Effect of temperature on alpha olefin sulfonate induced softening of gelatin hydrogels

Dynamic light scattering (DLS) and oscillatory rheology experiments were performed to study temperature dependence (T=10-25 degrees C) of the interactions in hydrogels of gelatin with AOS (alpha olefin sulfonate, anionic surfactant) for surfactant concentrations in the range 25-100 mM, chosen larger than cmc (approximately 8mM). The network mesh size (xi) values deduced from fastmode diffusivity (D(f)) data obtained from dynamic structure factor measurements, S(q, t) approximately exp(-D(f)q(2)t) (for t相似文献   

Experimental and theoretical DFT (B3LYP,X3LYP,CAM-B3LYP and M06-2X) study on electronic structure,spectral features,hydrogen bonding and solvent effects of 4-methylthiadiazole-5-carboxylic acid

Detailed structural, electronic and spectroscopic study of 4-methylthiadiazole-5-carboxylic acid, one of the simplest 1,2,3-thiadiazole derivatives has been performed using density functional theory at four different functionals (B3LYP, X3LYP, CAM-B3LYP and M06-2X). The two possible conformers and their dimeric forms have been investigated for the stability and hence for the calculation of molecular properties of the title compound. Vibrational analysis has been performed with the help of experimental FT-IR and FT-Raman spectra. NBO analysis has been performed to estimate the N–H—O=C hydrogen bond strength and to evaluate the intra and inter molecular charge transfer in the system. Intermolecular hydrogen-bond strength has also been computed using Atoms in Molecules (AIM) theory. To visualise spatial domain, key sites of electron transitions and electron density difference between ground as well as excited states, and their 2D and 3D plots have been computed. Solvent effect on the intermolecular hydrogen bonding have also been investigated using solvents of different polarities. Non-linear optical properties, molecular electrostatic potential surface map (MESP), thermodynamic potentials at different temperatures have also been computed and plotted.     

Solvent polarity effect on excited-state lifetime of carotenoids and some dyes

The theory demonstrating the role of medium at the fluorescence quenching of polar compounds in solutions is briefly presented. It has been shown, that the rate of S(1) --> X(n) nonradiative conversion between the intramolecular charge transfer states depends on the permanent dipole moments in the ground (S(0)) and excited (S(1), X(n)) states as well as on solvent polarity. A relation for the rate of nonradiative excited-state energy conversion has been obtained and employed to test the known literature data for solvent effect on the S(1)-state lifetime of some biologically significant carotenoids and dyes (phthalimides). For phthalimides, the solvent isotope effect on the S(1)-state energy conversion, when hydrogen is replaced by deuterium in the OH groups of alcohols and water, has been analyzed. Based on the data for fluorescence quenching in solvents of different polarity, the dipole moments in the intermolecular charge transfer S(1) state have been obtained for carotenoids (peridinin, fucoxanthin, uriolide acetate) and for hydrogen-bonding complexes, which are formed by 4-amino-, 4-methylamino-, and 4-dimethylamino-N-methylphthalimides in alcohols and water.     

Light scattering of bovine serum albumin solutions: Extension of the hard particle model to allow for electrostatic repulsion

The light scattering of bovine serum albumin (BSA) has been measured at protein concentration up to 90 g/L and at pH values between 4.4 and 7.6. The dependence of scattering on both protein concentration and pH may be quantitatively accounted for by a simple extension of the hard-sphere model for protein solutions [Ross, P. D. & Minton, A. P. (1977) J. Mol. Biol. 112 , 437–452] allowing for electrostatic repulsions between molecules. According to the extended model, the radius of the effective hard spherical particle representing BSA varies with the net electrical charge of the BSA molecule in a manner which may be calculated from electrostatic theory.     

A channel model with fluctuating barrier structures.

Following the theory 'Fluctuations of barrier structure in ionic channels' (L?uger, P., Stephan, W. and Frehland, E. (1980) Biochim. Biophys. Acta 602, 167-180), we constructed a model of a channels with several conformational states. The origin of these conformational states and the source for the transitions from one to the other are given explicitly for the presented model. In this work the effect of multiple conformational states on the ion transport process is analyzed. We considered a channel protein with two main barriers and one binding site. The site is surrounded by dipolar groups. The dipole moment of these groups can be reoriented by thermal activity and also by electrical interaction with the transported ions. Differently polarized states generate different activation energy barriers for the ions. The set of conformational states of the channel is constituted by all the possible polarized states of the binding site. Using the rate-theory analysis of ion transport (Gl?sstone, S., Laider, K.J. and Eyring, H. (1941) The theory of rate processes, McGraw-Hill, New York), the possible coupling between ion flux and the channel conformational transitions has been incorporated into the model by considering the dependence of the rate constants on the heights of the energy barriers. The resulting multistate kinetic equations have been solved numerically. It was shown that the simple saturation characteristic of the flux-concentration curve was obtained. For certain values of the model parameters, the channel shows a strongly different conductance for anions compared to cations. In fact, the model contains an interesting mechanism that exhibits selectivity with respect to the charge of the ions.     

