C6-oxidized cellulose: Ion interactions with mono- and divalent cations

The conformational behavior of different molecular weight fractions of a synthetic C6-oxidized derivative of cellulose were investigated by means of capillary viscometry, CD, and microcalorimetric measurements. Experiments were carried out in the presence of either monovalent or divalent counterions. The experimental data indicated that C6-oxidized cellulose can assume an ordered extended conformation at low ionic strength, induced by the intrachain repulsions of negative charges. This conformation was suggested to be very similar to the fully extended structure of cellulose. In addition to this, upon increasing the ionic strength, a conformational transition of the order-to-disorder type occurred. In fact, the screening of the electrostatic repulsions introduced a number of conformational kinks into the cellulosic backbone, which enabled the polymer to assume a more coiled conformation hence producing less viscous aqueous solutions. © 1998 John Wiley & Sons, Inc. Biopoly 45: 157–163, 1998     

Coulombic and noncoulombic effect of polyanions on cytochrome c structure

The properties of the complexes of ferricytochrome c with two different polyanions—poly(vinylsulfate) and poly(4-styrene-sulfonate)—with a comparable charge density but with the different size of the uncharged part of their molecules have been studied by means of optical spectroscopy, differential scanning calorimetry, and gel chromatography. Ferriccytochrome c formed a complex with the former one through coulombic interactions and remained in a native-like state. The addition of the second polyanion to a solution of ferric cytochrome c at a low ionic strength, pH 7.0, resulted in profound conformational change in the hydrophobic core of protein (opening of the heme crevice with a perturbation of the methionine 80-heme iron bond and the hydrophobic core of the protein). These may be understood as an involvement of noncoulombic (hydrophobic, H-bonding) interactions of the uncharged part of the polyanion molecule. Conformational changes and the observed shift in acidic transition from low spin to high spin state of ferric cytochrome c detected in the presence of the polyanions may have biological implication in understanding the origin of conformational changes in proteins induced in the course of their interaction with membrane lipids and membrane proteins. © 1998 John Wiley & Sons, Inc. Biopoly 46: 145–154, 1998     

High pressure effect on the main transition from the ripple gel P′β phase to the liquid crystal (Lα) phase in dipalmitoylphosphatidylcholine. Microcalorimetric study

Scanning microcalorimetry has been used to study the high pressure effect on the main transition from the ripple gel P′_β phase to the liquid crystal (L_α) phase in DPPC (dipalmitoylphosphatidylcholine). It has been demonstrated that an increase of the pressure by 200 MPa shifts the transition to higher temperatures by 36.4 degrees. The pressure increase does not affect the cooperativity of transition but reduces noticeably its enthalpy. The changes of the molar partial volume, isothermal compressibility as well as volume thermal expansibility during transition in DPPC suspension have been estimated. It has been shown that monovalent ions (Na⁺, Cl⁻) in solution slightly affect the main thermodynamic parameters of the transition. Calcium ions significantly decrease distinction in compressibility and thermal expansibility between liquid-crystal and ripple gel phases of lipid suspension, which in its turn reflects less difference in their volume fluctuations.     

Sorption of fluorinated herbicides to plant biomass-derived biochars as a function of molecular structure

Biochars produced at different heat treatment temperatures (HTT) are molecularly distinct and thus expected to show variable sorbent characteristics. We investigated the difference in sorption behavior of norflurazon (NORO) and fluridone (FLUN) to biochars from wood and grass feedstocks produced at different HTT. Amorphous biochars (HTT = 400 °C) exhibited the highest sorption parameter (K_OC) for the two herbicides, emphasizing the importance of amorphous structural arrangement of aromatic moieties in these chars. Negative correlation between biochar aromaticity and isotherm nonlinearity (n) suggests that the n values were related mainly to total aromatic C content, not to that in the individual phases. Sorption of FLUN and NORO to low-temperature biochars (HTT = 400 °C) was about 1100 times and 6400 times greater, respectively, than a sediment sample, confirming that applications of low-temperature biochars to arable soils may reduce the mobility of FLUN and NORO, thus preventing unwanted herbicide leaching and subsequent contamination of sensitive water bodies.     

How are pharmaceutical and personal care products (PPCPs) removed from urban wastewaters?

The presence of bioactive trace pollutants such as pharmaceuticals and ingredients of personal care products (PPCPs) in different environmental compartments (rivers, lakes, groundwaters, sediments, etc.) is an emerging issue due to the lack of existing information about the potential impact associated with their occurrence, fate and ecotoxicological effects. Due to the low PPCP concentrations reported in wastewaters (ppb or ppt) and their complex chemical structure, common technologies used in sewage and drinking water treatment plants may not be efficient enough to accomplish their complete removal. Information about physico-chemical characteristics such as acidity, lipophilicity, volatility and sorption potential is a useful tool to understand the different removal patterns observed. In order to perform an accurate overall mass balance along the different units of sewage treatment plants, it is necessary to gather information not only about the presence of micropollutants in the aqueous phase, but also on the fraction sorbed onto solids. Since only some PPCPs are very well eliminated by conventional sewage treatment configurations, new strategies such as modification of operating conditions (e.g. solids retention time), implementation of new technologies (e.g. biomembrane reactors) or additional advanced post-treatment steps (e.g. oxidation, adsorption, membranes) have been suggested for an increased efficiency.     

