scholarly journals Molecular Growth Pathways in Silica Sol-Gel Polymerization

1988 ◽  
Vol 121 ◽  
Author(s):  
W. G. Klemperer ◽  
S. D. Ramamurthi
Keyword(s):  
Sol Gel ◽  
Molecular Size ◽  
Weight Fraction ◽  
Degree Of Polymerization ◽  
Partial Hydrolysis ◽  
Linear Polymers ◽  
Mole Percent ◽  
Molecular Weights ◽  
Low Degree ◽  
Acidic Conditions

ABSTRACTCapillary gas chromatography has been used to monitor the stoichi-ometries, structures, and abundances of low molecular weight polysilicate esters formed by partial hydrolysis of methanolic tetramethylorthosili-cate and redistribution of methanolie hexamethyoxydisiloxane under acidic (HC1) and basic (KOH) conditions. The polysilicate molecular size distributions, expressed in terms of mole percent of total silicon present as a function of degree of polymerization, show maxima near the number average degree of polymerization under acidic conditions. Under basic conditions, the distribution has its maximum at the monomer percent and extends to very high molecular weights, yielding a distribution far broader than the one observed under acidic conditions. These features are in agreement with covalent network theories of silica gelation, as opposed to particle aggregation theories. Weight fraction distributions of the type observed under acidic conditions are characteristic of linear polymers with a low degree of crosslinking and weight fraction distributions of the type observed under basic conditions are characteristic of branched polymers with high degree of crosslinking. The low degree of crosslinking obtained under acidic conditions is observed to arise from steric crowding that discourages branching in polysilicate structures.

Structure of Polybutadienes

1967 ◽  
Vol 40 (5) ◽  
pp. 1529-1543 ◽  
Author(s):  
W. S. Bahary ◽  
D. I. Sapper
Keyword(s):  
Light Scattering ◽  
Molecular Size ◽  
Structural Features ◽  
Melting Point Depression ◽  
Linear Polymers ◽  
Long Chain Branching ◽  
Molecular Weights ◽  
Catalyst Systems ◽  
Molecular Size Distribution

Abstract Polybutadienes made with six different catalyst systems were examined: (1) butyllithium, (2) “nickel-based”, (3) alfin, (4) “titanium-based”, (5) “cobalt-based”, and (6) free radical emulsion. The microstructure and macrostructure of the polybutadienes have been determined and are compared to the results published in the literature. These polybutadienes may be considered to be random terpolymers of cis, trans, and vinyl addition of butadiene. The glass transition temperature is specified by the vinyl content. The crystalline melting points of the high trans and also the high cis polybutadienes obey to a high measure Flory's equation for melting point depression of a random terpolymer. The molecular weights of the polybutadienes have been determined by light scattering and osmometry and the degree of long chain branching has been determined by the branching index, 〈g′〉. The macro-structural features of the linear polymers are confirmed by fractionation. However, the polydispersities calculated from fractionation data do not agree with those determined from light scattering and osmometry for the branched samples. The discrepancy is attributed to the method of characterization of the fractions. A distinction is made between molecular weight distribution and molecular size distribution.

scholarly journals Effect of molecular size of 125I-labelled poly(vinylpyrrolidone) on its pinocytosis by rat visceral yolk sacs and rat peritoneal macrophages

1981 ◽  
Vol 196 (1) ◽  
pp. 49-55 ◽  
Author(s):  
R Duncan ◽  
M K Pratten ◽  
H C Cable ◽  
H Ringsdorf ◽  
J B Lloyd
Keyword(s):  
Molecular Weight ◽  
Molecular Size ◽  
Weight Fraction ◽  
Cell Types ◽  
Peritoneal Macrophages ◽  
Yolk Sac ◽  
High Molecular Weight Fraction ◽  
Molecular Weights ◽  
Molecular Weight Distributions

