Effect of Hofmeister Ions on Transport Properties of Aqueous Solutions of Sodium Hyaluronate

Tracer diffusion coefficients obtained from the Taylor dispersion technique at 25.0 °C were measured to study the influence of sodium, ammonium and magnesium salts at 0.01 and 0.1 mol dm⁻³ on the transport behavior of sodium hyaluronate (NaHy, 0.1%). The selection of these salts was based on their position in Hofmeister series, which describe the specific influence of different ions (cations and anions) on some physicochemical properties of a system that can be interpreted as a salting-in or salting-out effect. In our case, in general, an increase in the ionic strength (i.e., concentrations at 0.01 mol dm⁻³) led to a significant decrease in the limiting diffusion coefficient of the NaHy 0.1%, indicating, in those circumstances, the presence of salting-in effects. However, the opposite effect (salting-out) was verified with the increase in concentration of some salts, mainly for NH₄SCN at 0.1 mol dm⁻³. In this particular salt, the cation is weakly hydrated and, consequently, its presence does not favor interactions between NaHy and water molecules, promoting, in those circumstances, less resistance to the movement of NaHy and thus to the increase of its diffusion (19%). These data, complemented by viscosity measurements, permit us to have a better understanding about the effect of these salts on the transport behaviour of NaHy.     

Interactions of Some Hofmeister Cations with Sodium Dodecyl Sulfate in Aqueous Solution

In this work, we have investigated the influence of some alkali metal ions on the Krafft temperature (T_K) and critical micelle concentration (CMC) of a classical ionic surfactant, sodium dodecyl sulfate (SDS), over a wide range of temperature. The alkali metal cations such as Li⁺, Na⁺, Cs⁺, and K⁺ are found to affect the solubility and hence the T_K of the surfactant. It was observed that kosmotropic Li⁺ lowers the T_K of the surfactant. Due to the common ion effect, the solubility of SDS decreases in the presence of Na⁺, resulting in an increase in the T_K. On the other hand, chaotropic K⁺ and Cs⁺, capable of forming contact ion pairs with the chaotropic dodecyl sulfate ion, lower the solubility and hence elevate the T_K. In terms of decreasing the T_K, the ions follow the trend: Li⁺ > Na⁺ > Cs⁺ > K⁺ except for 0.0025 M CsCl. The added cations screen the charge of the micelle surface and facilitate closer packing of the surfactant with a consequent decrease in the CMC. In terms of the effectiveness in lowering the CMC, the ions follow the order: Cs⁺ > K⁺ > Na⁺ > Li⁺. In the presence of added electrolytes, the γ_CMC values are found to be lower than the corresponding values in pure water. The thermodynamic parameters (Gibbs free energy, enthalpy, and entropy changes) of micellization were calculated to gain insights into the mechanism of the process.     

Partition Coefficients of Alkaloids in Biphasic Ionic-Liquid-Aqueous Systems and their Dependence on the Hofmeister Series

The aim of this work is to test the potential of hydrophobic phosphonium-based ionic liquids for the extraction of caffeine and nicotine from aqueous phases through the determination of the alkaloids' partition coefficients. It was found that the caffeine partitioning for the ionic-liquid-rich phase increases with the ionic liquid hydrogen-bonding accepting capability (or water content), while for nicotine a nearly opposite behavior was observed. In addition, both the influence of the ionic concentration of the aqueous solution (ranging from 0.0 mol · kg^?1 to 3.0 mol · kg^?1), and the salt nature (with K- and Na-based salts), in the partitioning of caffeine for the ionic-liquid-rich phase were investigated. The influence of the inorganic salt nature in the alkaloid partitioning for the ionic-liquid-rich phase closely follows the Hofmeister series.     

Influence of Some Hofmeister Anions on the Krafft Temperature and Micelle Formation of Cetylpyridinium Bromide in Aqueous Solution

In this work, the effect of some Hofmeister anions on the Krafft temperature (T_K) and micelle formation of cetylpyridinium bromide (CPB) have been studied. The results show that more chaotropic anions increase, while the less chaotropic ones lower the T_K of the surfactant. More chaotropic I^? and SCN^? form contact ion pairs with the cetylpyridinium ion and reduce the electrostatic repulsion between the CPB molecules. As a result, these ions show salting‐out behavior, with a consequent increase in the T_K. In contrast, less chaotropic Cl^? and NO₃^? increase the activity of free water molecules and enhance hydration of CPB molecules, showing a decrease in the T_K. A rather unusual behavior was observed in the case of SO₄^2? and F^?. These strong kosmotropes shift from their usual position in the Hofmeister series and behave like moderate chaotropes, lowering the T_K of the surfactant. Because of the high charge density and the strong tendency for hydration these ions preferentially remain in the bulk. Rather than forming contact ion pairs, these ions stay away from the CPB molecules, decreasing the T_K of the surfactant. In term of decreasing the T_K, the ions follow the order NO₃^? > SO₄^2? > Cl^? > F^? > Br^? > SCN^? > I^?. The critical micelle concentration (CMC) of the surfactant decreases significantly in the presence of these ions due to the screening of the micelle surface charge by the excess counterions. The decreasing trend of the CMC in the presence of the salts follows the order SCN^? > I^? > SO₄^2? > NO₃^? > Br^? > Cl^? > F^?.     

