bluuebunny/crossref_metadata_2025 huggingface dataset:
Recent Advances in the Physics and Chemistry of Rubber. III. The Solubility and Swelling of Rubbers
Authors: Gee Geoffrey
Published: February 2011

In Parts I and II we have built up a picture of the molecular structure of a piece of rubber, which we have envisaged as a mass of interpenetrating chains, each of considerable length, but randomly kinked and in constant thermal motion, so that its shape is continually changing. Vulcanization restricts the possible motions of the mass by introducing permanent connections between pairs of chains at a series of irregularly spaced points. The purpose of Part III is to show how the picture can be extended to account for the behavior of such a system in contact with a liquid. If we imagine a liquid as a mass of more or less spherical molecules in constant thermal motion, it is clear that, when a liquid is brought into contact with a rubber, there is a tendency for molecules of liquid to diffuse into the rubber structure. Considering first the case of an unvulcanized rubber, we should expect the liquid to enter in increasing amounts, thereby separating the rubber chains and giving them very much greater freedom of motion, until finally some of them begin to find their way out of the main body of rubber and into the liquid. The rubber would thus be observed first to swell and then slowly to disperse until a uniform mixture of rubber and liquid is produced. This is, of course, the behavior actually observed when raw rubber is brought into contact with a liquid in which it is soluble. It is important to emphasize that the driving force which causes the mixing is simply the thermal motion of the components, and is not essentially dependent on any molecular attraction between rubber and liquid. It can be given a quantitative measure in terms of the thermodynamic concept of the increase of entropy consequent on mixing, but this development will not be considered here, our purpose being only to discuss the essential physical basis of the phenomenon.
Systems Manifesting Superposed Elastic and Viscous Behavior
Authors: Tobolsky A. V. , Andrews R. D.
Published: February 2011

Actual substances exhibit a very complicated behavior under mechanical stresses which cannot be described by classical elasticity theory nor by the classical theory of the hydrodynamics of viscous fluids. A general molecular theory describing the behavior of matter under stress is discussed and related to previous investigations and to experimental observations. Particular attention is devoted to rubberlike substances for which the classical theories are definitely inadequate. Experimental results on relaxation and creep of rubbers are interpreted in terms of modern structural concepts. It is found that these substances exhibit three regions of stress-temperature-time dependence. At intermediate temperatures there is a region of relative stability in which the statistical-thermodynamic theory of rubber elasticity is valid. At elevated temperatures, relaxation and creep are caused by chemical changes involving the rupture and formation of primary valence bonds. These chemical changes, which are responsible for the aging of rubber, can be isolated and studied by appropriate experimental techniques. At low temperatures relaxation and creep are caused by the slipping of secondary interchain bonds which are breaking and reforming in times comparable to experimental times of measurement. Theories are advanced to explain the observed stress-temperature-time behavior of rubbers over the entire temperature range studied.
Objective Laboratory Testing of the Processability of Elastomers
Authors: White L. M. , Ebers E. S. , Shriver G. E.
Published: February 2011

Ananalysis is made of the types of adverse behavior encountered in compounding and fabricating dry-mixed elastomers on a factory scale, with an attempt to ascribe the different modes of behavior to semifundamental properties of the elastomer and its compounds. On the basis of this analysis, four simple tests—filler stiffening, compound viscosity, length shrinkage, and rugosity—are proposed for determining the processing properties of elastomers on a laboratory scale. Extended correlations of predictions made from these tests with factory data demonstrate their reliability and usefulness in laboratory evaluation of new rubberlike materials. Much of the background information referred to in this and the following paper (page 833) was accumulated by the rubber industry at large working on the government-sponsored rubber program through the Research and Development Section, Rubber Reserve Company, and therefore has been subject to the usual secrecy orders. For this reason much of the earlier literature has not been published in the usual channels. However, every effort has been made to recognize contributions, made but not released, by other investigators by reference to their names and organizations.
The Vulcanization of Rubber with Phenol Formaldehyde Derivatives. I
Authors: van der Meer S.
Published: February 2011

Referring to Part I, describing the methylene quinone theory of the vulcanization of rubber with phenol-formaldehyde derivatives, in this paper the arguments in favor of that theory are considered in detail. The results of the investigations in question can be summarized as follows. 1. The vulcanizing properties of the pseudophenol halides are based on the easy transformation of these compounds into methylene quinones, with liberation of gaseous hydrogen halide. 2. The vulcanizing properties of the phenol-dialcohols are also based on the formation of methylene quinones as intermediates, but only at higher temperatures. 3. Phenol-dialcohols vulcanize slowly at temperatures only slightly below their decomposition temperatures, and yield comparatively good vulcanizates. Pseudophenol halides vulcanize rapidly at temperatures considerably below their decomposition temperatures, and yield comparatively poor vulcanizates. 4. The vulcanization temperature of 4,6-dihydroxymethyl-2-methylphenol (about 200° C) is higher than that of 2,6-dihydroxymethyl-4-methylphenol (about 155° C), as in the first case the vulcanization is based on the formation of an o-methylene quinone as well as a p-methylene quinone, and in the second case on the formation of o-methylene quinones exclusively. Generally these last compounds are formed more easily than the p-isomers. 5. The vulcanizing properties of 2,6-dihydroxymethyl-4-methylphenol at 155° C are reduced by the addition of 4,6-dihydroxymethyl-2-methylphenol, in consequence of the formation of molecular complexes which are unable to form o-, but only p-methylene quinones. 6. The vulcanizing properties of phenol-formaldehyde derivatives are entirely destroyed by hexamethylenetetramine, as that substance combines with the methylene quinones first formed. 7. The vulcanization reactions of the phenol-formaldehyde derivatives are not based on the formation of an irregular knot of entangled rubber and resin molecules, but on primary chemical bonds between these two. 8. The vulcanizing properties of the esters of the phenol-dialcohols, as well as those of the pseudophenol halides, are based on the formation of methylene quinones as intermediates, with liberation of acids. The higher fatty acid esters of 2,6-dihydroxymethyl-4-methylphenol are unstable, with the liberation of acids already at room temperature. 9. Compounds which may be supposed to be derived from phenol-dialcohols by a change in their configuration do not show vulcanizing properties if the formation of methylene quinones is impossible. If a repeated formation of these intermediates is only possible to a very limited extent, as is the case with phenol-monoalcohols, vulcanizing properties are also present on a minor scale.
Compression-Tear Test for Susceptibility to Road-Cracking of Synthetics
Authors: Trepp S. G. , Ward A. L. , Chaney N. K.
Published: February 2011