Rates of pinocytosis of different molecular-weight distributions of 125I-labelled poly(vinylpyrrolidone) by rat visceral yolk sacs and rat peritoneal macrophages were measured in vitro. Four preparations of mean molecular weights 50 000, 84 000, 700 000 and 7 000 000, were used. Macrophages captured the highest-molecular-weight preparation more rapidly than the other preparations. In contrast, rate of capture by the yolk sac decreased with increasing molecular weight. Incubations with a very-high-molecular-weight fraction derived from the 7 000 000-average-mol. wt. preparation clearly demonstrated that very large polymer molecules are not accumulated by the yolk sac, but are preferentially captured by macrophages. Analysis of the 125I-labelled poly(vinylpyrrolidone) internalized by the two cell types confirmed that low-molecular-weight material is preferred by the yolk sac, whereas the macrophage is less discriminating.

Molecular Weight Defined in Sol-Gel Analysis and Its Application to Evaluate Branching

1995 ◽  
Vol 68 (2) ◽  
pp. 287-296 ◽  
Author(s):  
Asahiro Ahagon
Keyword(s):  
Molecular Weight ◽  
Crosslink Density ◽  
Sol Gel ◽  
Average Molecular Weight ◽  
Degree Of Polymerization ◽  
Gel Point ◽  
Linear Polymers ◽  
Molecular Parameter ◽  
Branch Points ◽  
Number Average Molecular Weight

Abstract It is considered that many “linear” polymers are actually branched; however, it is difficult to show this with ordinary methods for an arbitrarily chosen polymer. Branching can be regarded as premature crosslinking below the gel point. Attention is then paid to the well-established Charlesby-Pinner Equation used for sol-gel analysis in crosslinking studies. It contains the number average degree of polymerization before crosslinking as a parameter. The molecular parameter is considered here to be that of the virtual linear polymer which would be obtained by unlinking any branch points contained in the polymer. Evidence is shown to support this. It is then possible to estimate the total number of linear components on an average molecule of a branched polymer by taking the ratio of the number average molecular weight measured by two methods, i.e., sol-gel analysis and an ordinary method like GPC. Further information about the branching structure can be obtained by additional measurements of effective crosslink density for a series of polymers obtained from similar polymerization processes.

Thermomechanical Characterization of the Molecular Weight of Linear Polymers Exemplified by Natural Rubber

1964 ◽  
Vol 37 (1) ◽  
pp. 99-102
Author(s):  
B. Ya Teitelbaum ◽  
K. F. Gubanov
Keyword(s):  
Molecular Weight ◽  
Experimental Studies ◽  
Thermomechanical Properties ◽  
Linear Polymers ◽  
Molecular Weights ◽  
Calculated Molecular Weight ◽  
Low Degree ◽  
Wide Range ◽  
High Elasticity

Abstract In the previous work of Kargin and Slonimskii and that of Kargin and Sogolov who studied the behavior of polymers over a wide range of temperature, it was shown that the shape of thermomechanical curves depends on magnitude of molecular weight of the polymers. As a result of investigation of theory and actual experimental studies in which polyisobutylene was employed, it was demonstrated that molecular weight could be estimated on the basis of thermomechanical properties. This suggested a relationship between the magnitude of molecular weight M found from the thermomechanical curves and that which was determined from glass temperatures Tg and fluid temperatures Tf. For practical use of this relationship, it is necessary to know the magnitude of the segments and two empirical constants. These values can be found by calculation of molecular weights of three different fractions of the polymer. This can be accomplished experimentally by any independent method. Once these magnitudes are determined, it is necessary to find, by means of the thermomechanical curve, the values Tg and Tf, in order to calculate the molecular weight of any sample of the same polymer. Because of the low degree of accuracy of determination of these values, and because of the peculiar differences, the reliability of the calculated molecular weight cannot be great, especially since the equation utilizes the logarithm of the molecular weight figure and not the molecular weight itself. Apparently the graphic solution is simpler than analytical methods: by means of the data of thermomechanical studies for various fractions of known molecular weights it is possible to graph the dependence of M or log Mon Tf−Tg. From what has been said, it is evident that we may use the demonstrated method only for polymers of high elasticity, and furthermore, only for those fractions in which Tf−Tg is greater than zero.

