Viscosity of semiflexible chitosan solutions: influence of concentration, temperature, and role of intermolecular interactions

The influence of polymer concentration and temperature on the rheological behavior of chitosan solution was studied. The threshold concentrations for the different viscometric regimes were determined and the different power laws exponents were calculated and compared with those predicted from models. Different observations and the high values of these exponents within the high concentration region lead to consideration of the presence of intermolecular interactions as soon as the polymer concentration is larger than the overlap concentration. The activation energy was determined as a function of the polymer concentration, and its evolution was compared with theoretical predictions. A gel-sol transition was demonstrated at high concentrations.     

Evidence for "diminishing returns" from the scaling of stem diameter and specific leaf area

Research indicates that increases in total leaf area (A(T)) may fail to keep pace with increases in total leaf mass (M(L)) across plants differing in size (e.g., as measured by stem diameter, D). This "diminishing returns" hypothesis predicts that the scaling exponent for A(T) vs. M(L) will be less than one and that the exponent for specific leaf mass (i.e., A(T) / M(L)) vs. D will be negative. These predictions were examined using data from 46 plants ranging between 0.125 cm ≤ D ≤ 0.485 m across 25 woody dicot species. Standardized major axis slopes were used to quantify scaling exponents and random effects models were used to quantify species and size effects on the numerical values of exponents. The exponents for A(T) vs. M(L) and A(T) / M(L) vs. D differed among species and different species groupings. In general, the exponent for A(T) vs. M(L) was less than one and the exponent for A(T) / M(L) vs. D was negative, as predicted. However, random effects models indicated that species effects overshadowed size effects, although size effects were statistically significant. The diminishing returns hypothesis therefore receives statistical support, i.e., although the numerical values of exponents are "species-dependent," they are less than unity, as predicted by theory.     

Determination of the viscometric constants for chitosan

The viscometric constants a and K_m in the Mark-Houwink equation have been determined for chitosan in 0.1 m acetic acid 0.2 m sodium chloride solution, using the approach of Sharples and Major. The number-average molecular weights were determined by absorbance measurements on solutions of the phenylosazone derivatives. The values obtained a = 0.93, K_m = 1.81 × 10^?3 cm³ g¹ differ considerably from those reported previously by Lee but are in agreement with values found for other ionic polysaccharides having related β-(1 → 4)-linked structures.     

7种木本植物的分支指数与代谢指数

West、Brown和Enquist提出的植物分形网络模型(简称WBE模型)认为: 植物的分支指数(1/a, 1/b)决定植物的代谢指数, 当分支指数1/a、1/b分别为理论值2.0、3.0时, 代谢速率与个体大小的3/4次幂成正比, 但是恒定的3/4代谢指数并不能全面地反映植物的代谢情况。基于分支指数的协同变化, Price、Enquist和Savage对WBE模型进行扩展, 提出植物分支参数协同变化模型(简称PES模型)。该文借助于PES模型分析了7种木本植物的分支指数和代谢指数。结果表明: 物种间叶面积与叶生物量呈异速生长关系, 基于叶面积得到的分支指数1/a和代谢指数θ在物种间无显著差异, 基于叶生物量得到的分支指数1/a、1/b和代谢指数θ在物种间均存在显著差异, 但基于叶面积和叶生物量分别拟合出的整体分支指数1/a、1/b和代谢指数θ与理论值均无显著差异, 且用叶面积作为代谢速率的替代指标比用叶生物量分析得出的代谢指数与理论值更接近。今后研究应当关注植物叶面积与叶生物量的异速生长关系对植物代谢速率及相关功能特性的影响。     

Branching and metabolic exponents in seven woody plants

West、Brown和Enquist提出的植物分形网络模型(简称WBE模型)认为: 植物的分支指数(1/a, 1/b)决定植物的代谢指数, 当分支指数1/a、1/b分别为理论值2.0、3.0时, 代谢速率与个体大小的3/4次幂成正比, 但是恒定的3/4代谢指数并不能全面地反映植物的代谢情况。基于分支指数的协同变化, Price、Enquist和Savage对WBE模型进行扩展, 提出植物分支参数协同变化模型(简称PES模型)。该文借助于PES模型分析了7种木本植物的分支指数和代谢指数。结果表明: 物种间叶面积与叶生物量呈异速生长关系, 基于叶面积得到的分支指数1/a和代谢指数θ在物种间无显著差异, 基于叶生物量得到的分支指数1/a、1/b和代谢指数θ在物种间均存在显著差异, 但基于叶面积和叶生物量分别拟合出的整体分支指数1/a、1/b和代谢指数θ与理论值均无显著差异, 且用叶面积作为代谢速率的替代指标比用叶生物量分析得出的代谢指数与理论值更接近。今后研究应当关注植物叶面积与叶生物量的异速生长关系对植物代谢速率及相关功能特性的影响。     