One of the outstanding weaknesses of GR-S rubber in tire-tread formulations is a pronounced tendency to crack in road service. In general cracks originate at the bottom of cuts or of moulded grooves in the tread, but spontaneous cracking may originate from local weak spots in the interior of the tread. Properly formulated natural rubber stocks are not susceptible to this type of failure, and usual laboratory and plant criteria and test methods developed by long experience for natural rubber formulations have been proved inadequate and misleading with respect to the evaluation of the susceptibility of GR-S rubber to this type of failure. These considerations have led to the development of the compression-tear test for susceptibility to cut growth which is the subject of this paper. The underlying principle of the test is to develop, under static easily controlled laboratory conditions, the type of strain which is the normal resultant of impact shocks of indeterminate severity under road service conditions. When pressure is applied at the surface of a cut or groove in a tire tread, the usual result is to pinch the walls of the cut together at the surface and to force them apart midway of the cut, thus producing a shearing force on the rubber under compression at the bottom of the cut. The U. G. I. compression-tear test is designed to set up a shearing force under conditions of high compression at elevated temperatures at the bottom of a standardized cut, and to measure the rate of cut growth with time.
The Weber Color Test for the Identification of Natural Rubber
Authors: Parker I. F. C. , Wake W. C.
Published: February 2011

The Weber color reaction, mentioned in a recent note, has become of importance in detecting natural rubber in mixtures in which it may be considerably diluted with synthetic rubber or nonrubber materials. The detailed instructions for carrying out the test are given elsewhere, and Stern has published a table which shows also the colors obtained when the test is applied to rubbers other than the natural product. It is clear from this table, and is confirmed by our experience, that the strong violet color developed is distinctive for natural rubber and gutta-percha, provided that the material has been extracted with acetone. However, color reactions in organic chemistry are rarely found to be as specific as earlier workers have claimed, and work is being carried out in these laboratories to establish the limitations of the reaction when applied to rubberlike materials. With very few exceptions, synthetic rubbers and rubberlike materials available at present do not give a positive result with this test, although very faint violet colors, which cannot be confused with a positive result, are sometimes obtained. Those giving any violet color are listed in Table I.
II. Effect of Coagulants on the Quality of Rubber
Authors: Siddiqui Rafat Husain , Mathur M. L.
Published: February 2011

1. Whatever coagulant is used for coagulation, a certain proportion of inorganic components, proteins and resins (1/9, 1/7, 1/5, respectively) of those originally present in latex remains adsorbed on rubber. 2. One-half of the total solids are eliminated with serum during coagulation. 3. The quality of rubber does not vary with a coagulant. 4. The molecules of latex are saclike bodies consisting of an inner core of rubber surrounded by protective films of resins and proteins, and the intervening spaces are filled with serum components. A puncture in the latex sac expels the serum components and brings about a collapse of the protective films which get adsorbed on rubber and these fused sacs float in serum as cream. By further fusion of cream particles a spongy coagulum of rubber is formed. 5. Coagulation is brought about because of profound changes in latex produced by physical and chemical agencies which destroy the stability of the system by elimination of resins, proteins and serum components, by neutralization of the charge on the rubber, and by the disruption of electrical, molecular and cohesive forces that pervade latex.
Free and Forced Vibration Methods in the Measurement of the Dynamic Properties of Rubbers
Authors: Moyal J. E. , Fletcher W. P.
Published: February 2011

Previous work on the shear elastic modulus and damping factor of rubber has been carried out chiefly by two methods. Some workers have deduced these quantities from the natural frequency and rate of decay of the free vibrations of a simple system comprising a mass and a rubber spring; others have obtained the values from the resonance curve of such a system under forced vibration excited by a known harmonic force of variable frequency. The derivation of the shear modulus and damping factor from the experimental results is in both cases based on the assumption for rubber of a simple mechanical model consisting of a spring with a viscous dashpot in parallel. In order to ascertain whether the results from the two methods (more particularly for the damping factor) correspond, measurements have been carried out by both methods on the same rubber test piece on the same mechanical system and under identical conditions. The approximate agreement between the results thus obtained justifies the basic assumptions underlying these methods.
Physical Examination of Brass Deposits
Authors: Buchan S. , Rae W. D.
Published: February 2011

Microscopic examination of average brass deposits revealed a fairly uniform deposit of thickness varying from 0.0006 to 0.00004 inch, the brass deposit being thinner at the centre of the plate than at the edges. β-brass was obtained at points where porosity occurred in the base metal. The deposit was collected in aggregates or hillocks dispersed fairly evenly over the plate, a condition which was confirmed by examination under the electron microscope. With this instrument it was demonstrated that bad bonding brass was nonuniform over the surface, a fact further substantiated by subsequent x-ray analysis. Differences in crystallite size and in degree of crystalline orientation appeared to have no consistent effect on the bonding properties of the brass. The brass deposit showed, however, a high degree of preferred orientation, as is usual with electrodeposits. As regards the preparation of the base metal, the use of too much oil and too high a speed of machining appeared to have a detrimental effect. This appeared to be due to the fact that a nonuniform state of strain was produced over the surface as samples of mild steel of various degrees of strain, but uniform over the surface, gave consistently good adhesion.
The Infrared Spectra of Compounds of High Molecular Weight
Authors: Thompson H. W. , Torkington P.
Published: February 2011