Novel Inorganic Hydrogels Based on The Polymerization of Cyanometalate Transition Metal Complexes With [PdCl4]2-: A New Approach To Ceramic And Alloy Precursors

1994 ◽  
Vol 346 ◽  
Author(s):  
Andrew B. Bocarsly ◽  
Gireesh Kumar ◽  
Marija Heibel
Keyword(s):  
Transition Metal ◽  
Metal Ion ◽  
Sol Gel ◽  
Metallic Matrix ◽  
Linear Polymers ◽  
New Approach ◽  
Square Planar ◽  
Delafossite Structure ◽  
Cyanide Ligand ◽  
Sol Gel Transition

ABSTRACTThe reaction of a wide variety of cyanometalate complexes of the general form [M(CN)x]n- (where M= a transition metal ion) with square planar [PdCl4]2- in aqueous solution leads to the formation of linear polymers. Polymerization occurs via substitution of chloride ligands on the Pd(II) centers, by the nitrogen end of the cyanide ligand to generate extended bridging cyanide structures. Upon generation at room temperature polymer solutions of this type under go a sol-gel transition to generate robust hydrogels having water content in excess of 95%. In the case of the cyanocobaltate/tetrachloropalladate gel, pyrolysis at 900°C produces ferromagnetic Pd/Co metallic alloys having novel morphological character. Materials formed with a hydrogel having a 2:1 Pd to Co stoichiometry are found to be “sponge-like”. When placed in water, the metallic matrix swells becoming pliable and holding up to seven equivalents of water per metal site. The conductivity and magnetic properties of this material are maintained in the swollen state. Sintering of the Pd/Co hydrogel in air generates the layered oxide, PbCoO2 having a delafossite structure.

Effect of extractant and molecular size on the optical and chemical properties of soil humic acids

Soil Research ◽  
1969 ◽  
Vol 7 (3) ◽  
pp. 229 ◽  
Author(s):  
JHA Butler ◽  
JN Ladd
Keyword(s):  
Molecular Weight ◽  
Amino Acid ◽  
Humic Acids ◽  
Gel Filtration ◽  
Chemical Properties ◽  
Molecular Size ◽  
Carboxyl Content ◽  
Peptide Bonds ◽  
Molecular Weights ◽  
Amino Acid Contents

Humic acids extracted from soil with sodium pyrophosphate have greater proportions of lower molecular weight material, less acid-hydrolysable amino acid nitrogen contents, but greater carboxyl contents and extinction values (260 and 450 nm) than humic acids extracted subsequently from the same sample with alkali. Humic acids extracted with alkali from fresh soil samples have intermediate values. Extinction values at 260 nm are directly correlated with carboxyl contents for a given soil. Different crop histories have no significant effect on the measured properties of the extracted humic acids. An alkali-extracted humic acid has been fractionated by gel filtration into seven fractions of different nominal molecular weight ranges. As the molecular weights of the fractions increase, both aliphatic C-H (based on infrared absorption at 2900 cm-1) and acid-hydrolysable amino acid contents increase, whereas extinction values at 260 nm and carboxyl contents decrease. The infrared spectra of the high molecular weight fractions have peaks at 1650 and 1510 cm-1 which correlate with acid-hydrolysable amino acid contents and which correspond to amide I and II bands of peptide bonds. Alkaline hydrolysis to split peptide bonds eliminates both these peaks. The spectra also have peaks at 1720 and 1210 cm-1 which correlate with the carboxyl content.