Mismatch dependent uracil/thymine-DNA glycosylases excise exocyclic hydroxyethano and hydroxypropano cytosine adducts

Exocyclic adducts of DNA bases, such as etheno- and hydroxyalkano- ones, are generated by a variety of bifunctional agents, including endogenously formed products of lipid peroxidation. In this work we selectively modified cytosines in the 5'-d(TTT TTT CTT TTT CTT TTT CTT TTT T)-3' oligonucleotide using: chloroacetaldehyde to obtain 3,N(4)-alpha-hydroxyethano- (HEC) and 3,N(4)-etheno- (epsilonC), acrolein to obtain 3,N(4)-alpha-hydroxypropano- (HPC) and crotonaldehyde to obtain 3,N(4)-alpha-hydroxy-gamma-methylpropano- (mHPC) adducts of cytosine. The studied adducts are alkali-labile which results in oligonucleotide strain breaks at the sites of modification upon strong base treatment. The oligonucleotides carrying adducted cytosines were studied as substrates of Escherichia coli Mug, human TDG and fission yeast Thp1p glycosylases. All the adducts studied are excised by bacterial Mug although with various efficiency: epsilonC >HEC >HPC >mHPC. The yeast enzyme excises efficiently epsilonC>HEC>HPC, whereas the human enzyme excises only epsilonC. The pH-dependence curves of excision of eC, HEC and HPC by Mug are bell shaped and the most efficient excision of adducts occurs within the pH range of 8.6-9.6. The observed increase of excision of HEC and HPC above pH 7.2 can be explained by deprotonation of these adducts, which are high pK(a) compounds and exist in a protonated form at neutrality. On the other hand, since epsilonC is in a neutral form in the pH range studied, we postulate an involvement of an additional catalytic factor. We hypothesize that the enzyme structure undergoes a pH-induced rearrangement allowing the participation of Lys68 of Mug in catalysis via a hydrogen bond interaction of its epsilon-amino group with N(4) of the cytosine exocyclic adducts.     

Subunit interactions in the first component of complement, C1

Interactions between C1q and other subunits of C1 were analyzed by sucrose gradient ultracentrifugation. A zone of dilute, radioiodine labelled C1q was sedimented through uniform concentrations of either C1r2C1s2, C1r2, C1r2 or C1s(2). The dissociation constants were found to be 3 x 10(-9) M and 6 x 10(-9) M for C1r2C1s2 and C1r2 binding respectively. Hill coefficients of 1 indicated no cooperativity in these bindings. Positive cooperativity was found in binding of C1s to C1q. Dissociation constants of 2 x 10(-6) M and 5 x 10(-8) M were obtained form computer modelling of a two step binding mechanism. No interaction was detected between C1q and activated C1r2. The data indicate that most of the interactions between C1q and C1r2C1s2 originates from a strong binding to the C1r2 moiety of the zymogen complex. This interaction is lost upon activation of C1r2.     

Evidence for linkage of the central core disease locus to the proximal long arm of human chromosome 19

Central core disease of muscle (CCD; MIM 117000) is a rare inheritable myopathy that is frequently found in association with susceptibility to malignant hyperthermia (MHS). This observation has prompted us to perform a linkage study in CCD families using various chromosome 19q probes that are linked to the MHS locus and map close to the ryanodine receptor gene (RYR1), a strong MHS candidate gene. Our genetic linkage data support a location of the CCD gene on proximal 19q13.1 and thus suggest that CCD and MHS may be allelic.     

The impact of urea on viscosity of hydroxethyl cellulose and observed mobility of deoxyribonucleic acids