Many methods are being used at present to explore the reasons for the differences in physical behavior of various types of polymers, plastics, rubbers and other compounds of high molecular weight. The peculiar rheological and electrical properties of many of these substances must be connected with the internal molecular structure and with the way in which the molecules can pack together in the solid and liquid states. Valuable information has already been obtained using the diffraction of x-rays, and some chemical methods have also given useful indications of the nature of the polymerization processes. The determination of molecular weights and chain lengths of fiberlike polymers has also led to important correlations. No method, however, has provided all the information which might enable us to formulate rules correlating properties with structure. It is clear that any method which can examine the sample without the use of chemical reagents is of advantage, and from this standpoint spectroscopy should be useful. The infrared absorption spectra of substances of this type consist essentially of bands which correspond to the absorption of characteristic vibration frequencies of the whole molecule, or of particular units within it. Since, theoretically, no two molecules having a different nuclear skeleton have the same set of vibrational frequencies, we may expect small differences between the spectra of closely related molecules, and a careful analysis of the vibrational spectra may reveal the occurrence of special groups, or the arrangement of the nuclear skeleton within these molecules. For this analysis reference data from the spectra of simple related molecules may first be required. Apart from giving such fundamental structural information, however, the infrared spectra can be used empirically for many practical purposes. Small differences in the properties of samples of the same polymer can sometimes be correlated empirically with small differences in their spectra. The effect of different plasticizing or vulcanizing agents, leading for instance to cross-linking, can also be explored by spectral changes. On the fundamental side too, it is valuable from the standpoint of molecular dynamics to assemble data on long-chain polymeric substances as a basis for the calculation of the vibration frequencies of these molecules as systems of weighted chains. If the molecular dynamics could be understood more completely, it might prove a useful adjunct to the consideration of thermodynamic properties.
Gas Permeability and the Microstructure of Polymers
Authors: Reitlinger S. A.
Published: February 2011

1. The permeability to gas of high molecular-weight polymers is closely connected with the character of the interaction between separate links of adjacent macromolecules, which is governed by the form of the chain and the energy of the intermolecular bonds. 2. The magnitude of permeability increases with increases in the curvature of the principal-valence chains and in the dimensions of the side groups, decreases with increase in the energy of the intermolecular bonds, and is independent of the length of the main valence chains. 3. A comparison of the values of the activation energies and gas permeabilities of a series of polymers makes reasonable the assumption that the principal paths for the penetration of hydrogen molecules lie along the interface between the nonpolar groups of the macromolecular chains.
Mechanism of Rubber Cracking
Authors: Powell E. F. , Gough V. E.
Published: February 2011

Rubber and rubberlike polymers, in common with other materials which deteriorate on exposure to oxidizing or similar agents, eventually crack under normal atmospheric service conditions. The present paper confines itself to the factors affecting the type and appearance of the cracking which eventually occurs when a surface film of a rubber object (particularly when stressed) hardens and deteriorates in strength from any cause whatsoever. The importance of an understanding of the effects of exposure conditions on the character of the cracking produced cannot be too highly emphasized. This is so even if interest is confined solely to simple tests on new protective paints on an acceptance basis rather than research into surface deterioration. It is probable that many protective agencies have been accepted or rejected for extensive production tests because the initial laboratory tests have either not been representative of service or have been inadequate in scope. This still remains a major problem. The theory presented here has gradually taken shape over a period of some ten years and appears to describe adequately the general findings on the whole gamut of cracking, viz., fine check cracking and isolated deep cracks produced under service and laboratory conditions, the latter covering flexing, roof exposure, ozone and similar tests.
Relations between the Quality of Latex and Its Chemical Composition
Authors: Martin George
Published: February 2011

One of the chief technical difficulties when latex is used industrially for the manufacture of rubber articles is that there is no method available for determining whether or not successive shipments of latex are suitable for any particular process of manufacture. Two samples of latex may be similar in appearance and have nearly the same chemical properties with respect to dry rubber content, total solids and alkalinity, yet one sample may be in excellent condition, whereas the other sample is on the point of coagulating. When these two samples are mixed with compounding ingredients, one remains quite fluid, while the other thickens or even coagulates. Then again, when treated with a coagulant, one sample gels in a normal way and under conditions compatible with good processing, whereas the other sample gels either too rapidly or too slowly, or coagulates to an unusable mass. It is safe to say that there is no generally acceptable method with which it is possible to judge the quality of latex, and the different procedures which have been suggested cannot be regarded as satisfactory. Rubber planters have called attention many times to the large variations in the properties of natural latex. Preserved latex is perhaps even more variable, for new factors then enter and influence its properties, e.g., the effects of bacteria before any preservatives are added to the latex, and chemical reactions which take place between certain components of the latex and the preservatives. In addition, the properties of latex change continuously with age, which is extremely limited compared with that of dry rubber.
The Fibrous Properties and Abrasion Resistance of Synthetic Rubber Compounds
Authors: Kusov A.
Published: February 2011

1. A method of measuring the tear resistance of rubber compounds was developed. This method has a number of advantages over other methods (Goodrich, Heidensohn, Goodyear, etc.), including the following. (a) The symmetrical shape and the large surface of tearing (20 sq. cm.). This excludes the possibility of short, accidental tears, and enables better observation of the nature of the tear. (b) Owing to the small size of the clamped portion of the specimen compared to the size of the tearing surface, “end effects” are largely eliminated. (c) Tearing forces are registered periodically (every 10 seconds), and it is possible in this way to determine the total energy expended on tearing, and the nature of its changes. (d) The experiments are easy to perform, and the apparatus is simple. 2. The addition of carbon black (10–100 per cent) to synthetic rubber compounds increases considerably the tear resistances of the vulcanized products. The best results are obtained with compounds containing between 50 and 75 per cent of carbon black. 3. A zinc oxide content of between 8 and 14 per cent improves the tear resistances of compounds of both synthetic and natural rubbers. 4. Compounds with increased fibrous structure show increased abrasion resistance when the fiber direction is parallel to the movement of the abrading surface. 5. Compounds cured for short times only show low tear resistances when made of synthetic rubbers of both low (0.31) and high (0.87) plasticity. The best results are obtained with compounds made of synthetic rubber of medium plasticity (0.53 and 0.40) (see Figure 4). 6. When comparing tear resistances, it is of the utmost importance to maintain the thickness of test-specimens within narrow limits. It is desirable to keep variations within 10–15 per cent. 7. The weakening of the uncut portion of a test-specimen with increase in depth of cut is less pronounced with compounds of synthetic rubber than it is with natural rubber compounds, particularly in the case of overcured samples. With synthetic compounds, this weakening effect varies 2–3 times; with natural rubber compounds it is 3.5–6.5 times. The relation between tear resistance and depth of cut is shown in Figure 5 and Table VI. 8. Carbon black compounds of both synthetic and natural rubbers exhibit various structural forms of tearing. Synthetic rubber compounds with low tear resistances show simple and smooth tearing surfaces, usually in the prolongation of the cut, or at a slight angle to it (Figure 1, type A or intermediate between A and B). Synthetic compounds with high tear resistances show complicated tearing surfaces (Figures 6 and 7, types C, D, E and F).
Metal‐Free One‐Pot Oxidative Amination of Aromatic Aldehydes: Conversion of Benzaldehyde to