Sorption of GR-S Type of Polymer on Carbon Black. III. Sorption by Commercial Blacks

1953 ◽  
Vol 26 (1) ◽  
pp. 102-114 ◽  
Author(s):  
I. M. Kolthoff ◽  
R. G. Gutmacher
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Intrinsic Viscosity ◽  
Benzene Solution ◽  
Weight Fraction ◽  
High Molecular Weight Fraction ◽  
Molecular Weights ◽  
Bound Rubber ◽  
Flow Through ◽  
Peculiar Behavior

Abstract The sorption capacities toward GR-S five commercial carbon blacks are in decreasing order: Spheron-6, Vulcan-1, Philblack-0, Sterling-105, Philblack-A. Apparently, the sorption is not related to surface area. The sorption on Vulcan-1 of GR-S from its solutions in seven different solvents or mixtures of solvents increases with decreasing solvent power for the rubber. The sorption curves of two “cold rubbers,” polymerized at −10 and +5° respectively, showed little difference from that of 50° GR-S. Previous heating of carbon black in nitrogen at 500 or 1100° increased the sorption by about 20 per cent over unheated carbon. Air-heating of carbon black at 425° did not cause a difference in the sorption from benzene solution, but produced an increase in the sorption of rubber from n-heptane solution. In the range 75% butadiene-25% styrene to 5% butadiene-95% styrene, there is practically no effect of the degree of unsaturation on the sorption. Polystyrene of high intrinsic viscosity exhibits a peculiar behavior with furnace blacks. Vulcan-1 sorbed microgel as well as the sol fraction from n-heptane solutions of GR-S containing microgel (conversion 74.7 and 81.5 per cent). There was no appreciable difference in the amount of sorption of rubber fractions having average molecular weights varying from 433,000 to 85,000. There is little change in the amount sorbed after two hours of shaking, but the intrinsic viscosity of the residual rubber decreases with time. The low molecular-weight rubber is sorbed more rapidly, but is slowly replaced by the more tightly sorbed high molecular weight fraction. Partial fractionation of a rubber sample can be achieved by allowing the rubber solution to flow through a column of weakly sorbing carbon black. A large portion of the sorbed rubber can be recovered from the column by washing it with a good solvent such as xylene. Bound rubber is produced by intimate mixing of equal parts of carbon black and rubber swollen in chloroform, when the mixture is dried in vacuum at 80° or at room temperature. Milling is not essential to get bound rubber.

scholarly journals Characterization of proteins from the cytoskeleton of Giardia lamblia

1983 ◽  
Vol 59 (1) ◽  
pp. 81-103 ◽  
Author(s):  
R. Crossley ◽  
D.V. Holberton
Keyword(s):  
Molecular Weight ◽  
Sodium Dodecyl Sulphate ◽  
Giardia Lamblia ◽  
Polyacrylamide Gel Electrophoresis ◽  
Sodium Dodecyl ◽  
Gel Filtration ◽  
Molecular Size ◽  
Molecular Weights

Proteins from the axonemes and disc cytoskeleton of Giardia lamblia have been examined by sodium dodecyl sulphate/polyacrylamide gel electrophoresis. In addition to tubulin and the 30 X 10(3) molecular weight disc protein, at least 18 minor components copurify with the two major proteins in Triton-insoluble structures. The most prominent minor bands have the apparent molecular weights of 110 X 10(3), 95 X 10(3) and 81 X 10(3). Protein of 30 X 10(3) molecular weight accounts for about 20% of organelle protein on gels. In continuous 25 mM-Tris-glycine buffer it migrates mostly as a close-spaced doublet of polypeptides, which are here given the name giardins. Giardia tubulin and giardin have been purified by gel filtration chromatography in the presence of sodium dodecyl sulphate. Well-separated fractions were obtained that could be further characterized. Both proteins are heterogeneous when examined by isoelectric focusing. Five tubulin chains were detected by PAGE Blue 83 dye-binding after focusing in a broad-range ampholyte gel. Giardin is slightly less acidic than tubulin. On gels it splits into four major and four minor chains with isoelectric points in the pI range from 5.8 to 6.2. The amino acid composition of the giardin fraction has been determined, and compared to Giardia tubulin and a rat brain tubulin standard. Giardins are rich in helix-forming residues, particularly leucine. They have a low content of proline and glycine; therefore they may have extensive alpha-helical regions and be rod-shaped. As integral proteins of disc microribbons, giardins in vivo associate closely with tubulin. The properties of giardins indicate that in a number of respects - molecular size, charge, stoichiometry - their structural interaction with tubulin assemblies will be different from other tubulin-accessory protein copolymers studied in vitro.

