates with other organozinc species.
The Acyloin Condensation
Authors: Bloomfield Jordan J. , Owsley Dennis C. , Nelke Janice M.
Published: March 2011

The acyloin condensation usually involves the reductive dimerization of a carboxylic ester, although acid chlorides and the anhydrides have been used. The reducing agent is in an alkali metal and the product is an ene‐diolate. Two gram‐atoms of metal are required for each mole of ester with the concomitant formation of a mole of akoxide and one‐half mole of the ene‐diolate. Oxidation of acyloins to diketoes can be accomplished by a variety of reagents. Acyloins can be reduced to ketones by various modifications of the Clemmenson technique. Under mild conditions the ketone will dominate. This chapter presents a complete picture of both the linear and cyclic acyloin condensation with particular emphasis on developments since 1960. The discussion is closely limited to the acyloin condensation and its modifications.
Alkenes from Tosylhydrazones
Authors: Shapiro Robert H.
Published: March 2011

In 1952, Bamford and Stevens observed that tosylhydrazones of aliphatic ketones yielded alkenes when treated with the sodium salt of ethylene glycol in boiling ethylene glycol. In addition to the alkene, molecular nitrogen, and p‐toluenesulfinate anion were produced. This chapter reviews such syntheses of alkenes from tosylhydrazones and the formation of cyclopropanes and acetylenes from tosylhydrazones because the several reactions involved are so closely interrelated. The four major reaction types are reviewed here: (1) base‐induced decomposition of tosylhydrazones in protic solvents and (2) in aprotic solvents (3) reactions of tosylhydrazones with alkyllithium reagents and (4) fragmentation reactions of alpha, beta‐epoxytosylhydrazones and analogous systems. Reactions 1 and 2 are called the protic and aprotic Bamford‐Stevens reaction.
Ester Cleavages
via
S

N

2‐Type Dealkylation
Authors: Mc Murry John
Published: March 2011

The cleavage of esters to furnish carboxylic acids is a common organic transformation that is usually carried out in a routine manner by acidic or basic hydrolysis. It often happens, however, particularly in the synthesis of natural products, that the substrate ester is sensitive to hydrolytic conditions. For such sensitive materials a number of mild, neutral methods of ester cleavage have been devised. Those methods that occur with displacement of carboxylate by SN2 dealkylation are the subject of this chapter.
Arylation of Unsaturated Compounds by Diazonium Salts (The
M
eerwein Arylation Reaction)
Authors: Rondestvedt Christian S.
Published: March 2011

The arylation of unsaturated compounds by diazonium salts with copper salt catalysis was first disclosed by Meerwein. Meerwein arylation proceeds best when the double bond is activated by an electron attracting groups such as carbonyl, cyano, aryl, vinyl, ethynyl or chloro. The net result is the union of the aryl group with the carbon atom beta to the activating group, either by substitution of a beta‐hydrogen atom of by addition of Ar and Cl to the double bond. The generally accepted mechanism of the reaction involves the aryl radical from the diazonium salt, though the manner of its formation and subsequent reaction is still controversial
Practical aspects of the oral new anticoagulants
Authors: DeLoughery Thomas G.
Published: March 2011

After years of only oral vitamin K antagonists, there are new many new antithrombotic agents in development and on entering the marketplace. This review will analyze clinical trial results for these new agents—especially dibigatran, rivaroxaban, and apixiban. Also to be discussed are practical aspects of use of these new agents such monitoring, reversal, and use before procedures. Am. J. Hematol. 2011. © 2011 Wiley‐Liss, Inc.
Laboratory testing for cryoglobulins
Authors: Motyckova Gabriela , Murali Mandakolathur
Published: March 2011