N

‐Benzoyl Pyrrolidine
Authors: Ekoue‐Kovi Kekeli , Wolf Christian
Published: February 2011

Benzaldehyde

Pyrrolidine

N
‐Benzoyl pyrrolidine

tert
‐Butyl hydroperoxide
A Practical and Scalable Synthesis of
N
‐Halo Compounds: 2‐Chloro‐6,7‐Dimethoxy‐1,2,3,4‐Tetrahydroisoquinoline
Authors: Zhong Yong‐Li , Bulger Paul G.
Published: February 2011

2‐Chloro‐6,7‐dimethoxy‐1,2,3,4‐tetrahydroisoquinoline

6,7‐Dimethoxy‐1,2,3,4‐tetrahydroisoquinoline hydrochloride

Sodium hypochlorite

tert
‐Butanol
Stereoselective Synthesis of 3‐Arylacrylates by Copper‐Catalyzed Syn Hydroarylation
Authors: Kirai Naohiro , Yamamoto Yoshihiko
Published: February 2011

2‐Octynoic acid, methyl ester

Boronic acid, phenyl

Acetic acid, copper (1+) salt

2‐Octenoic acid, 3‐phenyl‐, methyl ester
Preparation of (

S

)‐3,3'‐Bis‐morpholinomethyl‐5,5',6,6',7,7',8,8'‐octahydro‐1,1'‐bi‐2‐naphthol
Authors: Turlington Mark , Pu Lin
Published: February 2011

Paraformaldehyde

Morpholine

Morpholinomethanol

(
S
)‐5,5′,6,6′,7,7′,8,8′‐Octahydro‐1,1′bi‐2‐napthol [(
S
)‐H
8
BIBOL]

(S
)‐3,3′‐Bismorpholinomethyl 5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐bi‐2‐naphthol
Catalytic Asymmetric Addition of an

in

‐

situ

Prepared Arylzinc to Cyclohexanecarboxaldehyde: (

R

)‐(+)‐α‐cyclohexyl‐3‐methoxy‐benzenemethanol
Authors: DeBerardinis Albert M. , Turlington Mark , Pu Lin
Published: February 2011

Lithium acetylacetonate

3‐Iodoanisole

Diethyl zinc

(
S
)‐3,3'‐Bis‐morpholinomethyl‐5,5',6,6',7,7'8,8'‐octahydro1‐1'‐bi‐2‐naphthol

Cyclohexanecarboxaldehdye

(R)‐(+)‐alpha‐Cyclohexyl‐3‐methoxy‐benzenemethanol
Microwave‐Assisted Synthesis of 1,3‐Dimesitylimidazolinium Chloride
Authors: Hans Morgan , Delaude Lionel
Published: February 2011

Lithium acetylacetonate

3‐Iodoanisole

Diethyl zinc

(S)‐3,3'‐Bis‐morpholinomethyl‐5,5',6,6',7,7'8,8'‐octahydro1‐1'‐bi‐2‐naphthol

Cyclohexanecarboxaldehdye

(R)‐(+)‐alpha‐Cyclohexyl‐3‐methoxy‐benzenemethanol
Synthesis of Substituted Indazoles via [3+2] Cycloaddition of Benzyne and Diazo Compounds
Authors: Shi Feng , Larock Richard C.
Published: February 2011

Ethyl diazoacetate

2‐(Trimethylsilyl)phenyl trifluromethanesulfonate

Tetrabutylammonium fluoride
Palladium‐Catalyzed Cross‐Coupling Using an Air‐Stable Trimethylaluminum Source. Preparation of Ethyl 4‐Methylbenzoate
Authors: Vinogradov Andrej , Woodward Simon
Published: February 2011

Trimethylaluminum

DABCO

Pd2(dba)3

X‐Phos

Ethyl 4‐bromobenzoate
Synthesis of Dimethyl 2‐Phenylcyclopropane‐1,1‐Dicarboxylate Using an Iodonium Ylide Derived from Dimethyl Malonate
Authors: Goudreau Sébastien R. , Marcoux David , Charette André B.
Published: February 2011

Potassium hydroxide

Dimethyl malonate

Iodosobenzene diacetate

Bis[rhodium(a,a,a′a′‐tetramethyl‐1,3‐benznedipropionic acid)]

Styrene

Thiourea
Preparation of Ethyl 1‐Benzyl‐4‐Fluoropiperidine‐4‐Carboxylate
Authors: Kong Jianshe , Meng Tao , Ting Pauline , Wong Jesse
Published: February 2011

Disiopropylamine

n
‐Butyllithium

Ethyl isonipectoate

Benzyl bromide

Ethyl 1‐benzylpiperidine‐4‐carboxylate

N
‐Fluorobenzenesulfonimide
Cyclohexene Imine
Authors: Watson Iain D. G. , Afagh Nicholas , Yudin Andrei K.
Published: February 2011

Cyclohexene oxide, 98%

Triphenylphosphine, 99%

Sodium azide, 99.5%
Synthesis of Tetraorganosilanes: (Chloromethyl)Dimethylphenylsilane
Authors: Murakami Kei , Yorimitsu Hideki , Oshima Koichiro
Published: February 2011

Bromobenzene

Magnesium

Dichloro(
N,N,N′N′
‐tetramethylethylenediamine)zinc

Chloro(chloromethyl)dimethylsilane

(Chloromethyl)dimethylphenylsilane
1,3,5‐Triacetylbenzene
Authors: Alaimo Peter J. , Marshall Amanda‐Lynn , Andrews David M. , Langenhan Joseph M.
Published: February 2011

trans
‐4‐Methyl‐3‐buten‐2‐one

1,3, 5‐Triacetylbenzene
One‐Pot Diazotization and Heck Reaction of Methyl Anthranilate: 2‐(3‐Oxopropyl)Benzoic Acid Methyl Ester
Authors: Zaragoza Florencio
Published: February 2011

