Home About us Contact
|
Home About us Contact | ||
|
|
||
Good Solvent (good + solvent)
Selected AbstractsPreparing titania aerogel monolithic chromatography columns using supercritical carbon dioxideJOURNAL OF SEPARATION SCIENCE, JSS, Issue 11 2010Ruohong Sui Abstract The search for a method to fabricate monolithic inorganic columns has attracted significant recent attention due to their unique ability in separation applications of various biomolecules. Silica and polymer based monolithic columns have been prepared, but titania and other metal oxide monoliths have been elusive, primarily due to their fragility. This article describes a new approach for preparing nanostructured titania based columns, which offer better performance over conventional particle packed columns for separating a wide variety of biomolecules including phosphopeptides. TiO2 monolithic aerogels were synthesized in separation columns using in situ sol-gel reactions in supercritical carbon dioxide (scCO2) followed by calcination, and compared to those prepared in heptanes. The characterization results show that scCO2 is a better solvent for the sol-gel reactions, providing lower shrinkage with the anatase TiO2 monolith composed of nanofibers with very high surface areas. The monolithic columns show the ability to isolate phosphopeptides with little flow resistance compared to conventional titania particle based microcolumns. [source] Effect of solvent concentration on the extraction kinetics and diffusivity of Cyclosporin A in the fungus Tolypocladium inflatumBIOTECHNOLOGY & BIOENGINEERING, Issue 1 2007May Ly Abstract The kinetics of solid-liquid extraction and extraction yields of the immunosuppressant drug Cyclosporin A (CyA) from the mycelia of Tolypocladium inflatum were examined in this study. A 2 L stirred, baffled vessel was used to extract CyA from wet mycelia mass. Three different organic solvents were used, namely, methanol, acetone, and isopropanol at different concentrations in aqueous mixtures at room temperature. It was found that the best solvent was acetone at 50% v/v concentration achieving 100% extraction of CyA from the mycelia of T. inflatum. Although acetone proved to be the better solvent for CyA extraction, further studies were performed using methanol. A linear relationship was found between extraction yield of CyA and methanol concentration with 100% CyA extraction at 90% v/v methanol. The partition coefficients of CyA between the solid mycelia phase and the aqueous solvent phase were found to decrease exponentially with increasing methanol concentration. A liquid extraction model was developed based on the diffusion equation to correlate the kinetic data of CyA extraction from the solid mycelia of T. inflatum. Non-linear regression analysis of experimental data was used with the diffusion equation in order to calculate the effective diffusivities of CyA in the mycelia of T. inflatum. For all three organic solvents used, the effective diffusivities of CyA were found to be between 4.41,×,10,15 and 6.18,×,10,14 m2/s. This is the first time CyA effective diffusivities in T. inflatum are reported in the literature. Biotechnol. Bioeng. 2007;96: 67,79. © 2006 Wiley Periodicals, Inc. [source] Unique Phase-Separation Structures of Block-Copolymer Nanoparticles,ADVANCED MATERIALS, Issue 17 2005H. Yabu Block-copolymer nanoparticles with lamellar phase-separation structures (see Figure) have been prepared by a slow-precipitation process. Regular-sized polymer nanoparticles are formed after evaporation of a good solvent from a polymer solution containing a non-volatile poor solvent and a volatile good solvent. [source] Physicochemical characterization of carrageenans,A critical reinvestigationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Gisela Berth Abstract Kappa-, iota-, and lambda-carrageenan (food grade) were analyzed by static light scattering (MALS in batch mode) in 0.1M NaNO3 at 25 and 60°C, earlier heated up to 90°C or not. At 25°C, there was a strong tendency for a concentration-dependent aggregation in the order lambda < kappa < iota. At 60°C, all samples were molecularly dispersed. The strongly temperature-dependent refractive index increments (equilibrium dialysis) differ. Data interpretation in terms of the wormlike chain model using the Skolnik-Odijk-Fixman approach led to an intrinsic persistence length around 3 to 4 nm and expansion factors as high as 1.5 and above in a thermodynamically good solvent for all three types. Triple-detector HPSEC (DRI, MALS, viscometry) on the three commercial samples plus a degraded (by acidic hydrolysis) kappa-carrageenan in the same solvent/eluant at 60°C yielded a uniform and slightly curved [,]- M relationship for 5 × 103 , M/(g mol) , 3 × 106 and a nearly identical molar mass dependence of the radius of gyration. HPSEC at 25°C on kappa-carrageenan confirmed formation of soluble aggregates. Special emphasis was put on analytical and methodological aspects. The reliability of the experimental data was demonstrated by analogous measurements on dextran calibration standards. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Solid-supported amphiphilic triblock copolymer membranes grafted from gold surfaceJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2009Ekaterina Rakhmatullina Abstract Gold-supported amphiphilic triblock copolymer brushes composed of two hydrophilic poly(2-hydroxyethyl methacrylate) (PHEMA) blocks and a hydrophobic poly(n -butyl methacrylate) (PBMA) middle part were synthesized using a surface-initiated ATRP. Attenuated total reflectance Fourier transform infrared spectroscopy, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), ellipsometry, contact angle measurements, and atomic force microscopy were used for the characterization of PHEMA- co -PBMA- co -PHEMA brushes. The PM-IRRAS analysis revealed an increase of the chain tilt toward the gold surface during growth of the individual blocks. We suggest that the orientation of the amphiphilic polymer brushes is influenced by both the chain length and the interchain interactions. Additionally, a detachment of the polymer membranes from the solid support and subsequent gel permeation chromatography analyses allowed us to establish their compositions. We applied block-selective solvents (water and hexane) as well as a good solvent for the whole polymer chain (ethanol) to study the morphology and solvent responsive behavior of the amphiphilic brushes. The presented results could serve as a good starting point for the fabrication of functional solid-supported membranes for biosensing applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1,13, 2009 [source] Thermosensitive noncovalently bonded block copolymerlike micelles from interpolymer complexesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2004Dimitra Topouza Abstract Interpolymer complexes between polystyrene- b -poly(2-vinylpyridine), (PS-P2VP), and poly(methacrylic acid) (PMAA), have been studied in dioxane. Dioxane is a good solvent for PS-P2VP copolymers but it is a nonsolvent for PMAA at room temperature. In this way noncovalent bonded micelles are formed after mixing the solutions of the polymers at 60 °C and then allowing them to cool at room temperature. Static and dynamic light scattering as well as viscosity measurements have been used to study the dependence of aggregate mass and size as a function of the molar ratio of functional groups in PS-P2VP/PMAA mixtures, as well as temperature. Plots of apparent average molecular weight and hydrodynamic radius of the aggregates versus amine to carboxyl group ratio show a maximum at a ratio close to one. The size of the aggregates decreases at higher ratios because of the formation of more stable micelles with smaller cores. In all cases rather compact structures were formed, as evidenced by viscometry. The mass of the aggregates was found to decrease by an increase in temperature while hydrodynamic radii were increased. This was attributed to the increase of the thermodynamic quality of the solvent toward PMAA as temperature increases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6230,6237, 2004 [source] Effect of solvent quality on kinetics of tethered layer formationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2004Heqing Huang Abstract We conducted a study of the effect of solvent quality on the kinetics of formation of a layer of polymer chains tethered to a solid substrate. In these experiments, tethering was accomplished by means of chemical bond formation between reactive sites on the surface and the end-functional groups of the polymer chains in solution. All experimental variables were held constant except for the ,-parameter between the polymer and solvent. Variation in the ,-parameter was achieved by use of a series of nonpolar, organic solvents. The distinct three-regime kinetics, typical of tethering reactions run in a good solvent and in the absence of segmental adsorption, was observed over the range of values for the ,-parameter. As expected, an increase in the ,-parameter (a decrease in solvent quality) did result in increased tethering density, but, contrary to expectation, no increase in tethering rate was observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5530,5537, 2004 [source] Liquid Chromatography of Synthetic Polymers under Limiting Conditions of Insolubility IIIMACROMOLECULAR SYMPOSIA, Issue 1 2007Application of Monolithic Columns Abstract Summary Performance was evaluated of silica based commercial monolithic rod-like columns in liquid chromatography of synthetic polymers under limiting conditions of enthalpic interactions (LC LC). LC LC employs the barrier effect of the pore permeating and therefore slowly eluting small molecules toward the pore excluded, fast eluting macromolecules. Phase separation (precipitation) barrier action was applied in present study. The barrier was created either by the narrow pulse of an appropriate nonsolvent injected into the column just before the sample solution (LC LC of insolubility , LC LCI) or by the eluent itself. In the latter case, the polymer sample was dissolved and injected in a good solvent (LC LC of solubility , LC LCS). In LC LCI, polymer species cannot break thru the nonsolvent zone while in LC LCS they cannot enter eluent, which is their precipitant. Therefore, polymer species keep moving in the zone of their original solvent. Macromolecules eluting under the LC LC mechanism leave the column in the retention volume (VR) roughly corresponding to VR of the low molar mass substances and can be efficiently separated from the polymer species non-hindered by the barrier action. The known advantages of monoliths were confirmed. From the point of view of LC LCI and LC LCS the most important quality of monolithic columns represents their excellent permeability, which allows both working at high flow rates and injecting very high (in the range of 5%) sample concentrations. Monolithic column tolerate also extremely high molar mass samples (M>10,000 kg,·,mol,1). On the other hand, the mesopores (separation pores) of the tested monoliths exhibited rather small volume and wide size distribution. These shortcomings partially impair the permeability advantage of monoliths because in order to obtain high LC LC separation selectivity a tandem of several monolithic columns must be applied. Presence of large mesopores also reduces applicability of monolithic columns for molar masses below about 50 kg,·,mol,1 because VRs of polymers eluted behind the barrier are similar to that of freely eluting species. The non- negligible break-thru phenomenon was observed for the very high polymer molar masses largely eluting behind the barrier. It is assumed that the fraction of very large mesopores present in the monoliths or association/microphase separation of macromolecules may be responsible for this phenomenon. This is why the presently marketed SiO2 monolithic columns are mainly suitable for the fast purification of the LC LC eluting macromolecules from the polymeric admixtures non-hindered by the barrier-forming liquid. Still, monolithic columns have large potential in the LC LCI and LC LCS procedures provided size (effective diameter) of the mesopores can be reduced and their volume increased. [source] End-Anchored Polymers: Compression by Different Mechanisms and Interpenetration of Apposing LayersMACROMOLECULAR THEORY AND SIMULATIONS, Issue 2 2005Mark D. Whitmore Abstract Summary: This paper presents a systematic study of the compression of end-anchored polymer layers by a variety of mechanisms. We treat layers in both good and , solvents, and in the range of polymer densities that is normally encountered in experiments. Our primary technique is numerical self-consistent field (NSCF) theory. We compare the NSCF results for the different mechanisms with each other, and with those of the analytic SCF theory. For each mechanism, we calculate the density profiles, layer thicknesses, and free energies, all as functions of the degree of polymerization and surface coverage. The free energy and the deformation of each layer depend on the compression mechanism, and they can be very different from the ASCF theory. For example, the energy of compression can be as much as three times greater than the analytical SCF (ASCF) prediction, and it does not reduce to simple, universal functions of the reduced distance between the surfaces. The overall physical picture simplifies if the free energy is expressed in terms of the layer deformation, rather than the reduced surface separation. We also examine and quantify the interpenetration of layers, discuss why ASCF theory applies better to some compression mechanisms than others, and end with comments on the difficulties in extracting quantitative information from surface-forces experiments. Comparisons of forces of compression in a good solvent for the three different systems, as functions of D/nb. The lower three curves are for ,*,=,3, and the upper three are for ,*,=,23. [source] Termination in Dilute-Solution Free-Radical Polymerization: A Composite ModelMACROMOLECULAR THEORY AND SIMULATIONS, Issue 5 2003Gregory B. Smith Abstract Literature data are summarized for the chain-length-dependence of the termination rate coefficient in dilute solution free-radical polymerizations. In essence such experiments have yielded two parameter values: the rate coefficient for termination between monomeric free radicals, k, and