Cryoglobulins are immunoglobulins that precipitate below 37°C and can cause multiorgan damage. There are three types of cryoglobulins: Type I (also called simple), which is mostly associated with monoclonal gammopathy and/or other hematologic disorders and Type II and Type III (known as mixed cryoglobulins), which are associated with infectious and systemic diseases. Testing for cryoglobulins is complicated by lack of reference range, standards, and stringency in maintaining testing temperature conditions. Identification of cryoprecipitate can be critical for patient care; therefore, correct testing conditions are crucial for reliable cryoglobulin testing. The patient's blood sample should be kept at 37°C initially to avoid premature precipitation of cryoglobulins and thereby decreasing the yield for subsequent identification. This could cause a false negative result. After warm centrifugation or warm cell precipitation, the clear serum is observed at 4°C for formation of cryoprecipitate. The cryoprecipitate is then washed in cold buffer, and the resulting precipitate is warmed to 37°C and subjected to further analysis by immunodiffusion and immunofixation. In addition to Meltzer's triad of purpura, weakness and arthralgias, cryoglobulinemias have protean manifestations involving skin, joints, kidney, nervous system, as well as the hematopoietic system. The management of cryoglobulinemia especially in patients with organ damage remains difficult. Treatment of cryoglobulinemia focuses on management of the underlying lymphoproliferative disorder or infectious or systemic causes. Medical management may also include corticosteroids and other immunosuppressive agents and plasmapheresis. Rituximab therapy seems to abrogate the aberrant B cell response. Am. J.Hematol. 86:500–502, 2011. © 2011 Wiley‐Liss, Inc.
No significant improvement in the outcome of patients with Waldenström's macroglobulinemia treated over the last 25 years
Authors: Kastritis Efstathios , Kyrtsonis Marie‐Christine , Hatjiharissi Evdoxia , Symeonidis Argiris , Michalis Eurydiki , Repoussis Panagiotis , Tsatalas Konstantinos , Michael Michael , Sioni Anastasia , Kartasis Zafiris , Stefanoudaki Ekaterini , Voulgarelis Michael , Delimpasi Sosana , Gavriatopoulou Maria , Koulieris Efstathios , Gika Dimitra , Vervesou Elissavet , Konstantopoulos Konstantinos , Kokkini Garyfalia , Zomas Athanasios , Roussou Paraskevi , Anagnostopoulos Nikolaos , Economopoulos Theofanis , Terpos Evangelos , Zervas Konstantinos , Dimopoulos Meletios A.
Published: March 2011

The treatment of Waldenström's macroglobulinemia (WM) has changed over the last decades, mainly because of the introduction of nucleoside analogues and of rituximab while novel agents such as bortezomib have been recently introduced. We performed an analysis to investigate whether the outcome of patients with WM has improved over the last years, compared to that of patients who started treatment before new drugs became widely available, especially as part of the frontline treatment. We analyzed 345 symptomatic patients with WM: 130 who initiated treatment before and 215 who started treatment after January 1, 2000. Patients who started treatment in the latter group were older and had more often elevated beta2‐microglobulin but the other characteristics were similar between the two groups. Most patients who started treatment before January 1, 2000 were treated upfront with alkylating agent‐based regimens and most patients who started treatment after January 1, 2000 received rituximab‐based regimens as initial treatment. Objective response (63 and 59%, respectively) and median overall survival, OS, (106.5 months for Group A and is estimated at 94 months for Group B, P = 0.327) were similar. There was also no difference regarding OS or cause specific survival (CSS) in each risk group according to IPSSWM. Our observation may be explained by the indolent course of WM in several patients and by the lack of profound cytoreduction in patients with high‐risk disease. Possible differences in the 15‐ or 20‐year survival rate between the two groups may be detected with further follow‐up of these patients. Am. J. Hematol. 2011. © 2011 Wiley‐Liss, Inc.
Integration of field and captive studies for understanding the behavioral ecology of the squirrel monkey (Saimirisp.)
Authors: Zimbler‐DeLorenzo Heather S. , Stone Anita I.
Published: March 2011

Captive and field studies both provide valuable and complementary information that lead to a better understanding of a species' behavioral ecology. Here, we review studies from wild, captive, and semi‐free ranging populations of squirrel monkeys (Saimirisp.), in order to (a) provide a more current (1985–2010) review ofSaimiribehavioral ecology and (b) illustrate that integrating data collected in a variety of settings is an effective approach to addressing ecological questions in primates. Captive environments, such as zoological facilities and research colonies, can be advantageous to researchers by allowing longitudinal studies of behavior and reproduction, as well as providing opportunities for gathering data on life history, because physiological and life history data are known for individual animals. Studies of field populations can provide contextual information regarding the adaptive nature of behaviors that are studied in captivity. Squirrel monkeys are small, neotropical primates that have extensively been used in captive research. As the last in‐depth review ofSaimiribiology was published in 1985 [Rosenblum & Coe, The squirrel monkey. New York: Academic Press], we review studies since conducted onSaimiriecology, life history, social behavior, reproduction, and conservation. Our review indicates that there is much variation in socioecology and life history traits betweenSaimirispecies and, surprisingly, also between populations of the same species studied at different locales. In addition, much is known about squirrel monkey reproductive physiology, basic ecology, and vocal communication, but data are still lacking in the fields of life history and some adaptive components and social behavior. In particular, longitudinal studies in the field would be particularly relevant for a genus with a slow life history such asSaimiri. Finally, few data (captive or wild) are available onS. ustusandS. vanzolinii, though at least one of these species is threatened. Am. J. Primatol. 73:607–622, 2011. © 2011 Wiley‐Liss, Inc.
Iron(III), cobalt(II) and copper(II) complexes bearing 8‐quinolinol encapsulated in zeoliteY for the aerobic oxidation of styrene
Authors: Yang Ying , Ding Hong , Hao Shijie , Zhang Ying , Kan Qiubin
Published: March 2011