Methyl anthranilate

Allyl alcohol

Methyl‐2‐(3‐oxopropyl)enzoate
Synthesis of Ynamides by Copper‐Mediated Coupling of 1,1‐Dibromo‐1‐Alkenes with Nitrogen Nucleophiles. Preparation of 4‐Methyl‐

N

‐(2‐Phenylethynyl)‐

N

‐(Phenylmethyl)Benzenesulfonamide
Authors: Coste Alexis , Couty François , Evano Gwilherm
Published: February 2011

4‐Methyl‐
N
‐(phenylmethyl)benzenesulfonamide

P
‐Toluenesulfonyl chloride

Triethylamine

(2,2‐Dibromoethenyl0benzene

Carbon tetrabromide

Triisopropyl phosphite

Benzaldehyde

4‐Methyl‐
N‐(
2‐phenylethynyl)‐
N
‐(phenylmethyl)benzenesulfonamide

Cesium carbonate

N,N‐
Dimethylethylenediamine
Preparation and [2+2] Cycloaddition of 1‐Triisopropylsiloxy‐1‐Hexyne with Methyl Crotonate: 3‐Butyl‐4‐Methyl‐2‐Triisopropylsiloxy‐Cyclobut‐2‐Enecarboxylic Acid Methyl Ester
Authors: Shubinets Valeriy , Schramm Michael P. , Kozmin Sergey A.
Published: February 2011

Methyl crotonate

Triisopropylsilyl trifluoromethanesulfonate

Trifluoromethanesulfonanimide

Silver carbonate
Synthesis of Enamides from Ketones: Preparation of

N

‐(3,4‐Dihydronaphthalene‐1‐Yl)Acetamide
Authors: Zhao Hang , Vandenbossche Charles P. , Koenig Stefan G. , Singh Surendra P. , Bakale Roger P.
Published: February 2011

3,4‐Dihydronaphthalene‐1(2
H
)‐one oxime

Hydroxylamine hydrochloride

a‐Tetralone

N
‐(3,4)dihydronaphthalene‐1‐yl)acetamide

Triethylphosphine

Acetic anhydride
Safe and Scalable Preparation of Barluenga's Reagent
Authors: Chalker Justin M. , Thompson Amber L. , Davis Benjamin G.
Published: February 2011

Tetrafluoroboric acid

Silver carbonate

Pyridine

Iodine

Bis(pyridine)iodonium (I) terafluoroborate
Palladium‐Catalyzed Alkyl‐Alkyl Suzuki Cross‐Couplings of Primary Alkyl Bromides at Room Temperature: (13‐Chlorotridecyloxy)Triethylsilane
Authors: Lou Sha , Fu Gregory C.
Published: February 2011

8‐Bromo‐1‐octanol

Dichlorotriphenylphosphorane

Imidazole

4‐Penten‐1‐ol

Chlorotriethylsilane

Triethyl(pent‐4‐enoxy)silane

9‐BBN

Palladium(II) acetate

Bicyclohexylphosphine

Tripotassium phosphate monohydrate

(13‐Chlorotridecyloxy)trietylsilane
Synthesis of Chiral Pyridine Bis(Oxazoline) Ligands for Nickel‐Catalyzed Asymmetric Negishi Cross‐Couplings of Secondary Allylic Chlorides with Alkylzincs: 2,6‐Bis[(4

R

)‐4,5‐Dihydro‐4‐ (2‐Phenylethyl)‐2‐Oxazolyl]‐ Pyridine
Authors: Lou Sha , Fu Gregory C.
Published: February 2011

L‐Homophenylalanine

D‐Homophenylalanine, ethyl ester hydrochloride

Lithium aluminum hydride

(
S
)‐2‐Amino‐4‐phenylbutan‐1‐ol

(
R
)‐2‐Amino‐4‐phenylbutan‐1‐ol

2,6‐Pyridinedicarbonitrile

Zinc trifluormethanesulfonate

2,6‐Bis[4
R
)‐4,5 dihydro‐4(2‐phenylethyl)2‐oxazolyl]pyridine
Nickel‐Catalyzed Asymmetric Negishi Cross‐Couplings of Racemic Secondary Allylic Chlorides with Alkylzincs: (

S

,

E

)‐Ethyl 6‐(1,3‐Dioxolan‐2‐Yl)‐4‐Methylhex‐2‐Enoate
Authors: Lou Sha , Fu Gregory C.
Published: February 2011

Ethyl(
E
)‐4‐oxo‐2‐butenoate

Methylmagnesium

Ethyl (
E
)‐4‐hydroxy‐2‐pentanoate

Dichlorotriphenylphosporate

Ethyl (
E
)‐4‐chloro‐2‐enaote

2‐(1,3‐Dioxolan‐2‐yl)ethyl bromide

2‐[2‐(1,3‐Dioxolan‐2‐yl)ethyl]zinc

Nickel(II) chloride, dimethoxyethane adduct

2,6‐Bis(S)‐4,5‐dihydro‐4‐(2‐phenylethyl)2‐oxazoyl]pyridine

(S,E)‐Ethyl‐6‐(1,3‐dioxolan‐2‐yl)‐4‐methyllhex‐2‐enolate
One‐Pot Synthesis of 5

H

‐Indazolo‐[3,2‐

B

]benzo[

d

]‐1,3‐Oxazine: Two Efficient Preparative Methods
Authors: Solano Danielle M. , Butler Jeffrey D. , Haddadin Makhluf J. , Kurth Mark J.
Published: February 2011

2‐Nitrobenzaldehyde

2‐Aminobenzyl alcohol

2‐Picoline borane

5
H‐
Indazolo‐[3,2b]benzo[d]‐1,3‐oxazine

2‐Nitrobenzyl bromide

Diisopropylethyl amine
Preparation of Chiral and Achiral Triazolium Salts: Carbene Precursors with Demonstrated Synthetic Utility
Authors: Vora Harit U. , Lathrop Stephen P. , Reynolds Nathan T. , Kerr Mark S. , de Alaniz Javier Read , Rovis Tomislav
Published: February 2011

