Organobismuth compounds. I. Studies on triphenylbismuth(V) derivatives, Ph3BiX2

1970 ◽  
Vol 48 (16) ◽  
pp. 2488-2493 ◽  
Author(s):  
R. G. Goel ◽  
H. S. Prasad

Triphenylbismuth(V) acid derivatives of the type, Ph3BiX2, where X = halide, nitrate, cyanate, acetate, haloacetate, or cyanoacetate have been prepared. Infrared spectra (4000 to 200 cm−1 region), electrical conductances, and molecular weights of these compounds have been studied to elucidate their structural features and chemical constitution. The molecular weight and conductance data show that these compounds behave as molecular species in benzene or nitromethane. The infrared spectroscopic results also indicate non-ionic five-coordinate structures. Bi—X stretching frequencies have been assigned for the difluoride, dichloride, dinitrate, dicyanate, and diacetate. These frequencies occur in the region 410–240 cm−1.

1969 ◽  
Vol 47 (24) ◽  
pp. 4607-4612 ◽  
Author(s):  
R. G. Goel

Tetraphenylantimony halides, pseudohalides, carboxylates, nitrate, sulfate, selenate, and chromate have been synthesized. The infrared spectra, molecular weights, and electrical conductances of these compounds have been investigated to elucidate the chemical constitution. The compounds have molecular, monomeric constitution in benzene solutions. Infrared results indicate that with the exception of the acetate and the oxalate, all the compounds have 5-coordinate structures. The acetate is 6-coordinate in the solid state and 5-coordinate in bromoform or chloroform solution. The oxalate is indicated to be 6-coordinate in the solid state as well as in chloroform solution. The electrical conductivities of the bromide, chloride, thiocyanate, trifluoroacetate, and the nitrate in nitromethane correspond to those of 1:1 electrolyte. The conductivities of the other compounds indicate little dissociation in this solvent.


1932 ◽  
Vol 5 (2) ◽  
pp. 136-140
Author(s):  
H. Staudinger ◽  
W. Feisst

Abstract The molecular concept in organic chemistry is based upon the fact that the molecules, whose existence is proved by vapor density determinations, enter into chemical reactions as the smallest particles. If now it is assumed that organic molecular colloids like rubber are dissolved in dilute solution in molecular form then it must be proved that in the chemical transposition of macromolecules as well no change in the size of the macromolecules occurs. In the case of hemicolloids, therefore for molecular colloids with an average molecular weight of 1000 to 10,000, this has been proved by the reduction of polyindenes, especially of polysterenes, to hydroproducts with the same average molecular weight, and also by the fact that cyclorubbers do not change their molecular weight upon autoöxidation. The molecular weights of hemi-colloidal hydrocarbons are therefore invariable. This is much more difficult to prove in the case of rubber, although there are many more ways in which unsaturated rubber can be transposed than the stable polysterenes, polyindenes, and poly cyclorubbers. In most of the reactions with rubber, as in its action with nitrosobenzene, oxidizing agents, hydrogen halides, and halogens, an extensive decomposition takes place as a result of the instability of the molecule, which is referred to in another work. Therefore derivatives of rubber are not formed, but derivatives of hemi-colloidal decomposition products. The catalytic reduction of rubber in the cold appears to be the most suitable process of making it react without changing its molecular size in order to prove that in a chemical transposition its molecular weight remains the same.


1939 ◽  
Vol 12 (4) ◽  
pp. 789-793 ◽  
Author(s):  
W. Harold Smith ◽  
Henry J. Wing

Abstract Some investigators believe that rubber consists of associated molecules, and others accept Staudinger's view that long-chain molecules are formed by polymerization. Pummerer, Andriessen and Gündel have obtained a molecular weight as low as 600. Meyer and Mark believe that it is approximately 5,000, although they calculated on the basis of osmotic pressures values as high as 350,000. They, as well as Pummerer, consider that rubber is an associated colloid and that high molecular weights are caused by aggregates, sometimes called micelles. Staudinger, however, considers that the long-chain rubber molecule itself has a molecular weight of 200,000 or even 350,000, and that products with lower values, which may be formed in rubber, result from degradation. if the molecules are small it might be possible to distil them if their vapor pressure could be sufficiently increased, but none would distil without decomposition if the molecules are very large. Because the vapor pressure of rubber below its decomposition temperature is low, it appeared of interest to attempt to distil the material in a molecular still. Paraffin wax and sugar, both substances of relatively high molecular weight, have been successfully distilled in this type of apparatus. Subsequent to the work described in this paper, the molecular weight of sol rubber prepared at this Bureau was determined by Kraemer and Lansing of E. I. du Pont de Nemours & Co., Inc. They used the Svedberg method of sedimentation equilibrium in an ultracentrifuge with ethereal solutions of sol rubber. The temperature of the solutions during determinations was approximately 10° C, and an average value of 460,000 was obtained. There was evidenced of a mixture of molecular species.


1972 ◽  
Vol 18 (10) ◽  
pp. 1614-1617
Author(s):  
J. B. Campbell ◽  
T. Grunberger

The molecular weights of the interferons appearing in the serum of mice injected intravenously with Mengo virus and with poly I:C are about 28 000 and 45 000 respectively. Since there is evidence that some forms of interferon are more potent than others, it is suggested that molecular-weight estimations might provide a convenient marker for more systematic studies of the efficacy of interferon preparations and inducing substances for clinical use.