A series of Fe(III), Co(II) and Cu(II) complexes of 8‐quinolinol were encapsulated into the supercages of zeoliteY and characterized by X‐ray diffraction, SEM, N2 adsorption/desorption, FT‐IR, UV–vis spectroscopy, elemental analysis, ICP‐AES and TG/DSC measurements. The encapsulation was achieved by a flexible ligand method in which the transition metal cations were first ion‐exchanged into zeolite Y and then complexed with 8‐quinolinol ligand. The metal‐exchanged zeolites, metal complexes encapsulated in zeolite–Y plus non‐encapsulated homogeneous counterparts were all screened as catalysts for the aerobic oxidation of styrene under mild conditions. It was found that the encapsulated complexes always showed better activity than their respective non‐encapsulated counterparts. Moreover, the encapsulated iron complex showed good recoverability without significant loss of activity and selectivity within successive runs. Heterogeneity test for this catalyst confirmed its high stability against leaching of active complex species into solution. Copyright © 2011 John Wiley & Sons, Ltd.
Adsorption of Remazol Brilliant Violet‐5R reactive dye from aqueous solution by cocoa pod husk‐based activated carbon: kinetic, equilibrium and thermodynamic studies
Authors: Bello Olugbenga Solomon , Siang Tan Tong , Ahmad Mohd Azmier
Published: March 2011

The adsorption of Remazol Brilliant Violet‐5R (RBV‐5R) reactive dye on cocoa pod husk activated carbon (CPHAC) was investigated in batch process. The effects of initial dye concentration, contact time, solution temperature and pH were evaluated. The equilibrium data were fitted into Langmuir, Freundlich, Temkin and Dubinin‐Radushkevich isotherm models. It was found that Freundlich model fitted the adsorption data most. The kinetic data were fitted into pseudo‐first‐order, pseudo‐second‐order, Elovich and intraparticle diffusion models. Adsorption of RBV‐5R dye on CPHAC was best described by pseudo‐second‐order kinetic model. The adsorption of RBV‐5R dye was favored at acidic pH. Thermodynamic parameters such as standard free energy ΔG0, standard enthalpy ΔH0 and standard entropy ΔS0 were calculated. The adsorption interaction of RBV‐5R reactive dye on the adsorbent was found to be feasible, spontaneous and endothermic. The adsorption process followed a physisorption mechanism. © 2011 Curtin University of Technology and John Wiley & Sons, Ltd.
Exergy analysis and flowsheet modification of PT. PUSRI II Palembang's reformer unit for the production of synthesis gas from natural gas
Authors: Djoni Bustan Muhammad , Mahadzir Shuhaimi , Kharismadewi Dian
Published: March 2011

Several processes which produce synthesis gas from natural gas have been analyzed by the exergy method. To minimize the exergy losses associated to chemical reaction, it is important to manage the exergy losses through the analysis, reconsidering the chemical path. A generally applicable and schematic way of performing exergy analysis and dealing with their results are illustrated. It is integrated to the modified flowsheeting reformer. As petrochemical industry in Indonesia, PT. Pupuk Sriwijaya II Palembang uses natural gas as a raw material to produce synthesis gas through the primary and the secondary reformers in a series. In the modified flowsheeting reformer, partial oxidation process has been added before the primary reformer and the secondary reformer has been eliminated from the process pathways. The exergy method of analysis has been implemented for each process, in order to calculate the exergies of the material streams along with the energy and mass‐balance calculations both in the modified flowsheeting reformer and in a series process of the primary and the secondary reformers. And, the results of the calculations of the modified flowsheeting reformer in the process proposed modification are then compared to the results of the calculations of the series process of reformers in the existing conventional process. From the analysis, the overall exergy losses in a series process of the primary and secondary reformers can be reduced until 61.33%, by applying the modified flowsheeting reformer. Copyright © 2011 Curtin University of Technology and John Wiley & Sons, Ltd.
Evolution of the precipitation kinetics, morphology, and permeation performance of phenolphthalein poly(ether sulfone) hollow‐fiber membranes with polyvinylpyrrolidones of different molecular weights as additives
Authors: Lang Wan‐Zhong , Chu Lian‐Feng , Guo Ya‐Jun
Published: March 2011