A comparative spectroscopic study of two non-haem iron proteins lacking labile sulphide from Desulphovibrio gigas.

The ultraviolet visible, and near infrared spectrum of a two-iron protein from Desulphovibrio gigas, a new type of non-haem iron protein lacking labile sulphide, is compared with that of D. gigas rubredoxin. The charge transfer band maxima of rubredoxin at 495 and 565 nm are less separated in the new protein implying a higher symmetry of the two iron centres. The existence of a spin-spin interaction between the two iron centres in the new protein is suggested by the magnetic susceptibility measurements of the oxidized and reduced states of both proteins, which gives a smaller value per iron centre for the new protein. The oxidized form of the two iron-protein has a complex EPR spectrum with signals at g values of 8.97, 7.72, 5.73, 4.94, and 1.84. An EPR titration gives a value of --35 +/- 15 mV for the two signals at g values of 7.72 and 5.73. Rubredoxin has the characteristic spectrum of rubredoxins with two signals at g values of 9.4 and 4.27.     

Comparative study on electronic structures and optical properties of indoline and triphenylamine dye sensitizers for solar cells

The computations of the geometries, electronic structures, dipole moments and polarizabilities for indoline and triphenylamine (TPA) based dye sensitizers, including D102, D131, D149, D205, TPAR1, TPAR2, TPAR4, and TPAR5, were performed using density functional theory, and the electronic absorption properties were investigated via time-dependent density functional theory with polarizable continuum model for solvent effects. The population analysis indicates that the donating electron capability of TPA is better than that of indoline group. The reduction driving forces for the oxidized D131 and TPAR1 are slightly larger than that of other dyes because of their lower highest occupied molecular orbital level. The absorption properties and molecular orbital analysis suggest that the TPA and 4-(2,2diphenylethenyl)phenyl substituent indoline groups are effective chromophores in intramolecular charge transfer (IMCT), and they play an important role in sensitization of dye-sensitized solar cells (DSCs). The better performance of D205 in DSCs results from more IMCT excited states with larger oscillator strength and higher light harvesting efficiency. While for TPA dyes, the longer conjugate bridges generate the larger oscillator strength and light harvesting efficiency, and the TPAR1 and TPAR4 have larger free energy change for electron injection and dye regeneration.     

The electronic and magnetic properties of rubredoxin: a low-temperature magnetic circular dichroism study

Oxidized rubredoxin from Clostridium pasteurianum has been investigated by magnetic circular dichroism (MCD) spectroscopy over the temperature range 1.5 to 150 K and at magnetic fields between 0 and 4.5 tesla. The results show that studies of the temperature and field dependence of MCD transitions afford insight into the polarization of electronic transitions for ground states with large g-value anisotropy, in addition to estimates of ground-state g values and zero-field splitting parameters. In agreement with the assignment made by Eaton and Lovenberg (Eaton, W.A. and Lovenberg, W. (1973) in Iron-Sulfur Proteins, Vol. II (Lovenberg, W., ed.), pp. 131-162, Academic Press, New York), the ultraviolet-visible spectrum of oxidized rubredoxin is assigned to two S----Fe(III) charge transfer transitions (both 6A1----6T2 under tetrahedral symmetry), each spanning a range of 650-430 nm and 430-330 nm, respectively. The observed splitting in each of these transitions is attributed to a predominant axial distortion in the excited state resulting in effective D2d symmetry.     

芦芽山亚高山草甸、云杉林土壤有机碳、全氮含量的小尺度空间异质性

分析比较了山西芦芽山不同海拔处分布的亚高山草甸（样地A,海拔2756.3 m;样地B,海拔2542.3 m）和云杉林（样地C,海拔2656.8 m;样地D,海拔2387.2 m）土壤有机碳和全氮的小尺度空间异质性特征。结果表明：相同植被类型下海拔较高的样地有机碳含量较高（A：49.84 g/kg,B：38.33 g/kg,C：47.06 g/kg,D：40.67 g/kg）,而较低海拔的样地土壤有机碳含量的异质性较高;除样地A以外的其他3个样地均表现为高度空间依赖性。亚高山草甸土壤全氮含量的异质性远远高于云杉纯林,四个样地中均表现出强的空间自相关性。亚高山草甸样地土壤有机碳和全氮含量均在较大尺度上空间自相关,云杉纯林样地则表现为较小尺度的空间自相关变异。     

The intrinsic pKa values for phosphatidylcholine, phosphatidylethanolamine, and phosphatidylserine in monolayers deposited on mercury electrodes.