1962 ◽  
Vol 40 (12) ◽  
pp. 2234-2242 ◽  
Author(s):  
Roland Rivest

The following coordination complexes of titanium (IV) have been prepared: TiCl4•2CO(NH2)2, TiCl4•CO(NHCH3)2, TiCl4•2CO(NHCH3)2, 2TiCl4•2NH2CON(C6H5)2, 2TiCl4•2CO(NHC6H5)2 TiCl4•2CS(NH2)2, 2TiCl4•CS(NHC2H5)2, 2TiCl4•NH2CSN(C6H5)2, and 2TiCl4•CS(NHC6H5)2; their infrared spectra have been measured and their molecular weight determined. For urea and its derivatives the coordination to titanium (IV) is always through the oxygen atom. The phenyl derivatives of urea led to dinuclear complexes which were best explained by assuming halogen bridging between the titanium atoms. Thiourea and its derivatives gave complexes in which coordination occurred through one of the nitrogens in the case of thiourea and through both nitrogens in the case of the derivatives. Halogen bridging was again assumed to explain the formation of the dinuclear complexes.


1965 ◽  
Vol 38 (1) ◽  
pp. 103-111 ◽  
Author(s):  
V. L. Hansley ◽  
H. Greenberg

Abstract Control of molecular weight of alfin catalyzed diene polymers has been demonstrated for polymers of butadiene, isoprene, styrene, piperylene and combinations of these. The 1,4-dihydro derivatives of benzene and naphthalene are effective molecular weight moderators. The known microstructure of alfin polymers remains unchanged with the use of these agents. Molecular weight controlled alfin gums process readily on standard rubber machinery. Oil extenders or softeners, although not necessary, are easily incorporated. The feasibility of continuous processing has been demonstrated for the production of catalyst, moderators and polymers on pilot plant scale. A wide series of polymers and copolymers at predetermined molecular weights and compositions have been produced in the same pilot plant. Alfin polybutadiene with limited amounts of styrene is essentially a solution type SBR. Alfin copolymers with styrene and/or isoprene have undergone preliminary road tests in tires. Wear and heat build-up data indicate performance to be intermediate between SBR and polybutadiene.


Author(s):  
George F. Leeper

Elementary fibrils, about 35 Å wide, have been demonstrated for cellulose by a variety of techniques. More recently, they have been demonstrated for xylan, chitin, and mannan. However, their existence has not been previously reported for any of the water soluble polysaccharides.Pectic acid molecules of about 200,000 molecular weight and enzymatically abbreviated derivatives with molecular weights of 60,000 and 9,000 were negatively stained at various pH values with 2% phosphotungstic acid to demonstrate elementary fibrils. The width and degree of fasciation of these elementary fibrils varies with pH. Pectic acid elementary fibrils exhibit a 64 Å dimensional stability above a certain pH value which varies inversely with molecular weight. Below this pH, elementary fibrils exhibit a marked increase in width. At still lower pH values, the elementary fibrils are no longer demonstrable, presumably because of their dissociation to a molecular species.


2013 ◽  
Vol 109 (03) ◽  
pp. 471-478 ◽  
Author(s):  
Marcelo Lima ◽  
Christian Viskov ◽  
Frederic Herman ◽  
Angel Gray ◽  
Eduardo de Farias ◽  
...  

SummaryUltra-low-molecular-weight heparins (ULMWHs) with better efficacy and safety ratios are under development; however, there are few structural data available. The main structural features and molecular weight of ULMWHs were studied and compared to enoxaparin. Their monosaccharide composition and average molecular weights were determined and preparations studied by nuclear magnetic resonance spectroscopy, scanning ultraviolet spectroscopy, circular dichroism and gel permeation chromatography. In general, ULMWHs presented higher 3-O-sulphated glucosamine and unsaturated uronic acid residues, the latter being comparable with their higher degree of depolymerisation. The analysis showed that ULMWHs are structurally related to LMWHs; however, their monosaccharide/oligosaccharide compositions and average molecular weights differed considerably explaining their different anticoagulant activities. The results relate structural features to activity, assisting the development of new and improved therapeutic agents, based on depolymerised heparin, for the prophylaxis and treatment of thrombotic disorders.


1987 ◽  
Vol 113 ◽  
Author(s):  
R. I. A. Malek ◽  
D. M. Roy

SUMMARYThe development of an improved method of trimethylsilylation [1] made possible the assessment of different polysilicate fractions in hydrated cement pastes, as a means of structural characterization. Several laboratories have presented various gas-liquid chromatographic data on the polysilicate derivatives of C-S-H [2–5]. Identification of the different molecular weight fractions has been made, in most laboratories, by matching the gasliquid chromatographic peaks with the gel permeation chromatographic peaks. The success of this matching process is always dependent on type of instruments, length of columns and temperature range.In the present investigation, a mass spectrometer, in direct contact with the gas-liquid chromatograph, was used to identify the molecular weight of each of the fractions separated from the chromatograph. The technique was applied to determine the molecular weights and abundances of different polysilicate species in hydrated fly ash pastes.


1969 ◽  
Vol 47 (14) ◽  
pp. 2661-2663 ◽  
Author(s):  
R. C. Mehrotra ◽  
S. R. Bindal

Derivatives of gallium of the type: Ga(i-C3H7O)3−xligx (x = 1, 2, or 3; and H lig = acetylacetone, methyl and ethyl acetoacetate, or methyl salicylate) have been synthesized by reacting gallium alkoxides with ligands in various molar ratios. The compounds are soluble in organic solvents and could be volatilized under reduced pressure. Their molecular weights have been determined ebullioscopically. The infrared spectra of some of the compounds have been studied.


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