Phenolphthalein poly(ether sulfone) (PES‐C) hollow‐fiber ultrafiltration (UF) membranes were fabricated by wet spinning and dry‐jet/wet spinning (10‐cm air gap) processes with polyvinylpyrrolidones (PVPs) of different molecular weights as additives. Light transmittance experiments were performed to obtain insight into the precipitation kinetics of PES‐C/PVP/N‐methyl‐2‐pyrrolidone (NMP) dope solutions. The morphology and permeation performance of the prepared PES‐C hollow‐fiber membranes were well characterized and elucidated with scanning electron microscopy and UF experiments in addition to the precipitation kinetics. The thermal and mechanical properties of the membranes were also studied. Experiments demonstrated that all PES‐C/PVP/NMP dope solutions experienced instantaneous demixing with pure water as the coagulant, and the precipitation rate decreased as the molecular weight of PVP increased. A double, fingerlike structure occurred in the PES‐C hollow‐fiber membranes spun with PVPs of low molecular weight (10,000, 24,000, or 58,000) as additives; however, a spongelike structure occurred in the PES‐C membranes with PVP with a molecular weight of 1,300,000 because of its very low precipitation rate. The pure water permeation (PWP) flux decreased and the rejection of lysozyme increased for the prepared PES‐C membranes as the molecular weight of PVP increased. The largest PWP flux of 149 L m−2 h−1 bar−1 was acquired for dry‐jet/wet‐spun PES‐C membranes with PVP with a molecular weight of 10,000 as an additive. The rejection of bovine serum albumin for the prepared PES‐C membranes was greater than 98%, and the rejection of lysozyme ranged from 47.1 to 89.4%; this indicated typical UF membranes. The decomposition temperature of the PES‐C membranes containing PVP was lower than that of the original polymer and decreased as the molecular weight of PVP increased. The break strain and the elongation at break were enhanced as the PVP molecular weight increased. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
Effect of the tie‐layer thickness on the delamination and tensile properties of polypropylene/tie‐layer/nylon 6 multilayers
Authors: Khariwala D. , Ling M. , Hiltner A. , Baer E.
Published: March 2011

This study examined the effect of the tie‐layer thickness on the delamination behavior of polypropylene/tie‐layer/nylon 6 multilayers. Various maleated polypropylene resins were compared for their effectiveness as tie‐layers. Delamination failure occurred cohesively in all the multilayer systems. Two adhesion regimes were defined according to the change in the slope of the linear relationship between the delamination toughness and the tie‐layer thickness. The measured delamination toughness of the various tie‐layers was quantitatively correlated to the length of the damage zone that formed at the crack tip. In addition, the effect of the tie‐layer thickness on the multilayer tensile properties was correlated with the delamination behavior. The fracture strain of the multilayers decreased with decreasing tie‐layer thickness. An examination of the prefracture damage mechanism of the stretched multilayers revealed a good correlation with the delamination toughness of the tie‐layers. In thick tie‐layers (>2 μm), the delamination toughness was great enough to prevent the delamination of the multilayers when they were stretched. In thin tie‐layers (<2 μm), the delamination toughness of all the tie‐layers was low; consequently, delamination led to premature fracture in the stretched multilayers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Polypropylene/wasted poly(ethylene terephthalate) fabric composites compatibilized by two different methods: Crystallization and melting behavior, crystallization morphology, and kinetics
Authors: Zhidan Lin , Juncai Shen , Chao Chen , Xiuju Zhang
Published: March 2011