a power-law exponent e quantifying how kt values decrease with increasing chain length. All indications are that the value e,,,0.16 in good solvent is accurate, however the values of k which have been deduced are considerably lower than well-established values for small molecule radicals. This seeming impasse is resolved by putting forward a ,composite' model of termination: it is proposed that the value e,,,0.16 holds only for long chains, with e being higher for small chains , the value 0.5 is used in this paper, although it is not held to dogmatically. It is then investigated whether this model is consistent with experimental data. This is a non-trivial task, because although the experiments themselves and the ways in which they are analyzed are elegant and not too complicated, the underlying theory is sophisticated, as is outlined. Simulations of steady-state polymerization experiments are first of all carried out, and it is shown that the composite model of termination both recovers the e values which have been found and beautifully explains why these experiments considerably underestimate the true value of k. Simulations of pulsed-laser polymerizations find the same, although not quite so strikingly. It is therefore concluded that our new termination model, which retains the virtue of simplicity and in which all parameter values are physically reasonable, is consistent with experimental data. Taking a wider view, it seems likely that the situation of the exponent e varying with chain length will not just be the case in dilute solution, but will be the norm for all conditions, which would give our model and our work a general relevance. Normalized chain length distributions from PLP simulations. [source] Synthesis, static, and dynamic light scattering studies of soluble aromatic polyamidePOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 9 2008Sonia Zulfiqar Abstract Aromatic polyamide was synthesized via condensation polymerization of 4-aminophenyl sulfone (APS) with isophthaloyl chloride (IPC) using N,N -dimethyl acetamide (DMAc) as a solvent under anhydrous conditions. The purified aramid was studied by laser light scattering (LLS) in dimethyl sulfoxide (DMSO), a thermodynamically good solvent at 20°C. Static and dynamic light scattering studies permitted to determine the weight average molecular weight , radius of gyration , second virial coefficient A2, the hydrodynamic radius RH, and the diffusion coefficient D. Light scattering experiments were conducted at five concentrations ranging from 0.27 to 2.5,g/L. LLS measurement is also a very useful technique to study the aggregation or association in a polymer system as long as the large "clusters" are reasonably stable in time. The intensity autocorrelation function obtained on the quasi-elastically scattered light showed a simple diffusive relaxation mode. The ratio of radius of gyration to the hydrodynamic radius, i.e. ,,,1.3 indicates that the polyamide chain has coil conformation in DMSO at 20°C. Copyright © 2008 John Wiley & Sons, Ltd. [source] Grafting of hyperbranched poly(amidoamine) onto carbon black surfaces using dendrimer synthesis methodologyPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10 2001Norio Tsubokawa Abstract To modify carbon black surface, the surface grafting of hyperbranched poly(amidoamine) onto the surface by using dendrimer synthesis methodology was investigated. Carbon black having amino groups (initiator sites) was prepared by the reduction of surface nitro groups introduced by nitration of aromatic rings. It was found that hyperbranched poly(amidoamine) was propagated from carbon black surface by repeating two processes: (1) Michael addition of methyl acrylate (MA) to surface amino groups and (2) amidation of the resulting esters with ethylenediamine: the percentage of poly(amidoamine) grafting reached to 96.2% after 10th-generation. The grafting of hyperbranched poly(amidoamine) onto polystyrene-bead as a model compound of carbon black was also achieved by the above procedures. However, the theoretical propagation of poly(amidoamine) dendrimer was not achieved, because of steric hindrance of grafted polymer. Hyperbranched poly(amidoamine)-grafted carbon black gave a stable dispersion in a good solvent for poly(amidoamine). Copyright © 2001 John Wiley & Sons, Ltd. [source] Solvent-dependent conformation of amylose tris(phenylcarbamate) as deduced from scattering and viscosity dataBIOPOLYMERS, Issue 9 2009Taichi Fujii Abstract The z -average mean-square radius of gyration ,S2,z, the particle scattering function P(k), the second virial coefficient, and the intrinsic viscosity [,] have been determined for amylose tris(phenylcarbamate) (ATPC) in methyl acetate (MEA) at 25°C, in ethyl acetate (EA) at 33°C, and in 4-methyl-2-pentanone (MIBK) at 25°C by