The influence of urea on the viscosity of hydroxyethyl cellulose (HEC), and the state and separation of double-stranded DNA, was studied by viscometry, fluorometry, and capillary electrophoresis. The results show that double logarithm plots of specific viscosity against the volume fraction of HEC in very dilute polymer solutions are linear, the slopes of which decrease from 0.96 in 0M to 0.29 in 7M urea. The linear regression plots converge at 0.0029 g/mL, the entanglement threshold of HEC. The inclusion of urea in HEC solution thus provides an accurate method of determining its entanglement threshold from such plots. Above the entanglement threshold of HEC, urea has no effect on the specific viscosity of HEC. Results also show that urea has no effect on double-stranded DNA. No change in fluorescence was observed when increasing amounts of urea were added to a fixed concentration of DNA. To examine the influence of urea on the migration of DNA in HEC, the separation of DNA was carried out by polymer-solution capillary electrophoresis in HEC solutions containing 0 or 7M urea using unmodified capillary. Observed mobilities were used in data reduction. It was found that a parallel relationship exists between the observed mobilities and the true mobilities. In buffers containing no urea, the pseudo-free solution mobility appears to be independent of the DNA size. It was also observed to be independent of the electric field below 300 V/cm, but relates exponentially to it in 7M urea. The pseudo-retardation constants obtained by Ferguson-like plots were observed to be positive for smaller DNA molecules below 300 V/cm and increasing linearly with electric field in 0M urea, but nearly constant in 7M urea.     

Interpenetrating biopolymer network based hydrogels for an effective drug delivery system

Discovery of hydrogels has resulted in developing competent controlled-release drug delivery systems. Present study describes the synthesis and characterization of novel pH responsive hydrogels of chitosan, hydroxyl ethyl cellulose (HEC) and polyol prepared by physical blending of the three components in different ratios. Vegetable oil derived polyol seems to act as a filler and cross linking agent. The synthesized hydrogels were characterized using FT-IR spectroscopy, thermo gravimetric analysis (TGA), Optical microscopy and scanning electron microscopy (SEM). Equilibrium swelling behavior of hydrogels in water and different buffers with pH values (2, 4, 7.3, and 8) indicated the sustained expansion of the films in different pH solutions.     

A study of the chain stiffness and extension of alginates, in vitro epimerized alginates, and periodate-oxidized alginates using size-exclusion chromatography combined with light scattering and viscosity detectors

A series of alginates isolated from the stem and leaf of a brown algae (Laminaria hyperborea), bacterial mannuronan, in vitro epimerized mannuronans, and periodate oxidized alginates were analyzed by size-exclusion chromatography (SEC) combined with online multiangle laser light scattering (MALS) and viscometry (collectively abbreviated SMV). Selected samples were also analyzed off-line using low-angle laser light scattering and capillary viscometry. Excellent agreement between the two methods was obtained for properly purified samples. In contrast, abnormal results were obtained for some industrial samples due to the presence of particulate material. Naturally occurring alginates and in vitro epimerized mannuronans were found to obey essentially the same RG-M and [eta]-M relations, and hence, the same Mark-Houwink-Sakurada (MHS) equations (valid for I = 0.10 M): 20 000 g/mol < M < 100 000 g/mol, [eta] = 0.0054 .M(1.00); 100 000 g/mol < M < 1 000 000 g/mol, [eta] = 0.071 .M(0.89). Application of the wormlike chain model to the [eta]-M data obtained by SMV yielded persistence lengths (q) of 15 nm for all alginates at an ionic strength of 0.17 M. Intrinsic viscosities corresponding to infinite ionic strength were estimated on the basis of Smidsr?d's B-parameter, and the wormlike chain model then yielded q = 12 nm. Periodate oxidized alginates showed, in contrast, a pronounced decrease in persistence length with increasing degree of oxidation, reaching values below 4 nm at 44% oxidation. Periodate oxidation also resulted in some depolymerization, even in the presence of a free-radical scavenger.     

PHYLOGENETICALLY INFORMED ANALYSIS OF THE ALLOMETRY OF MAMMALIAN BASAL METABOLIC RATE SUPPORTS NEITHER GEOMETRIC NOR QUARTER-POWER SCALING

The form of the relationship between the basal metabolic rate (BMR) and body mass (M) of mammals has been at issue for almost seven decades, with debate focusing on the value of the scaling exponent ( b , where BMR ∝ M^b ) and the relative merits of b = 0.67 (geometric scaling) and b = 0.75 (quarter-power scaling). However, most analyses are not phylogenetically informed (PI) and therefore fail to account for the shared evolutionary history of the species they consider. Here, we reanalyze the most rigorously selected and comprehensive mammalian BMR dataset presently available, and investigate the effects of data selection and phylogenetic method (phylogenetic generalized least squares and independent contrasts) on estimation of the scaling exponent relating mammalian BMR to M. Contrary to the results of a non-PI analysis of these data, which found an exponent of 0.67–0.69, we find that most of the PI scaling exponents are significantly different from both 0.67 and 0.75. Similarly, the scaling exponents differ between lineages, and these exponents are also often different from 0.67 or 0.75. Thus, we conclude that no single value of b adequately characterizes the allometric relationship between body mass and BMR.     