壳聚糖金属离子配合物吸附尿素性能研究

由于尿素吸附剂存在吸附容量低、吸附选择性差、生物相容性和血液相容性差等缺点,使人工肾和口服尿素吸附剂的应用受到限制．近几年,尿素吸附材料方面的研究进展较快,主要有：１９９０年,藤田良枝用活性炭作尿素吸附剂,吸附量为９０ｍｇ／ｇ（尿素初始浓度为２１００ｍｇ／Ｌ）,吸附容量低,且微炭粒易脱落,有造成栓塞的危险,不宜作人工肾材料［１］;１９９３年,何炳林等用交联聚丙烯酸固载化氧化β环糊精作尿素吸附材料,吸附容量较高,为８２１ｍｇ／ｇ（尿素的初始浓度为１３００ｍｇ／Ｌ）．由于其利用的是Ｓｃｈｉｆｆ…     

Thermodynamic analysis of the binding of component enzymes in the assembly of the pyruvate dehydrogenase multienzyme complex of Bacillus stearothermophilus

The peripheral subunit-binding domain (PSBD) of the dihydrolipoyl acetyltransferase (E2, EC 2.3.1.12) binds tightly but mutually exclusively to dihydrolipoyl dehydrogenase (E3, EC 1.8.1.4) and pyruvate decarboxylase (E1, EC 1.2.4.1) in the pyruvate dehydrogenase multienzyme complex of Bacillus stearothermophilus. Isothermal titration calorimetry (ITC) experiments demonstrated that the enthalpies of binding (DeltaH degrees ) of both E3 and E1 with the PSBD varied with salt concentration, temperature, pH, and buffer composition. There is little significant difference in the free energies of binding (DeltaG degrees = -12.6 kcal/mol for E3 and = -12.9 kcal/mol for E1 at pH 7.4 and 25 degrees C). However, the association with E3 was characterized by a small, unfavorable enthalpy change (DeltaH degrees = +2.2 kcal/mol) and a large, positive entropy change (TDeltaS degrees = +14.8 kcal/mol), whereas that with E1 was accompanied by a favorable enthalpy change (DeltaH degrees = -8.4 kcal/mol) and a less positive entropy change (TDeltaS degrees = +4.5 kcal/mol). Values of DeltaC(p) of -316 cal/molK and -470 cal/molK were obtained for the binding of E3 and E1, respectively. The value for E3 was not compatible with the DeltaC(p) calculated from the nonpolar surface area buried in the crystal structure of the E3-PSBD complex. In this instance, a large negative DeltaC(p) is not indicative of a classical hydrophobic interaction. In differential scanning calorimetry experiments, the midpoint melting temperature (T(m)) of E3 increased from 91 degrees C to 97.1 degrees C when it was bound to PSBD, and that of E1 increased from 65.2 degrees C to 70.0 degrees C. These high T(m) values eliminate unfolding as a major source of the anomalous DeltaC(p) effects at the temperatures (10-37 degrees C) used for the ITC experiments.     

Microcalorimetric study of the toxic effect of sodium selenite on the mitochondria metabolism of Carassius auratus liver

The fundamental thermogenesis curves of the metabolic process of liver mitochondria from Carassius auratus and the toxic effect of Na₂SeO₃ on it were studied by using an LKB-2277 bioactivity monitor, ampoule method, at 28°C. From the thermogenesis curves, the thermokinetic equations were established under different conditions. The kinetics show that a low concentration of Na₂SeO₃ (1–4 mg/L) had promoting action on the metabolism process of Carassius auratus liver mitochondria, but that a high concentration of Na₂SeO₃ (8–16 mg/L) inhibited the mitochondria metabolism.     

Compact dimension of denatured states of staphylococcal nuclease

Fluorescence and circular dichroism stopped-flow have been widely used to determine the kinetics of protein folding including folding rates and possible folding pathways. Yet, these measurements are not able to provide spatial information of protein folding/unfolding. Especially, conformations of denatured states cannot be elaborated in detail. In this study, we apply the method of fluorescence energy transfer with a stopped-flow technique to study global structural changes of the staphylococcal nuclease (SNase) mutant K45C, where lysine 45 is replaced by cysteine, during folding and unfolding. By labeling the thiol group of cysteine with TNB (5,5'-dithiobis-2-nitrobenzoic acid) as an energy acceptor and the tryptophan at position 140 as a donor, distance changes between the acceptor and the donor during folding and unfolding are measured from the efficiency of energy transfer. Results indicate that the denatured states of SNase are highly compact regardless of how the denatured states (pH-induced or GdmCl-induced) are induced. The range of distance changes between two probes is between 25.6 and 25.4 A while it is 20.4 A for the native state. Furthermore, the folding process consists of three kinetic phases while the unfolding process is a single phase. These observations agree with our previous sequential model: N(0) left arrow over right arrow D(1) left arrow over right arrow D(2) left arrow over right arrow D(3) (Chen et al., J Mol Biol 1991;220:771-778). The efficiency of protein folding may be attributed to initiating the folding process from these compact denatured structures.