Protein stabilization and enzyme activation in ionic liquids: specific ion effects

There are still debates on whether the hydration of ions perturbs the water structure, and what is the degree of such disturbance; therefore, the origin of the Hofmeister effect on protein stabilization continues to be questioned. For this reason, it is suggested to use the ‘specific ion effect’ instead of other misleading terms such as Hofmeister effect, Hofmeister series, lyotropic effect, and lyotropic series. This review first discusses the controversial aspect of inorganic ion effects on water structures, and several possible contributors to the specific ion effect of protein stability. Due to recent overwhelming attraction of ionic liquids (ILs) as benign solvents in many enzymatic reactions, this paper further evaluates the structural properties of ILs and molecular‐level interactions in neat ILs and their aqueous solutions. Next, the specific ion effects of ILs on enzyme stability and activity are systematically compared and it is concluded that (a) the specificity of many enzymatic systems in diluted aqueous IL solutions is roughly in line with the traditional Hofmeister series albeit some exceptions; (b) however, the specificity follows a different track in concentrated or neat ILs because other factors (such as hydrogen‐bond basicity, nucelophilicity, and hydrophobicity, etc.) are playing leading roles. In addition, some examples of biocatalytic reactions in IL systems that are guided by the empirical specificity rule are demonstrated. © 2015 Society of Chemical Industry     

Supramolecular Assembly and Binding in Aqueous Solution: Useful Tips Regarding the Hofmeister and Hydrophobic Effects

The self-assembly of structurally discrete entities, and supramolecular chemistry in general, continues to expand into the aqueous realm. To do so, however, requires a firm understanding of the properties of aqueous solution, and how these “change the rules” for binding and assembly relative to organic solvents. In this mini-review we highlight the state-of-the-art understanding of the supramolecular properties of water, and how these influence the design of hosts and self-assembling systems.     

Whole Cell Modeling: From Single Cells to Colonies

A great deal of research over the last several years has focused on how the inherent randomness in movements and reactivity of biomolecules can give rise to unexpected large-scale differences in the behavior of otherwise identical cells. Our own research has approached this problem from two vantage points – a microscopic kinetic view of the individual molecules (nucleic acids, proteins, etc.) diffusing and interacting in a crowded cellular environment; and a broader systems-level view of how enzyme variability can give rise to well-defined metabolic phenotypes. The former led to the development of the Lattice Microbes software – a GPU-accelerated stochastic simulator for reaction-diffusion processes in models of whole cells; the latter to the development of a method we call population flux balance analysis (FBA). The first part of this article reviews the Lattice Microbes methodology, and two recent technical advances that extend the capabilities of Lattice Microbes to enable simulations of larger organisms and colonies. The second part of this article focuses on our recent population FBA study of Escherichia coli, which predicted variability in the usage of different metabolic pathways resulting from heterogeneity in protein expression. Finally, we discuss exciting early work using a new hybrid methodology that integrates FBA with spatially resolved kinetic simulations to study how cells compete and cooperate within dense colonies and consortia.     

电导-紫外串联离子色谱法测定海水中的溴、碘离子

建立了电导-紫外串联离子色谱法测定海水中溴、碘离子的分析方法。样品采用滤膜净化处理,选用TSK Super ICA HR保护柱(4 mm×50 mm)和TSK gel Super IC-HR高性能分析柱(4 mm×250 mm),3.2 mmol/L Na2CO3-1.0 mmol/L Na HCO3为淋洗液。抑制电导和紫外检测器同时检测,碘离子使用紫外法检测以消除氯离子干扰。在优化条件下,整个分析过程8 min内完成。溴离子的方法检出限为2.2μg/L,碘离子的方法检出限为3.6μg/L,相对标准偏差(n=8)分别为1.36%~7.38%、1.97%~8.89%。采用加标法测定,回收率分别为94.5%~105.0%、94.9%~106.1%。     