scholarly journals Average molecular weight of surfactants in aerosols

2007 ◽  
Vol 7 (5) ◽  
pp. 13805-13838 ◽  
Author(s):  
M. T. Latif ◽  
P. Brimblecombe
Keyword(s):  
Molecular Weight ◽  
Surface Tension ◽  
Atmospheric Aerosols ◽  
Average Molecular Weight ◽  
Molecular Size ◽  
Weight Fraction ◽  
Ozone Exposure ◽  
Before And After ◽  
Fine Mode ◽  
Active Substances

Abstract. Surfactants in atmospheric aerosols determined as methylene blue active substances (MBAS) and ethyl violet active substances (EVAS). The MBAS and EVAS concentrations can be correlated with surface tension as determined by pendant drop analysis. The effect of surface tension was more clearly indicated in fine mode aerosol extracts. The concentration of MBAS and EVAS was determined before and after ultrafiltration analysis using AMICON centrifuge tubes that define a 5000 Da (5 K Da) nominal molecular weight fraction. Overall, MBAS and to a greater extent EVAS predominates in fraction with molecular weight below 5 K Da. In case of aerosols collected in Malaysia the higher molecular fractions tended to be a more predominant. The MBAS and EVAS are correlated with yellow to brown colours in aerosol extracts. Further experiments showed possible sources of surfactants (e.g. petrol soot, diesel soot) in atmospheric aerosols to yield material having molecular size below 5 K Da except for humic acid. The concentration of surfactants from these sources increased after ozone exposure and for humic acids it also general included smaller molecular weight surfactants.

Effect of acidity on the properties of silica-aluminas synthesized by sol-gel method

2020 ◽  
Vol 63 (7) ◽  
pp. 126-132
Author(s):  
Lyubov V. Furda ◽  
◽  
Evgenia A. Tarasenko ◽  
Sofya N. Dudina ◽  
Olga E. Lebedeva ◽  
...  
Keyword(s):  
Surface Area ◽  
Sol Gel ◽  
Molar Ratio ◽  
Active Centers ◽  
Indicator Method ◽  
Synthesis Conditions ◽  
Alkaline Conditions ◽  
Acidic Conditions ◽  
Amphoteric Properties ◽  
Hydrolysis Of

In the present work amorphous silica-aluminas were synthesized by the coprecipitation method during the hydrolysis of an alcohol solution of tetraethoxysilane (with a tetraethoxysilane: alcohol mass ratio of 1: 1) and 6% aqueous solution of aluminum nitrate at pH values of 1, 3, and 10. The Si/Al molar ratio for all synthesized samples were 4.72 (± 0.29). The amorphous character of the investigated materials was confirmed by X-ray phase analysis. According to the results of scanning electron microscopy, it was found that the resulting powders have particles with a size of 1-20 μm. It was shown that the conditions of synthesis affected the specific surface area and porosity of the materials under study. By the method of low-temperature adsorption-thermodesorption of nitrogen it was established that silica-aluminas obtained under acidic conditions were microporous materials. For the sample obtained under alkaline conditions (pH = 10), the contribution of macropores is very significant. A decrease in surface area is observed as the pH of the synthesis increases. The Hammett indicator method was used to identify and quantify surface centers of different acidity. All studied silica-aluminas are characterized by the presence of both Brønsted basic (pKax from 7 to 12.8) and acidic (pKax from 0 to 7) centers, and Lewis basic (pKax from -4.4 to 0) with a pronounced maximum at pKax = 1.02. It was found that the synthesis conditions had a significant effect on the concentration of active centers. The values of the Hammett function are practically the same for the 3 studied silica-aluminas and describe the studied samples as materials of medium acidity. The variety of Lewis and Brønsted centers on the surface indicates the amphoteric properties of the materials under study. This gives the samples the properties of polyfunctional sorbents and catalysts.

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