The intrinsic pKa values of the phosphate groups of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) and of the phosphate and carboxyl groups of phosphatidylserine (PS) in self-organized monolayers deposited on a hanging mercury drop electrode were determined by a novel procedure based on measurements of the differential capacity C of this lipid-coated electrode. In view of the Gouy-Chapman theory, plots of 1/C at constant bulk pH and variable KCl concentration against the reciprocal of the calculated diffuse-layer capacity Cd,0 at zero charge exhibit slopes that decrease from an almost unit value to vanishingly low values as the absolute value of the charge density on the lipid increases from zero to approximately 2 microC cm-2. The intrinsic pKa values so determined are 0.5 for PE and 0.8 for PC. The plots of 1/C against 1/Cd,0 for pure PS exhibit slopes that pass from zero to a maximum value and then back to zero as pH is varied from 7.5 to 3, indicating that the charge density of the lipid film passes from slight negative to slight positive values over this pH range. An explanation for this anomalous behavior, which is ascribed to the phosphate group of PS, is provided. Interdispersion of PS and PC molecules in the film decreases the "formal" pKa value of the latter group by about three orders of magnitude.     

Total Charge Movement per Channel : The Relation between Gating Charge Displacement and the Voltage Sensitivity of Activation

One measure of the voltage dependence of ion channel conductance is the amount of gating charge that moves during activation and vice versa. The limiting slope method, introduced by Almers (Almers, W. 1978. Rev. Physiol. Biochem. Pharmacol. 82:96–190), exploits the relationship of charge movement and voltage sensitivity, yielding a lower limit to the range of single channel gating charge displacement. In practice, the technique is plagued by low experimental resolution due to the requirement that the logarithmic voltage sensitivity of activation be measured at very low probabilities of opening. In addition, the linear sequential models to which the original theory was restricted needed to be expanded to accommodate the complexity of mechanisms available for the activation of channels. In this communication, we refine the theory by developing a relationship between the mean activation charge displacement (a measure of the voltage sensitivity of activation) and the gating charge displacement (the integral of gating current). We demonstrate that recording the equilibrium gating charge displacement as an adjunct to the limiting slope technique greatly improves accuracy under conditions where the plots of mean activation charge displacement and gross gating charge displacement versus voltage can be superimposed. We explore this relationship for a wide variety of channel models, which include those having a continuous density of states, nonsequential activation pathways, and subconductance states. We introduce new criteria for the appropriate use of the limiting slope procedure and provide a practical example of the theory applied to low resolution simulation data.     

Measures of entropy and complexity in altered states of consciousness

Quantification of complexity in neurophysiological signals has been studied using different methods, especially those from information or dynamical system theory. These studies have revealed a dependence on different states of consciousness, and in particular that wakefulness is characterized by a greater complexity of brain signals, perhaps due to the necessity for the brain to handle varied sensorimotor information. Thus, these frameworks are very useful in attempts to quantify cognitive states. We set out to analyze different types of signals obtained from scalp electroencephalography (EEG), intracranial EEG and magnetoencephalography recording in subjects during different states of consciousness: resting wakefulness, different sleep stages and epileptic seizures. The signals were analyzed using a statistical (permutation entropy) and a deterministic (permutation Lempel–Ziv complexity) analytical method. The results are presented in complexity versus entropy graphs, showing that the values of entropy and complexity of the signals tend to be greatest when the subjects are in fully alert states, falling in states with loss of awareness or consciousness. These findings were robust for all three types of recordings. We propose that the investigation of the structure of cognition using the frameworks of complexity will reveal mechanistic aspects of brain dynamics associated not only with altered states of consciousness but also with normal and pathological conditions.     

Density functional theory calculations of optical rotation: employment of ADZP and its comparison with other basis sets

Density function theory calculations of frequency dependent optical rotations ([alpha]omega) for 30 rigid chiral molecules are reported. Calculations have been carried out at the sodium D line frequency, using the augmented double zeta valence quality plus polarization functions (ADZP) basis set and the BP86 nonhybrid and B3LYP hybrid functionals. Gauge-invariant atomic orbitals were used to guarantee origin-independent values of [alpha]D. Comparison between corresponding results obtained with nonhybrid and hybrid functionals as well as with theoretical optical rotations reported in the literature is done. Excited electronic states of three molecules are also discussed in light of circular dichroism spectra and B3LYP and BP86 calculated excitation energies and rotatory strengths. One verifies that the B3LYP/ADZP results are in better agreement with experiment.     