Evidence for the localization of a malignant hyperthermia susceptibility locus (MHS2) to human chromosome 17q.

Malignant hyperthermia susceptibility is a lethal autosomal dominant disorder of skeletal muscle metabolism that is triggered by all potent inhalation anesthetic gases. Recent linkage studies suggest a genetic locus for this disorder on 19q13.1. We have previously reported three unrelated families diagnosed with MHS that are unlinked to markers surrounding this locus on 19q13.1. In this report we extend these observations and present linkage studies on 16 MHS families. Four families (25%) were found linked to the region 19q12-q13.2 (Zmax = 2.96 with the ryanodine receptor at theta = 0.0). Five families (31%) were found closely linked to the anonymous marker NME1 (previously designated NM23) on chromosome 17q11.2-q24 (Zmax = 3.26 at theta = 0.0). Two families (13%) were clearly unlinked to either of these chromosomal regions. In five additional families, data were insufficient to determine their linkage status (they were potentially linked to two or more sites). The results of our heterogeneity analyses are consistent with the hypothesis that MHS can be caused in humans by any one of at least three distinct genetic loci. Furthermore, we provide preliminary linkage data suggesting the localization of a gene in human MHS to 17q11.2-q24 (MHS2), with a gene frequency of this putative locus approximately equal to that of the MHS1 locus on 19q.     

Antioxidative Activities of Several Marine Polysaccharides Evaluated in a Phosphatidylcholine-liposomal Suspension and Organic Solvents

The antioxidative activities of several water-soluble marine polysaccharides, alginate (ALG), alginate sulfate (SALG), propylene glucolalginate sodium sulfate (PSS), propylene glucol mannuronate sulfate (PGMS), the oligosaccharide of chitosan (OLC), N,O-carboxymethyl chitosan (NOCC) and hydroxypropylated chitosan (HPC), were examined in a phosphatidylcholine (PC)-liposomal suspension containing the water-soluble radical emitter, 2,2′-azobis (2-amidinopropane) dihydrochloride. In the suspensions containing OLC and SALG, the initial rates of PC-OOH accumulation were 2.78×10^-8 Ms^-1 and 2.88×10^-8 Ms^-1, respectively, while all the polysaccharides tested showed antioxidative activity.

Liposoluble marine polysaccharides, hexanoyl chitin (HCH) and an N-benzoylhexanoyl chitosan (NBHC) solution, also retarded the hydroperoxide accumulation of methyl linoleate by effectively trapping peroxide radicals in organic solvents when the radical chain reaction had been initiated by 2,2′-azobis (2,4-dimethylvaleronitrile).

The kinetic data presented indicate that the alginate and chitin derivatives can be expected to play a role in the antioxidative mechanism of biological systems.     

Intrinsic viscosity of bovine serum albumin conformers

Intrinsic viscosity of bovine serum albumin (BSA) at different pH values (2.7, 4.3, 7.4, 8 and 10) has been determined, as well as the Mark-Houwink constant and expansion factor. The traditional technique for data analysis using extrapolation to obtain intrinsic viscosity values shows an unusual behavior regarding concentration that can be observed in the values obtained for Huggins' and Kraemer's constants.     

The ratio and allometric scaling of speed, power, and strength in elite male rugby union players

This study compared the effectiveness of ratio and allometric scaling for normalizing speed, power, and strength in elite male rugby union players. Thirty rugby players (body mass [BM] 107.1 ± 10.1 kg, body height [BH] 187.8 ± 7.1 cm) were assessed for sprinting speed, peak power during countermovement jumps and squat jumps, and horizontal jumping distance. One-repetition maximum strength was assessed during a bench press, chin-up, and back squat. Performance was normalized using ratio and allometric scaling (Y/X), where Y is the performance, X, the body size variable (i.e., BM or BH), and b is the power exponent. An exponent of 1.0 was used during ratio scaling. Allometric scaling was applied using proposed exponents and derived exponents for each data set. The BM and BH variables were significantly related, or close to, performance during the speed, power and/or strength tests (p < 0.001-0.066). Ratio scaling and allometric scaling using proposed exponents were effective in normalizing performance (i.e., no significant correlations) for some of these tests. Allometric scaling with derived exponents normalized performance across all the tests undertaken, thereby removing the confounding effects of BM and BH. In terms of practical applications, allometric scaling with derived exponents may be used to normalize performance between larger rugby forwards and smaller rugby backs, and could provide additional information on rugby players of similar body size. Ratio scaling may provide the best predictive measure of performance (i.e., strongest correlations).     

