Anion‐Mediated Effects on the Size and Mechanical Properties of Enzymatically Crosslinked Suckerin Hydrogels

The suckerin family of proteins, identified from the squid sucker ring teeth assembly, offers unique mechanical properties and potential advantages over other natural biomaterials. In this study, a small suckerin isoform, suckerin‐12, is used to create enzymatically crosslinked, macro‐scale hydrogels. Upon exposure to specific salt conditions, suckerin‐12 hydrogels contracted into a condensed state where mechanical properties are found to be modulated by the salt anion present. The rate of contraction is found to correlate well with the kosmotropic arm of the Hofmeister anion series. However, the observed changes in hydrogel mechanical properties are better explained by the ability of the salt to neutralize charges in suckerin‐12 by deprotonization or charge screening. Thus, by altering the anions in the condensing salt solution, it is possible to tune the mechanical properties of suckerin‐12 hydrogels. The potential for suckerins to add new properties to materials based on naturally‐derived proteins is highlighted.     

Salting-in/Salting-out Mechanism of Carbon Dioxide in Aqueous Electrolyte Solutions

The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO₂ in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO₂ in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO₄ solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO₄ (0.012) should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO₄ is due to the strongly direct anion-CO₂ interaction. The inconsistency between Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute.     

利用基于Gouy-Chapman模型的离子有效电荷定量表征离子特异性效应

离子特异性效应在固-液界面反应中是普遍存在的. 近期研究指出, 在较低电解质浓度的某些体系中, 离子特异性效应可能并非来源于色散力、经典诱导力、离子半径或水合半径的大小等, 而是界面附近强电场中的离子极化作用. 这种作用可使界面附近的吸附态反号离子被强烈极化(高达经典极化的10⁴倍). 强烈极化的结果将导致离子在界面附近受到的库仑力远远超过离子电荷所能产生的库仑力, 这体现在离子的有效电荷将远大于离子的实际电荷. 因此胶体体系中基于这种强极化的离子有效电荷可以用来定量表征离子特异性效应的强度. 本研究在蒙脱石-胡敏酸混合悬液凝聚过程中发现了Na⁺、K⁺、Ca²⁺、Cu²⁺四种离子的离子特异性效应, 提出了基于激光散射技术测定离子有效电荷的方法, 并成功获得了被强烈极化后的离子有效电荷数值. 实验测得的Na⁺、K⁺、Ca²⁺、Cu²⁺四种离子的有效电荷值分别为: Z_{Na(effective)}=1.46, Z_K(effective)=1.86, Z_{Ca(effective)}=3.92, Z_{Cu(effective)}=6.48.该结果表明: (1) 离子在强电场中的极化将大大提高离子的有效电荷, 从而极大地增强离子所受的库仑作用力;(2) 离子的电子层数越多, 离子极化越强烈, 离子的有效电荷增加越多.     

Raman spectroscopy of alkali halide hydration: hydrogen bond relaxation and polarization

The solute–solvent interaction of salts has a striking impact on various biological and industrial processes but its mechanism remains yet mysterious despite intensive studies since 1888 when Franz Hofmeister established the salt series. A combination of confocal Raman spectroscopy and contact angle measurements has enabled us to resolve the hydrogen bond relaxation (O:H―O, HB) and the associated charge polarization dynamics at different molecular site because of alkali halides hydration. Results show consistently that salt hydration softens the O:H phonon but stiffens H―O phonon cooperatively. The extent of HB relaxation and polarization is proportional to the electronegativity difference and ionic radius, following the order of Hofmeister series: X (R/η) = I (2.2/2.5) > Br (1.96/2.8) > Cl (1.81/3.0) > F (1.33/4.0) ≈ 0 for anions, and Y(R/η) = Na (0.98/0.9) > K (1.33/0.8) > Rb (1.49/0.8) > Cs (1.65/0.8) for cations. Observations suggest that ions create each an electric field that aligns, stretches, and polarizes water molecules, which relaxes the O:H―O bond cooperatively, depresses the molecular dynamics, and enhances the hydration shell viscosity and the skin stress. Exercises also demonstrate that Raman spectroscopy performs as a powerful tool for probing the molecular‐site‐resolved HB network relaxation dynamics in terms of phonon stiffness, molecular fluctuation dynamics, and phonon abundance transition under external stimulus. Copyright © 2016 John Wiley & Sons, Ltd.     

Non-convergent perturbation theory and misleading inferences about parameter relationships: The case of superexchange

We discuss the well-known three-centre cation–anion–cation model for superexchange in insulating transition-metal compounds using limiting expansions for the Anderson–Hubbard model. We find that due to the interfering energy scales in the model, a limiting expression for the superexchange J$J$ for the idealized Mott–Hubbard (M–H) case t?U?Δ$t?U?\Delta$ cannot be formally defined. We further show that the decomposition of the superexchange into range-dependent components is formally invalid. The well-known t⁴$t^4$ superexchange expression, obtained from path-dependent series expansions, is not unique to these systems as it can also be obtained with many other different expansions, in which either the d$d$–p$p$ energy difference Δ$\Delta$ or the d$d$-electron correlation U$U$ can actually be small. Particularly for milder relationships between the parameters, i.e.  t?U?Δ$t?U?\Delta$, the reverse from the usual form of the series expansions can yield better agreement with the exact results. This implies that the fitting of experimental data to the simple expressions derived from path-dependent series expansions can lead to qualitatively incorrect relationships between the parameters, fictitiously within the M–H regime.     

基于超声波和云测试的油井液面测试系统研究

针对目前油井液面深度测试系统测量范围小、误差大、稳定性低的缺点,提出了基于声波法测动液面原理,利用时间序列分析技术、新息自适应卡尔曼滤波技术来实时检测回波信号,进而实现对油井液面深度的高精度测量和噪声处理;选用FPGA和云测试技术成功实现了油井液面深度测量系统的远程化和网络化。基于云测试的油井液面远程监测系统目前已在油田生产现场通过测试,测试结果表明,系统稳定,算法实时、高效,动液面深度测量误差小,测量精度高,能满足实际工程应用。     

结构模态参数的时序分析(ARMAV模型)识别法

本文简述了用时间序列分析(ARMAV 模型)识别结构模态参数的原理,对建模方法进行了分析,并对建模分析中至关重要的初值选择问题进行了讨论,提出了一种有效的初值的选取方法;在模拟计算部分中,用 Wilson-θ积分法模拟了一个三个自由度的振动和低信噪比、大阻尼振动和密集模态等复杂情形,对用时序方法(ARMAV 模型)识别模态参数的能力进行了检验;最后通过对实验数据进行有效的预处理后,用时序方法(ARMAV 模型)识别出一个真实结构(圆盘)的第一、二阶模态参数,并得到结构的完整振型.     

On the estimation of nonlinear time series models

In the present paper, a framework for parametric estimation in nonlinear time series is developed. Strong consistency and asymptotic normality of minimum Hellinger distance estimates for a determined class of nonlinear models are investigated. The main Interest for these estimates is motivated by their robustness under perturbations as it has been emphazized in Beran [2]. The first part of the paper is devoted to the study of some probabilistic properties which ensure the existence and the optimal properties of the estimates     

Ordered Large-Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large-size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting-in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large-pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large-pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.