Photodegradation in Encapsulated Silole‐Based Polymer: PCBM Solar Cells Investigated using Transient Absorption Spectroscopy and Charge Extraction Measurements

Light induced degradation has been observed in the performance of organic solar cells in the absence of oxygen and a detailed analysis of the effect of this photodegradation on optical and electrical features has been accomplished. This photodegradation study has been performed on encapsulated photovoltaic blend devices comprised of the silole‐based donor–acceptor polymer KP115 blended with [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM). Photodegradation induces an almost 20% decrease in power conversion efficiency, primarily as a result of a reduction in short circuit current, J_SC. The initial burn‐in phase of the photodegradation has been examined using a combination of transient absorption spectroscopy and charge extraction measurements, including photo‐CELIV (charge extraction by linearly increasing voltage) and time‐resolved charge extraction using a nanosecond switch. These measurements reveal a bimodal KP115 polaron population, comprised of both delocalised and localised/trapped charge carriers. The photodegradation results are consistent with an alteration of this bimodal KP115 polaron population, with the polarons becoming trapped in a broader, deeper density of localised states. Under laser illumination and at open circuit conditions, this enhanced trapping after light soaking inhibits charges from undergoing bimolecular recombination, leading to higher extracted charge densities at long times. At the lower charge densities operating at short circuit conditions and under continuous white light illumination, where bimolecular recombination is much less significant, the J_SC decreases after light soaking due to a reduction in the efficiency of trapped charge carrier extraction.     

Interpretation of protein folding psi values

The structural characterization of transition states is essential for understanding the mechanism of protein folding. Analyzing the effect of mutations on protein stability and folding kinetics in phi-value analysis is commonly used to gain information about the presence of side-chain interactions in transition states. Recently, specific binding of ligands to engineered binding sites was applied to monitor the formation of local structures in transition states (psi analysis). A surprising result from psi analysis was the presence of parallel folding pathways in all reported studies and a major discrepancy between phi and psi values measured in the same protein. Here, we show that psi values cannot be analyzed in the same way as other rate-equilibrium free energy relationships due to the involvement of bimolecular reactions that may have different dissociation constants for the native, unfolded and transition state. As a consequence, psi values reflect the relative binding energy (kappa) of the transition state only for the extreme values of kappa=0 or kappa=1. In all other cases, non-linear rate-equilibrium free-energy relationships (Leffler plots) are observed. This apparently indicates the presence of parallel folding pathways even if folding occurs over a single homogeneous transition state. Consequently, the results from Leffler plots do not yield information about the structural properties of the transition state. This explains the lack of agreement between results from psi analysis and other methods used to characterize protein folding transition states. We further show that the same considerations apply for the analysis of the effect of pH on protein folding.     

Time dependent – density functional theory characterization of organic dyes for dye-sensitized solar cells

We aim at providing better insight into the parameters that govern the intramolecular charge transfer (ICT) and photo-injection processes in dyes for dye-sensitised solar cells (DSSC). Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are utilized to study the geometry, electronic structure, electrostatic potential (ESP) and absorption spectrum, for a representative donor-π bridge-acceptor (D–π–A) dye for DSSC. The coplanar geometry of the dye (D1) facilitates strong conjugation and considerable delocalization originating the π CT interaction from donor to acceptor orbitals and the hyper-conjugative interactions involving Rydberg states. A model simulating the adsorption of the dye on the TiO₂ surface is utilized to estimate binding energies. The effect of fluorine substituents in the π-spacer on the quantum efficiency of DSSCs was investigated. Gibb’s free energy values, redox potentials, excited state lifetime, non-linear optical properties (NLO) and driving forces for D1 and its fluorinated derivatives were computed.     

Tuna cytochrome c at 2.0 A resolution. II. Ferrocytochrome structure analysis.