离子交换纤维对低浓度二甲胺水溶液吸附性能研究

对离子交换纤维(IEF)吸附二甲胺(DMA)的特性进行了研究。等温吸附线研究表明,离子交换纤维对二甲胺的吸附符合Freundlich和Langmuir等温吸附方程。热力学研究表明,Freundlich模型可以很好地模拟二甲胺在离子交换纤维上的交换行为,交换反应的ΔG0,ΔH0,ΔS0,交换过程为自发的吸热过程。动力学研究表明,离子交换纤维对二甲胺的吸附以液膜扩散为主,其交换行为可采用Boyd液膜扩散方程描述。     

谷壳对水中铜镉离子的生物吸附研究

研究了农业副产物谷壳对水中Cu2+、Cd2+的生物吸附过程及其影响因素,以间歇实验的方式考察了吸附时间、溶液初始pH值、谷壳用量、谷壳粒径、吸附温度、金属离子初始浓度等物化参数对吸附过程的影响,研究了其吸附热力学和动力学。结果表明谷壳对Cu2+、Cd2+的吸附均符合Langmuir和Freundlich等温吸附模式,都遵循拟二级动力学模型。利用谷壳做生物吸附剂去除废水中重金属离子,既是对农作物副产物的合理利用,也是重金属废水净化的一种有效方法,谷壳有望成为一种低成本有效、效果好的净化重金属废水的新型生物吸附剂。     

Removal of Cesium Ions from Aqueous Solution by Polyaniline: A Radiotracer Study

The present work deals with the study of uptake behavior of cesium ions by polyaniline applying a radiotracer technique. The parametric study reveals that the increase of adsorbate concentration (10⁻⁸ to 10⁻³ mol dm⁻³) and temperature (303 to 333 K) enhances the removal of the ions and from thermal and kinetic data it is inferred that the adsorption of cesium ions follows first order rate law, obeys Freundlich isotherm and is endothermic in nature. The radiation stability of polyaniline was also investigated by exposing it to a 11.1 GBq (Ra-Be) source associated with gamma dose of 1.72 Gyh⁻¹.     

水热法制备Mg-Fe类水滑石及对水中硫酸根离子吸附的研究

采用尿素分解水热合成法制备Mg-Fe类水滑石,并通过XRD,FF-IR表征.利用Mg-Fe类水滑石焙烧产物对水中硫酸根离子进行一定条件的吸附去除.结果表明,Mg-Fe类水滑石层间阴离子为碳酸根,结晶效果较好.焙烧后Mg-Fe类水滑石在pH =4～8,温度为35℃,对初始浓度500 mg/L硫酸根离子具有较好的吸附能力,90 min可快速达到吸附平衡,吸附数据表明该吸附符合准二级动力学方程,吸附等温线符合Langmuir吸附模型,最大吸附量为151.51 mg/g.     

Nuclear magnetic relaxation of water in ionic‐liquid solutions: determining the kosmotropicity of ionic liquids and its relationship with the enzyme enantioselectivity

The nuclear magnetic relaxations of water in ionic‐liquid (IL) solutions were examined at various IL concentrations in order to better understand their hydration behaviors (in terms of nuclear magnetic resonance (NMR) B′‐coefficients). From these B′‐values of ILs, the individual ion's B′‐coefficients were further calculated based on the additivity. These coefficients represent the hydration behavior (‘kosmotropicity’) of ILs in aqueous solutions. Using these data, a linear correlation was found between enzyme enantioselectivity in aqueous solution and the δ′ parameter (difference in NMR B′‐coefficients of anion and cation). In general, high enzyme enantiomeric ratios (E) could be achieved in solutions of ILs with high δ′ values. Copyright © 2007 Society of Chemical Industry     

Fuel Cells and Biofuel Cells: From Past to Perspectives

This review aims at summarizing the history and state‐of‐the‐art in the areas of fuel and biofuel cells. The paper is addressed to a broad audience including experts and particularly to newcomers and students. Some parts of the review, particularly about fuel cells of different kinds, are rather general and mostly addressed to students, however, sections related to biofuel cells are more specialized and will be interesting for researchers working in this novel and challenging area. Many aspects discussed in the article represent personal opinions of the authors. The article is aimed at providing interesting and easy for reading material representing more concepts than specific experimental data. If the readers get excited about the topic, the authors’ goals will be satisfied.     