Robust nonlinear parameter estimation in tracer kinetic analysis using infinity norm regularization and particle swarm optimization

In positron emission tomography (PET) studies, the voxel-wise calculation of individual rate constants describing the tracer kinetics is quite challenging because of the nonlinear relationship between the rate constants and PET data and the high noise level in voxel data. Based on preliminary simulations using a standard two-tissue compartment model, we can hypothesize that it is possible to reduce errors in the rate constant estimates when constraining the overestimation of the larger of two exponents in the model equation. We thus propose a novel approach based on infinity-norm regularization for limiting this exponent. Owing to the non-smooth cost function of this regularization scheme, which prevents the use of conventional Jacobian-based optimization methods, we examined a proximal gradient algorithm and the particle swarm optimization (PSO) through a simulation study. Because it exploits multiple initial values, the PSO method shows much better convergence than the proximal gradient algorithm, which is susceptible to the initial values. In the implementation of PSO, the use of a Gamma distribution to govern random movements was shown to improve the convergence rate and stability compared to a uniform distribution. Consequently, Gamma-based PSO with regularization was shown to outperform all other methods tested, including the conventional basis function method and Levenberg–Marquardt algorithm, in terms of its statistical properties.     

Power Law Distributions of Patents as Indicators of Innovation

The total number of patents produced by a country (or the number of patents produced per capita) is often used as an indicator for innovation. Here we present evidence that the distribution of patents amongst applicants within many countries is well-described by power laws with exponents that vary between 1.66 (Japan) and 2.37 (Poland). We suggest that this exponent is a useful new metric for studying innovation. Using simulations based on simple preferential attachment-type rules that generate power laws, we find we can explain some of the variation in exponents between countries, with countries that have larger numbers of patents per applicant generally exhibiting smaller exponents in both the simulated and actual data. Similarly we find that the exponents for most countries are inversely correlated with other indicators of innovation, such as research and development intensity or the ubiquity of export baskets. This suggests that in more advanced economies, which tend to have smaller values of the exponent, a greater proportion of the total number of patents are filed by large companies than in less advanced countries.     

沙柳丛生枝代谢指数的龄级效应

新陈代谢速率是植物最基本的生物学速率,与地表植被的水碳代谢过程密切相关.表征代谢速率及其替代指标(如叶生物量等)与个体大小间相关生长关系的代谢指数是生态学研究的一个热点,WBE模型论证的3/4恒定代谢指数最为经典,但也饱受争议.本研究以毛乌素沙地南缘沙柳为对象,检验了WBE模型的可用性,揭示代谢指数随丛生枝生长发育的变化规律.结果表明: 基于叶生物量和茎叶生物量估计的沙柳丛生枝代谢指数α为0.97,显著大于WBE模型的恒定指数3/4;分支半径指数1/a和分支长度指数1/b分别为2.67和3.83,均显著大于理论值2.0和3.0.分龄级估计的丛生枝分支半径指数和分支长度指数分别为2.64～3.24和2.86～4.30,各龄级代谢指数的估计值和计算值分别为1.01～1.29和0.94～1.13,龄级差异均不显著.斜率异质性检验表明,不同龄级的丛生枝共有代谢指数估计值1.08和计算值1.00、分支半径指数2.84和分支长度指数3.35,均显著大于理论值.在各龄级丛生枝共有代谢指数1.08下,代谢常数在y轴上的负向漂移幅度随龄级增加而显著增大.尽管枝龄未引起沙柳丛生枝代谢指数的显著变化,但在给定大小的枝条上,大龄枝较低龄枝的代谢活性下降明显.     

Determination of binding constants of lipopolysaccharides of different structure with chitosan

The interaction of endotoxins--lipopolysaccharides (LPS) different in degree of the O-specific chain polymerization--with 20- and 130-kD chitosan was studied using the competitive binding of LPS with the complex of chitosan-anionic dye (tropaeolin 000-2) and the direct binding of (125)I-labeled LPS with chitosan immobilized on Sepharose 4B. The interaction of 20-kD chitosan with LPS was non-cooperative, and immobilization of the polycation on Sepharose resulted in its binding to (125)I-labeled LPS with a positive cooperativity. The interaction of LPS possessing a long O-specific chain with 130-kD chitosan was characterized by negative cooperativity. Binding constants of LPS with the polycation and the number of binding sites per amino group of chitosan were determined. The interaction affinity and stoichiometry of the LPS-chitosan complexes significantly depend on the LPS structure and concentration in the reaction mixture. The increase in the length of carbohydrate chains of LPS results in increase in the binding constants and decrease in the bound endotoxin amount.