The x-ray crystal structure analysis of tuna ferrocytochrome c has been extended from 2.45 to 2.0 A resolution. The overall folding is unchanged and is the same as has been reported for tuna ferricytochrome c (Swanson R., Trus, B.L., Mandel, N., Mandel, G., Kallai, O.B., and Dickerson, R.E. (1977) J. Biol. Chem. 252, 759-755). No significant structural differences are observed between oxidation states. Difference map studies using reoxidized crystals of ferrocytochrome c confirm the absence of a conformation change. A detailed analysis of hydrogen bonding shows the presence of six beta or 310 bends of type II with obligatory glycines in the 3rd residue position. This explains 6 of the 10 nearly invariant glycines in the molecule. Close packing contacts account for three more, and only the invariant glycine 1 remains a mystery.     

Surface charges on chloroplast membranes as studied by particle electrophoresis.

1. Particle microelectrophoresis mobility studies have been conducted with chloroplast thylakoid membranes and with isolated intact chloroplasts. 2. The pH dependence of the electrophoretic mobility indicated that at pH values above 4.3 both membrane systems carry a net negative charge. 3. Chemical treatment of thylakoids has shown that neither the sugar residues of the galactolipids in the membrane nor the basic groups of the membrane proteins having pK values between 6 and 10 are exposed at the surface. 4. However, treatment with 1-ethyl-3(3-dimethylaminopropyl)carbodiimide, together with glycine methyl ester, neutralized the negative charges on the thylakoid membrane surface indicating the involvement of carboxyl groups which, because of their pH sensitivity, are likely to be the carboxyl groups of aspartic and glutamic acid residues. 5. The nature of the protein giving rise to the negative surface charges on the thylakoids is not known but is shown not to involve the coupling factor or the light harvesting chlorophyll a/chlorophyll b pigment . protein complex. 6. No significant effect of light was observed on the electrophoretic mobility of either thylakoids or intact chloroplasts. 7. The striking difference in the ability of divalent and monovalent cations to screen the surface charges was demonstrated and explained in terms of the Gouy-Chapman theory. 8. Calculations of the zeta-potentials for thylakoid membranes gave values for the charge density at the plane of shear to be in the region of one electronic charge per 1500--2000 A2. 9. The significance of the results is discussed in terms of cation distribution in chloroplasts and the effect of cations on photosynthetic phenomena.     

Chromatographic study of magnesium and calcium binding to immobilized human serum albumin

The use of immobilized human serum albumin (HSA) as a stationary phase in affinity chromatography has been shown to be useful in resolving optical antipodes or to investigate interactions between drugs and protein. However, to our knowledge, no inorganic ion binding has been studied on this immobilized protein type. To do this, the human serum albumin stationary phase was assimilated to a weak cation-exchanger by working with a mobile phase pH equal to 6.5. A study of the eluent ionic strength effect on ion retention was carried out by varying the buffer concentrations and the column temperatures. The thermodynamic parameters for magnesium and calcium transfer from the mobile to the stationary phase were determined from linear van’t Hoff plots. An enthalpy–entropy compensation study revealed that the type of interaction was independent of the mobile phase composition. A simple model based on the Gouy–Chapman theory was considered in order to describe the retention behavior of the test cations with the mobile phase ionic strength. From this theoretical approach, the relative charge densities of the human serum albumin surface implied in the binding process were estimated at different column temperatures.     

Mechanism of stimulation of renal phosphate transport by 1,25-dihydroxycholecalciferol

Vitamin D has been shown to stimulate renal phosphate transport and to alter membrane phospholipid composition. The present studies examine the possibility that the effects of 1,25(OH)2D3 on phosphate transport are related to its effects on membrane lipids. Arrhenius plots, which relate maximum rates of sodium dependent phosphate uptake into brush-border membrane vesicles to temperature were constructed. Phosphate transport was studied using brush-border membrane vesicles from normal, vitamin D-deficient, and physiologically replete (15 pmol/100 g body weight per 24 h) rats. These plots were triphasic with characteristic, lipid-dependent, slopes (M1,M2,M3) representing activation energies and transition temperatures (T1,T2). Physiologic 1,25(OH)2D3 repletion normalized these plots by stimulating phosphate transport at all temperatures, increasing T2 from 18 +/- 0.7 to 23.5 +/- 0.9 degrees C and decreasing M2 and M3 from -5.8 +/- 0.2 and -10.2 +/- 0.4 to -4.5 +/- 0.4 and -7.7 +/- 0.3, respectively. Pharmacologic (1.2 nmol/100 g per 3 h) 1,25(OH)2D3 treatment resulted in a change in the Arrhenius plot of phosphate transport to a biphasic one with a transition temperature of 30 degrees C. This effect was not blocked by cycloheximide. The Arrhenius plots of glucose transport were triphasic and unchanged with vitamin D repletion. These data support a liponomic mechanism of action for 1,25(OH)2D3 on phosphate transport.