light and small-angle X-ray scattering and viscometry as functions of the weight-average molecular weight in a range from 2 × 104 to 3 × 106. The first two solvents attain the theta state, whereas the last one is a good solvent for the amylose derivative. Analysis of the ,S2,z, P(k), and [,] data based on the wormlike chain yields h (the contour length or helix pitch per repeating unit) = 0.37 ± 0.02 and ,,1 (the Kuhn segment length) = 15 ± 2 nm in MEA, h = 0.39 ± 0.02 and ,,1 = 17 ± 2 nm in EA, and h = 0.42 ± 0.02 nm and ,,1 = 24 ± 2 nm in MIBK. These h values, comparable with the helix pitches (0.37,0.40 nm) per residue of amylose triesters in the crystalline state, are somewhat larger than the previously determined h of 0.33 ± 0.02 nm for ATPC in 1,4-dioxane and 2-ethoxyethanol, in which intramolecular hydrogen bonds are formed between the CO and NH groups of the neighbor repeating units. The slightly extended helices of ATPC in the ketone and ester solvents are most likely due to the replacement of those hydrogen bonds by intermolecular hydrogen bonds between the NH groups of the polymer and the carbonyl groups of the solvent. © 2009 Wiley Periodicals, Inc. Biopolymers 91: 729,736, 2009. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Functionalized Siloles: Versatile Synthesis, Aggregation-Induced Emission, and Sensory and Device ApplicationsADVANCED FUNCTIONAL MATERIALS, Issue 6 2009Zhen Li Abstract The synthesis of functionalized siloles has been a challenge because of the incompatibility of polar functional groups with the reactive intermediates in the conventional protocols for silole synthesis. In this work, a synthetic route for silole functionalization is elaborated, through which a series of functionalized siloles are successfully prepared. Whereas light emissions of traditional luminophores are often quenched by aggregation, most of the functionalized siloles show an exactly opposite phenomenon of aggregation-induced emission (AIE). The siloles are nonemissive when dissolved in their good solvents but become highly luminescent when aggregated in their poor solvents or in the solid state. Manipulation of the aggregation,deaggregation processes of the siloles enables them to play two seemly antagonistic roles and work as both excellent quenchers and efficient emitters. The AIE effect endows the siloles with multifaceted functionalities, including fluorescence quenching, pH sensing, explosive detection, and biological probing. The sensing processes are very sensitive (with detection limit down to 0.1,ppm) and highly selective (with capability of discriminating among different kinds of ions, explosives, proteins, DNAs, and RNAs). The siloles also serve as active layers in the fabrication of electroluminescent devices and as photosensitive films in the generation of fluorescence patterns. [source] Preparation of isotactic-rich poly(dimethyl vinylphosphonate) and poly(vinylphosphonic acid) via the anionic polymerization of dimethyl vinylphosphonateJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2010Takehiro Kawauchi Abstract A vinylphosphonate monomer, dimethyl vinylphosphonate (DMVP), has been polymerized by anionic initiators. Anionic polymerization of DMVP with tert -butyllithium (t -BuLi) in combination with a Lewis acid, tributylaluminum (n -Bu3Al), in toluene proceeded smoothly to give an isotactic-rich poly(dimethyl vinylphosphonate) (PDMVP) with relatively narrow molecular weight distribution. Although all the PDMVPs were soluble in water, the isotactic-rich PDMVP was insoluble in acetone and in chloroform which are good solvents for an atactic PDMVP prepared by radical polymerization. The isotactic-rich PDMVP showed higher thermal property than that of the atactic PDMVP. Moreover, we successfully prepared poly(vinylphosphonic acid) (PVPA) through the hydrolysis of the isotactic-rich PDMVP, which formed a highly transparent, self-standing film. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1677,1682, 2010 [source] Crystallization-Induced Phase Segregation Based on Double-Crystalline Blends of Poly(3-hexylthiophene) and Poly(ethylene glycol)sMACROMOLECULAR RAPID COMMUNICATIONS, Issue 6 2010Kui Zhao Abstract Crystallization-induced vertical stratified structures were constructed based on double-crystalline poly(3-hexylthiophene) (P3HT)/poly(ethylene glycol)s (PEG) systems at room temperature, in which the P3HT crystallinity and the mechanism were investigated. Vertical stratified microstructures with highly crystalline P3HT network on the surface were formed when depositing from marginal solvents, while lateral phase-separated structures or low P3HT crystallinity were observed for good solvents. The morphological differences came from the solvent effect. In marginal solvents, p -xylene and dichloromethane, P3HT large-scale