4,4a,9,9a‐Tetrahydro‐1‐oxa‐4‐azafluoren‐3‐one

(1
R
, 2
S
)‐(+)‐
cis
‐!‐Amino‐indol

2‐Pentafluorophenyl‐6,10b‐dihydro‐4
H
,5a
H
‐5‐oxa‐3,10c‐diaza‐2azoniacyclopenta[
c
]fluorene;tetraborate

Trimethyloxonium tetrafluoroborate

Pentafluorophenyhydrazine
Development of Chemical Probes for Biochemical Detection and Cellular Imaging of Myristoylated and Palmitoylated Proteins
Authors: Hannoush Rami N.
Published: February 2011

Fatty acylation of proteins regulates their spatial localization and activity in living cells. Methods to monitor fatty acylation are invaluable for studying its role in regulating protein dynamics. The protocols in this unit describe a procedure that involves metabolic labeling with ω‐alkynyl fatty acids for detecting and cellular imaging of fatty‐acylated proteins, namely myristoylated and palmitoylated proteins. Curr. Protoc. Chem. Biol. 3:15‐26 © 2011 by John Wiley & Sons, Inc.
Multiplexed Detection with Magnetic Nanoparticles
Authors: Wilson Robert
Published: February 2011

The sections in this article are

Introduction

Magnetism and Magnetic Particles

Separating and Mixing Magnetic Particles

Planar Arrays

Rotating Discs

Diagnostic Devices

Bio‐Barcode Assays Based on Magnetic Microspheres

Spectrally Encoded Suspension Arrays of Magnetic Microspheres

Magnetically Encoded Suspension Arrays

Summary and Conclusions
Magnetic Nanoparticles for Cancer Imaging and Therapy
Authors: Natarajan Arutselvan , Sundrarajan Rajeswari , DeNardo Sally J.
Published: February 2011

The sections in this article are

Introduction

Synthesis and Surface Modifications ofMNPsfor Biological Applications

Fabrication of the Magnetic Nanoparticle Core

Surface Coatings and Chemistry

Physico‐Chemical Characterization ofMNPs

Plasma Stability and Pharmacokinetic Profile of theMNPs

Development ofMNPsas Cancer Diagnosis and Imaging Agents

MNPsUsed inMRImaging for Cancer Diagnosis

MNPsUsed in Optical Imaging for Cancer Diagnosis

Ligand‐DirectedMNPsfor Cancer Imaging

Antibody‐DirectedMNPs

Antibody Fragment‐DirectedMNPs

Radioimmunonanoparticles

Annexin 5‐DirectedMNPs

Chemotherapeutic Drugs Loaded withMNPsfor Cancer Therapy

Lymph Node‐TargetingMNPs

Other NovelMNPsfor Cancer Targeting

MNPsApplied to Cancer Therapy

MNPsUtilized in Targeted Therapy for Cancer

Brain Tumor Therapy

Breast Cancer Therapy

MNPsin Hyperthermia and Thermal Ablation

MNPs‐Directed Toxicity
Core–Shell Magnetic Nanomaterials in Medical Diagnosis and Therapy
Authors: Melancon Marites P. , Li Chun
Published: February 2011

The sections in this article are

Introduction

Synthesis

Formation of the Magnetic Core

Coprecipitation from Solution

Thermal Decomposition

Microemulsions

Pyrolysis

Formation of the Core–Shell Structure

Inorganic Core with Organic Shell

Inorganic Core with Inorganic Shell

Applications: Magnetic Resonance Imaging

Applications: Hyperthermia and Thermal Ablation

Passive Targeting

Dextran‐Coated Magnetite

Aminosilan‐Coated Magnetic Particles

Magnetic Cationic Liposomes

Active Targeting

Antibodies

Peptides

Folic Acid

Laser‐Induced Hyperthermia/Thermal Ablation Therapy

Application: Drug Delivery

Summary and Perspectives

Acknowledgments
Magnetic Nanomaterials for Environmental Applications
Authors: Warner Marvin G. , Warner Cynthia L. , Addleman R. Shane , Yantasee Wassana
Published: February 2011

The sections in this article are

Introduction

The Aim of the Chapter

The Role of Nanomaterials in Environmental Detection

Synthesis and Functionalization of Magnetic Nanoparticles

Synthetic Strategies for Magnetic Metal Oxide Nanoparticles

Coprecipitation

Thermal Decomposition

Other Synthetic Methods

Functionalization of Magnetic Nanoparticles

Organic Ligand Modification

Stabilization with Polymers

Inorganic Stabilization with Silica or Carbon

Less Common Methods of Passivation

Magnetic Nanoparticles for the Separation and Detection of Analytes

Chemical Separations with Functionalized Magnetic Nanoparticles

High Magnetic Field Gradient Separation and Preconcentration

Electrochemical Detection Enhanced by Magnetic Nanomaterials for Preconcentration

Analyte Detection Using Magnetic Nanoparticles through Nonelectrochemical Methods

Summary and Future Perspective

Acknowledgments
Magnetic Core–Polymer Shell Nanoparticles: Synthesis and Biomedical Applications
Authors: Neoh Koon Gee , Tan Lihan , Kang En‐Tang
Published: February 2011

Magnetic core–polymer shell nanoparticles, with the core mainly in the form of magnetite (Fe3O4) or maghemite (γ‐Fe2O3), offer great opportunities for applications in biomedicine. Such a configuration provides a synergistic combination of the intrinsic properties of the magnetic core with special biochemical functions, achieved through proper tailoring of the polymer shell. Active research and development efforts on the applications of such nanoparticles are ongoing in biomedical areas, such as contrast agents for magnetic resonance imaging to achieve increasingly high spatial resolution, down to the cellular and even molecular level; delivery vehicles of drugs to targeted organs or tumors; and as a heating mediator for cancer thermotherapy (hyperthermia). The controllability of these nanoparticles with respect to their physico‐chemical properties, biodistribution and site specificity within the physiological environment, are major challenges which need to be addressed. In this chapter we review the synthetic routes of magnetic core–polymer shell nanoparticles, with emphasis on the tailoring of the polymer shell to confer the nanoparticles with desired properties for biomedical applications.
Magnetosomes: Bacterial Biosynthesis of Magnetic Nanoparticles and Potential Biomedical Applications
Authors: Staniland Sarah S.
Published: February 2011