Arsenic Removal from Aqueous Solution by Iron Oxide-Coated Biomass: Common Ion Effects and Thermodynamic Analysis

Abstract

A batch study showed that the presence of anions (sulfate, chloride, and nitrate) in solution did not affect the adsorption process of both As(V) and As(III) by iron oxide-coated A. niger biomass. It was found that the presence of Ca²⁺, Fe²⁺, and Mg²⁺ ions at a concentration of 200 mg/L in solution could increase the removal efficiency of As(V) by 86.5%, 95.4%, and 65.8%, respectively. Similarly, the presence of Ca²⁺, Fe²⁺, and Mg²⁺ ions at a concentration of 200 mg/L in solution could increase the removal efficiency of As(III) by 39.3%, 97%, and 8.4%, respectively. The batch adsorption-desorption study showed that the reactions between the arsenic species and the iron oxide-coated A. niger biomass were reversible. Desorption of As(V) and As(III) at neutral pH was approximately 15%. As(V) desorbed more than As(III) in acidic (pH 1.33) and alkaline (pH 12.56) solutions. At a pH of 1.33, 67% of the adsorbed As(V) desorbed, and the percentage of desorbed As(III) was only 47.1% in the same condition. At a solution pH of 12.56, 73.4% of the As(V), and 43.7% of As(III) desorbed. The thermodynamic study showed the spontaneous nature of the sorption of arsenic on IOCB. The high value of the heat of adsorption {ΔH ≈ ? 133 kJ/mol for As(V), and 88.9 k/mol for As(III)} indicated that the mechanism of arsenic sorption was chemisorption.     

Synthesis and Photobehavior of a New Dehydrobenzoannulene-Based HOF with Fluorine Atoms: From Solution to Single Crystals Observation

Hydrogen-bonded organic frameworks (HOFs) are the focus of intense scientific research due their potential applications in science and technology. Here, we report on the synthesis, characterization, and photobehavior of a new HOF (T12F-1(124TCB)) based on a dehydrobenzoannulene derivative containing fluorine atoms (T12F-COOH). This HOF exhibits a 2D porous sheet, which is hexagonally networked via H-bonds between the carboxylic groups, and has an interlayers distance (4.3 Å) that is longer than that of a typical π–π interaction. The presence of the fluorine atoms in the DBA molecular units largely increases the emission quantum yield in DMF (0.33, T12F-COOH) when compared to the parent compound (0.02, T12-COOH). The time-resolved dynamics of T12F-COOH in DMF is governed by the emission from a locally excited state (S1, ~0.4 ns), a charge-transfer state (S1(CT), ~2 ns), and a room temperature emissive triplet state (T1, ~20 ns), in addition to a non-emissive triplet structure with a charge-transfer character (T1(CT), τ = 0.75 µs). We also report on the results using T12F-ester. Interestingly, FLIM experiments on single crystals unravel that the emission lifetimes of the crystalline HOF are almost twice those of the amorphous ones or the solid T12F-ester sample. This shows the relevance of the H-bonds in the photodynamics of the HOF and provides a strong basis for further development and study of HOFs based on DBAs for potential applications in photonics.     

聚酰胺吸附硝基苯酚的热力学与机理探讨

探讨了水溶液中聚酰胺树脂吸附硝基苯酚的热力学特性及其机理，测定了不同温度下的吸附等温线。结果表明：在稀溶液中吸附硝基苯酚均符合Freundlich或Langmuri模型；聚酰胺对苦味酸、2，4—二硝基苯酚的吸附为熵驱动的吸热、熵增的自发过程；对对硝基苯酚的吸附为焓驱动的放热、熵减的自发过程；硝基苯酚主要以酚羟基及邻位硝基与聚酰胺中的酰胺基形成氢链吸附；吸附过程均具有物理吸附特征，主要为氢链吸附和范德华吸附。     

Liquid-Liquid Extraction of Acids by a Malonamide: II-Anion Specific Effects in the Aggregate-Enhanced Extraction Isotherms

Non-electrostatic ion-specific effects are strong for anions when water is involved. We study here the thermodynamic equilibrium of a water-in-oil microemulsion stabilized by a surface-active extractant in a Winsor-II regime. Acid extraction isotherms for different anions located differently in the Hofmeister series have been investigated. A Langmuir like model was written for the specific case of acids treated as electrolytes, describing acid extraction as the adsorption of extracted electrolytes on the polar/apolar interface of the aggregates. Except for sulfate, isotherms can be described at first approximation as simple Langmuir-type isotherms when plotted as a function of the acid activity in the aqueous phase. The validity of the model being hence demonstrated, acid extraction free energies could be derived and compared, taking into account the effect of the anion position in the Hofmeister series. The case of phosphate, chloride, and sulfate as kosmotropes can be distinguished. They are significantly extracted, only above a threshold since the sphere-to-rod transition of the reverse aggregates has to be triggered by high chemical potential of the acid required to compensate anion dehydration.