microcrystallites were generated in solution, which ensured the priority of P3HT crystalline sequence, and phase separation began in the liquid states. When the PEG matrix began to crystallize, great energy from which the second phase separation was induced drove P3HT crystallites to the surface, resulting in the formation of vertical stratified microstructures with highly crystalline P3HT network on the surface. The method, crystallization-induced phase segregation of crystalline,crystalline blends in marginal solvent, provides a facile way to construct vertically stratified structures, in which P3HT highly crystalline network is favored. [source] Robust Organic/Inorganic Hybrid Porous Thin Films via Breath-Figure Method and Gelation ProcessMACROMOLECULAR RAPID COMMUNICATIONS, Issue 20 2007Ke Zhang Abstract A novel organic/inorganic hybrid honeycomb patterned porous thin film was prepared using the breath-figure method combined with a sol-gel process. An in situ formed gelable block copolymer, formed by mixing poly(styrene- alt -maleic anhydride)- block -polystyrene (P(St- a -MAn)- b -PS) and 3-aminopropyltrimethoxysilane (APS), was used as the structure directing agent. The porous film produced was dipped into an acid aqueous solution to induce a sol-gel process in the wall of film. As a result of gelation, the structure of this film transformed into a crosslinked silica oxide hybridized with PS, and this film resisted those organic solvents which were once good solvents for the copolymer precursor. [source] Chemoenzymatic Synthesis of Amylose-Grafted ChitosanMACROMOLECULAR RAPID COMMUNICATIONS, Issue 7 2007Shun-ichi Matsuda Abstract An amylose-grafted chitosan has been synthesized by a chemoenzymatic method according to the following two reactions. First, maltoheptaose is introduced to chitosan by a reductive amination using sodium cyanotrihydroborate in a mixed solvent of 1.0 mol,·,L,1 aqueous acetic acid and methanol at room temperature to produce a maltoheptaose-grafted chitosan that has a well-defined molecular structure. A phosphorylase-catalyzed enzymatic polymerization of , - D -glucose 1-phosphate is then performed from the maltoheptaose-grafted chitosan to obtain the amylose-grafted chitosan. This material does not dissolve in any solvent, e.g., aqueous acetic acid and dimethyl sufoxide, which are good solvents for chitosan and amylose, respectively. [source] Free Radical Polymerization of Acrylonitrile in Green Ionic LiquidsMACROMOLECULAR SYMPOSIA, Issue 1 2004Liang Cheng Abstract Free radical polymerization of acrylonitrile (AN) in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 2,2;m1-azobisisobutyronitrile (AIBN) as initiator was investigated. Early investigations on polymerizations using ionic liquids indicate that they serve as especially good solvents to achieve high molecular weight polymers. Free radical polymerizations result in higher molecular weight polymers, for ionic liquids have low chain transfer constants and act to stabilize the active radical during the process of polymerization. The thermal stability of polymers synthesized in ionic liquids have be improved obviously than that in traditional solvents. [source] Monte Carlo study of cycloamylose: Chain conformation, radius of gyration, and diffusion coefficientBIOPOLYMERS, Issue 2 2002Yasushi Nakata Abstract Cyclic (1 , 4)-,- D -glucan chains with or without excluded volume have been collected from a huge number (about 107) of linear amylosic chains generated by the Monte Carlo method with a conformational energy map for maltose, and their mean-square radii of gyration ,S2, and translational diffusion coefficients D (based on the Kirkwood formula) have been computed as functions of x (the number of glucose residues in a range from 7 to 300) and the excluded-volume strength represented by the effective hard-core radius. Both ,S2,/x and D in the unperturbed state weakly oscillate for x < 30 and the helical nature of amylose appears more pronouncedly in cyclic chains than in linear chains. As x increases, these properties approach the values expected for Gaussian rings. Though excluded-volume effects on them are always larger in cycloamylose than in the corresponding linear amylose, the ratios of ,S2, and the hydrodynamic radius of the former to the respective properties of the latter in good solvents can be slightly lower than or comparable to the (asymptotic) Gaussian-chain values when x is not sufficiently large. An interpolation expression is constructed for the relation between the gyration-radius expansion factors for linear and cyclic chains from the present Monte Carlo data and the early proposed asymptotic relation with the aid of the first-order perturbation theories. © 2002 Wiley Periodicals, Inc. Biopolymers 64: 72,79, 2002 [source] | |||||||||||||||||||||||||