The sections in this article are

Introduction

Magnetic Nanoparticles for Medical Applications

Introduction

Requirements and Specifications for Biomedical Applications

Safety Aspects

Magnetic Properties

Particle Size and Shape

Particle Coatings

General Synthetic Methods

Precipitation

Thermal Decomposition

What Is Biomineralization? Biogenic Inorganic Materials

Magnetosomes: Biomineralization in Magnetic Bacteria

Bacteria Characterization

Magnetosome Characterization

Magnetosome Formation

Proteomics

Genetics

Mechanism

Progress and Applications of Novel Biomedical Magnetosome Materials

The Future for Biomedical Magnetosomes
Approaches to Synthesis and Characterization of Spherical and Anisometric Metal Oxide Magnetic Nanomaterials
Authors: Suber Lorenza , Peddis Davide
Published: February 2011

The sections in this article are

Introduction

Magnetism in Nanostructured Metal Oxides

Magnetism in Condensed Matter

Magnetic Anisotropy Energy

Magnetism in Small Particles: An Experimental Approach

Zero Field‐Cooled and Field‐Cooled Magnetization

Thermoremanent Magnetization

Magnetic Metal Oxides

Synthesis Methods for Spherical and Anisometric Iron Oxide Nanomaterials

Synthesis of Spherical and Anisometric Nanoparticles

Metal Salt Precipitation in Water

Sol–Gel

Microemulsions

Autocombustion Method

Surfactant‐Assisted Hydrothermal Treatment

Surfactant‐Assisted Ultrasound Irradiation

Ferrofluids

Surfactant‐Assisted Dehydration

Hydrophobic–Hydrophilic Phase Transfer

Core–Shell Spherical and Anisometric Particles

Core–Shell Fluorescent Magnetic Iron Oxide–Silica Particles

Synthesis of Anisometric Iron Oxide Nanocapsules

Maghemite and Magnetite Nanotubes

Solid Nanotube Template

Soluble Nanotube Template

Correlations between Synthesis and Magnetic Behavior in Iron Oxide Nanomaterials

Spherical and Anisometric Iron Oxide Particles

Spherical Magnetite (Fe3O4) Nanoparticles

Stable Iron Oxide Spherical Nanoparticle Dispersions (Ferrofluids)

Surfactant Effect

Anisometric Maghemite (γ‐Fe2O3) Particles

Core–Shell Nanoparticles

γ‐Fe2O3/Silica Core Coated with Gold Nanoshell

Effect of Particle Size and Particle Size Distribution on the Magnetic Properties of Magnetite/PDMSNanoparticles

Nanocomposites

Magnetic Properties of Cobalt Ferrite–Silica Nanocomposites Prepared by a Sol–Gel Autocombustion Technique

Ordered Mesoporous γ‐Fe2O3/SiO2Nanocomposites

Fe3O4/Polymethylmethacrylate

Iron Oxide Nanowires and Nanotubes

Fe3O4Nanowires

Fe3O4Nanowires and γ‐Fe2O3Nanotubes

Fe3O4and γ‐Fe2O3Tube‐in‐Tube Nanostructures

Conclusions and Perspectives
Approaches to the Synthesis and Characterization of Spherical and Anisotropic Magnetic Alloy Nanomaterials
Authors: Wellons Matthew S. , Lukehart Charles M.
Published: February 2011

The sections in this article are

Introduction

Magnetic Noble Metal Alloy Nanoparticles

Magnetic Early Transition Metal Alloy Nanoparticles

Summary and Future Perspectives
Polymer Thin Films for Biomedical Applications
Authors: Vendra Venkat K. , Wu Lin , Krishnan Sitaraman
Published: February 2011

The sections in this article are

Introduction

Biocompatible Coatings

Protein‐Repellant Coatings

PEGylated Thin Films

Non‐PEGylated Hydrophilic Thin Films

Thin Films of Hyperbranched Polymers

Multilayer Thin Films

Antithrombogenic Coatings

Surface Chemistry and Blood Compatibility

Membrane‐Mimetic Thin Films

Heparin‐Mimetic Thin Films

Clot‐Lyzing Thin Films

Polyelectrolyte Multilayer Thin Films

Polyurethane Coatings

Vapor‐Deposited Thin Films

Antimicrobial Coatings

Cationic Polymers

Nanocomposite Polymer Thin Films Incorporating Inorganic Biocides

Antibiotic‐Conjugated Polymer Thin Films

Biomimetic Antibacterial Coatings

Thin Films Resistant to the Adhesion of Viable Bacteria

Coatings for Tissue Engineering Substrates

PEGylated Thin Films

Zwitterionic Thin Films

Thin Films of Hyperbranched Polymers

Polyurethane Coatings

Polysaccharide‐Based Thin Films

Polyelectrolyte Multilayer Thin Films

Temperature‐Responsive Polymer Coatings

Electroactive Thin Films

Other Functional Polymer Coatings

Multilayer Thin Films for Cell Encapsulation

Patterned Thin Films

Polymer Thin Films for Drug Delivery

Polymer Thin Films for Gene Delivery

Conclusions
Thin Films on Titania, and Their Applications in the Life Sciences
Authors: Brand Izabella , Nullmeier Martina
Published: February 2011

The sections in this article are

Introduction

Titanium in Contact with a Biomaterial

Lipid Bilayers at the Titania Surface

Formation of Lipid Bilayers on the Titania Surface

Spreading of Vesicles on a TiO2Surface: Comparison to a SiO2Surface

Interactions: Lipid Molecule–Titania Surface

Structure and Conformation of Lipid Molecules in the Bilayer on the Titania Surface