Polypropylene (PP)/wasted poly(ethylene terephthalate) (PET) fabric composites and these composites modified by maleic anhydride grafted polypropylene (PP‐g‐MA) and reactive monomers were prepared with a twin‐screw extruder. The crystallization morphology, nonisothermal crystallization and melting behavior, crystallization kinetics, and isothermal crystallization kinetics were investigated with differential scanning calorimetry. The results indicated that the wasted fabric (WF) had a heterogeneous nucleation effect on PP in the composites, and this increased the crystallization temperature and induced PP to form transcrystallinity. PP‐g‐MA further increased the crystallization temperature; however, the reactive monomers weakened the heterogeneous nucleation effect of WF. Also, the premelting temperature affected the crystallization and melting behavior of the composites significantly. The Avrami equation and the Mo method provided a fairly satisfactory description of the crystallization kinetics. The crystallization activation energy, nucleation constant, and folding surface free energy of PP were markedly reduced in the PP/waste PET fabric composites and the compatibilized composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 00: 000–000, 2011
Different properties for poly(3,4‐ethylenedioxythiophene) films derived from single or multiple polymerization steps
Authors: Aradilla David , Estrany Francesc , Alemán Carlos
Published: March 2011

Films of poly(3,4‐ethylenedioxythiophene) were prepared with single and multiple electropolymerization steps, where the numbers of polymerization steps (n's) were 3, 5, and 7, with identical experimental conditions and total polymerization times (τ's). The electroactivity of the films prepared with multiple steps remained almost unaltered when n increased, with the ability of the films to store charge with n > 3 being smaller than that of the films with similar thicknesses but derived from a single electrodeposition step. In contrast, the stability of the films produced with n polymerization steps was significantly higher than that of the films derived from a single step with the same τ, with the difference between the two systems increasing with n, that is, τ used to yield the films. On the other hand, although the morphological and topological characteristics of the surface and the electrical conductivity were affected by the procedure used to produce the films, the organization of the polymer molecules in the crystalline phase, the thermal stability, and the electronic properties (ionization potential, electron affinity, and lowest π–π* transition energy) were practically identical in both cases. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Synthesis of poly(ethylene glycol)–dopamine conjugates and their controlled drug‐release behaviors
Authors: Zhang Juan , Liu Yi‐Feng , Bo Lan , Qiao Chang‐An
Published: March 2011

Dopamine (DA) was covalently linked via succinic anhydride spacers to poly(ethylene glycol)s (PEGs) with average molecular weights of 4000 (PEG4000), 6000 (PEG6000), and 10,000 (PEG10000). The chemical modification of the PEGs was conducted by a two‐step protocol: (1) the preparation of PEG having carboxylic end groups and (2) the synthesis of PEG4000–DA, PEG6000–DA, and PEG10000–DA. The controlled drug‐release studies were performed in pH 1.1, 7.4, and 9.0 buffer solutions, The results demonstrate that under the same conditions, the rate of hydrolysis for PEG10000–DA was the slowest among three prodrugs, and a greater amount of DA could be detected being released from the prodrug matrices in the presence of α‐chymotrypsin in a buffer solution with pH 8.0. Also, these novel prodrugs could slowly release the active drug molecules and improve the pharmacokinetics of DA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Effect of swelling and reactive dyeing on the accessibility of cotton to cellulase enzymes
Authors: Paul Roshan , Teli Mangesh D.
Published: March 2011

The main objective of this study was to determine the effect of intracrystalline and intercrystalline swelling agents and reactive dyes on the accessibility of cotton cellulose to commercial cellulase enzymes. Both types of swelling agents improved the accessibility, and intracrystalline swelling agents showed better results, as the accessibility to difficult‐to‐reach crystalline regions was increased. As expected, the reactive dyes inhibited the accessibility of the enzymes to some extent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Synthesis of graft copolymers of binary vinyl monomer mixtures onto acetylated Saccharum spontaneum L and characterization
Authors: Maiti Mithu , Jindal Rajeev , Kaith Balbir Singh , Jana Asim K.
Published: March 2011

Methylmethacrylate (MMA) + acrylamide (AAm), MMA + acrylonitrile (AN), and MMA + acrylic acid (AA) binary vinyl monomer mixtures were graft copolymerization onto acetylated Saccharum spontaneum L, was carried out and maximum graft yield (185.6 %) was found with MMA+AAm binary mixture. Synthesized graft co‐polymers were characterized with FT‐IR spectrophotometry, scanning electron microscopy (SEM), thermal analysis TGA/DTA/DTG, and X‐ray diffraction (XRD) techniques. Thermal stability of Ss‐g‐poly(MMA + AAm) was found to be more than that of natural, acetylated S. spontaneum fiber and other graft copolymers. Although on grafting, percentage crystallinity and crystallinity index were found to decrease but graft copolymers were found to exhibit more moisture, chemical, and thermal resistance. Also, it can be observed that the surface of the grafted fibers is highly rough in comparison with the ungrafted fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011