Structure of Phosphatidylcholine on the Titania Surface

Characteristics of Extracellular Matrix Proteins on the Titania Surface

Collagen Adsorption on Titania Surfaces

Morphology of Collagen Adsorbed on an Oxidized Titanium Surface

Adsorption of Collagen on a Hydroxylated Titania Surface

Morphology and Structure of Collagen Adsorbed on a Calcified Titania Surface

Conclusions

Structure of Collagen on the Titania Surface: Theoretical Predictions

Fibronectin Adsorption on the Titania Surface

Morphology of Fibronectin Adsorbed on the Titania Surface

Fibronectin–Titania Interactions

Structure of Fibronectin Adsorbed onto the Titania Surface

Atomic‐Scale Picture of Fibronectin Adsorbed on the Titania Surface: Theoretical Predictions

Conclusions

Conclusions

Acknowledgments
Preparation, Characterization, and Potential Biomedical Applications of Nanostructured Zirconia Coatings and Films
Authors: Liu Xuanyong , Xu Ying , Chu Paul K.
Published: February 2011

The sections in this article are

Introduction

Preparation and Characterization of Nano‐ZrO
2
Films

Cathodic Arc Plasma Deposition

Plasma Spraying

Sol–Gel Methods

Electrochemical Deposition

Anodic Oxidation and Micro‐Arc Oxidation

Magnetron Sputtering

Bioactivity of Nano‐ZrO
2
Coatings and Films

Cell Behavior on Nano‐ZrO
2
Coatings and Films

Applications of Nano‐ZrO
2
Films to Biosensors
Understanding and Controlling Wetting Phenomena at the Micro‐ and Nanoscales
Authors: Wang Zuankai , Koratkar Nikhil
Published: February 2011

The sections in this article are

Introduction

Wetting and Contact Angle

Design and Creation of Superhydrophobic Surfaces

Design Parameters for a Robust Composite Interface

Creation of Superhydrophobic Surfaces

Superhydrophobic Surfaces with Unitary Roughness

Superhydrophobic Surfaces with Two‐Scale Roughness

Superhydrophobic Surfaces with Reentrant Structure

Impact Dynamics of Water on Superhydrophobic Surfaces

Impact Dynamics on Nanostructured
MWNT
Surfaces

Impact Dynamics on Micropatterned Surfaces

Electrically Controlled Wettability Switching on Superhydrophobic Surfaces

Reversible Control of Wettability Using Electrostatic Methods

Electrowetting on Superhydrophobic Surfaces

Novel Strategies for Reversible Electrowetting on Rough Surfaces

Electrochemically Controlled Wetting of Superhydrophobic Surfaces

Polarity‐Dependent Wetting of Nanotube Membranes

Mechanism of Polarity‐Dependent Wetting and Transport

Potential Applications of Electrochemically Controlled Wetting and Transport

Summary and Future Perspectives

Future Perspectives

Acknowledgments
Quantum Dots for Cancer Imaging
Authors: Xiao Yan , Gao Xiugong
Published: February 2011

The sections in this article are

Introduction

Cancer

A Primer on Cancer Biology

The Importance of Early Cancer Detection and Diagnosis

The Role of Biomarkers in Cancer Early Detection and Diagnosis

Quantum Dots: Physics and Chemistry

Photophysical Properties ofQDs

Quantum Dot Chemistry

Synthesis

Surface Passivation

Water Solubilization

Bioconjugation

Cancer Imaging withQDs

In VitroScreening and Detection of Cancer Biomarkers Using Microarrays

In VitroCellular Labeling of Cancer Biomarkers

Labeling of Fixed Cells and Tissues

Live Cell Imaging in Cancer Cells

In VivoCancer Imaging

In VivoTracking of Cancer Cells

Tumor Vasculature Imaging

Sentinel Lymph Node Mapping and Fluorescence Lymphangiography

In VivoWhole‐Body Tumor Imaging in Animals

Multimodality Tumor Imaging

Dual‐FunctionalityQDsfor Cancer Imaging and Therapy

Quantum Dot Cytotoxicity and Potential Safety Concerns

Concluding Remarks and Future Perspectives

Acknowledgments
Multiplexed Bioimaging Using Quantum Dots
Authors: Byers Richard , Tholouli Eleni
Published: February 2011

The sections in this article are

Introduction

The Need for Novel Multiplex Imaging Systems

Quantum Dots

Optical Properties

Manufacture

Bioimaging Applications of Quantum Dots

Quantum Dot Use for Immunohistochemistry

Quantum Dot Use for
In Situ
Hybridization

Quantum Dot Use in Solid‐ and Liquid‐State Multiplex Detection Platforms

Translation to Clinical Biomarker Measurement

Quantitation

Imaging Analysis

Combinational Microscopy Methods

Clinical and Mechanistic Biological Applications

Cancer Molecular Profiling

Summary and Future Perspectives
Multiplexed Detection Using Quantum Dots
Authors: Kim Young‐Pil , Xia Zuyong , Rao Jianghong
Published: February 2011

The sections in this article are

Introduction

In Vitro
Multiplexed Analysis Using
QDs

DNA
Hydridization

Immunoassay

Assaying the Activity of Enzymes

FRET
‐Based Protease Detection with
QDs
as the Donor

BRET
‐Based Protease Detection with
QDs
as Acceptor

Other
In Vitro
Multiplexed Detection Systems

Multiplexed Imaging Using
QDs

Multiplexed Cellular Imaging

Multiplexed Imaging in Small Animals
Imaging and Tracking of Viruses Using Quantum Dots
Authors: Joo Kye‐Il , Tai April , Wang Pin
Published: February 2011

The sections in this article are

Introduction

Quantum Dot–Biomolecule Hybrids

Optical Properties ofQDs

FunctionalizedQDsConjugated with Biomolecules

Formation of Virus–QDNetworks

Decoration of Discretely Immobilized Virus withQDs

QDEncapsulation in Viral Capsids

Quantum Dots for Single Virus Tracking in Living Cells

Conventional Labeling for Single‐Virus Tracking in Live Cells

Problems Encountered in Single‐Virus Tracking

Use ofQDsfor Labeling Enveloped Viruses

Use ofQDsfor Labeling Nonenveloped Viruses

Quantum Dots for the Sensitive Detection of Virus and Infection

Monitoring the Progression of Viral Infection with FluorescentQDProbes

The Use of Two‐ColorQDsfor the Real‐Time Detection of Viral Particles and Viral Protein Expression

Viral Detection withpH‐SensitiveQDsin a Biological Motor

Conclusions

Acknowledgments