Hydrophobicity-induced drying transition in alkanethiol self-assembled monolayer—water interface

During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance. This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading to the possible creation of a hydrophobic interfacial gap.     

Sol–Gel-Derived Corrosion-Protection Coatings

There is a current need for alternative coatings that can provide corrosion resistance to metals or alloy surfaces due to the environmental hazards posed by conventional coatings. Herein, we report on novel organically-modified sol–gel coatings for the protection of metal and alloy surfaces. The basic concept of chemical conversion of metal surfaces is based on deposition of a hydrophobic, nonporous sol–gel barrier layer for surface protection and corrosion prevention. The properties of these organosilica coatings can be tuned by varying the composition of precursors. The evaluation of hydrophobicity, adhesive strength, and anticorrosion properties of organically-modified sol–gel derived coatings suggests their potential utility as technologically-compatible alternatives to conventional coatings.     

Influences of the Hydrophobicity of the Heme-binding Pocket on the Properties and Functions of Cytochrome b_5 Mutants

IntroductionElectrontransferreactionsarethekeystepsinphoto synthesis ,respirationandmanyotherbiochemicalprocess es.1Cytochromeb5isaredoxproteinexistingwidelyinnature ,whichactsasanelectron carrierduringvariouselectrontransferprocessesinthebiologicalsystem .2Cytochromeb5isamembraneproteinwithmolecularweightofapproximately 16kDa ,ofwhichthehydrophobicC terminaldomainanchorscytochromeb5tothemem brane ,andthehydrophilicN terminaldomaincontainshemeprostheticgroupandexhibitsthebiologicalfunctionsof…     

Adsorption Isotherm of Water Vapor and Its Large Hysteresis on Highly Ordered Mesoporous Silica

The first and second adsorption–desorption isotherms of water vapor on a new mesoporous material derived from kanemite have been measured. The isotherms show unusual type V isotherms and large hysteresis. The type V isotherms, which have never been observed for the other adsorbates, suggest that the mesoporous material has a hydrophobic surface, although the hydrophobicity decreased after treatment with water vapor because of rehydration of the surface. The significantly large hysteresis could be explained by the difference in contact angle between adsorption and desorption.     

Preparation of a novel molecularly imprinted polymer using a water-soluble crosslinking agent

A molecularly imprinted polymer was prepared using a water-soluble crosslinking agent. An ionic complex was utilized as the assembly for the template molecule and the functional monomer, and water as porogenic solvent during preparation of the imprinted polymer. The results of chromatographic evaluations for the prepared polymer suggested that the polymer had much lower hydrophobicity compared with usual octadecyl group bonded silica or the usual molecular imprinted polymer prepared from ethyleneglycol dimethacrylate, and the selective recognition ability for template molecule in the completely aqueous condition.     

Ti接枝MCM-41催化剂的结构设计及化学亲和选择性研究

 用二氯化钛茂作为活性物种的来源，利用Si－MCM－41催化剂表面羟基的反应性，得到了Ti接枝MCM－41催化剂的两种结构模型．结构表征结果表明，Ti接枝MCM－41催化剂不仅长程结构好，孔径分布均一，而且催化剂表面活性中心含量高．两种结构模型催化剂上芳烃羟化反应性能表明，Ti接枝MCM－41催化剂表面的亲水／憎水性可以在较宽的范围内调变，从而可实现控制芳烃羟化的化学亲和选择性．另外，研究结果还表明，Ti接枝MCM－41催化剂具有很好的活性稳定性．     

Optimization of Ormosil Films for Optical Sensor Applications

Recent work has indicated that Ormosil films, fabricated from organically modified precursors, produce better sensor performance for some specific applications, compared to films fabricated from conventional sol-gel precursors such as TEOS or TMOS. This paper aims to compare film properties and sensor behavior for films fabricated from tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) silica precursors and both methyltrimethoxysilane (MTMS) and methyltriethoxysilane (MTES) organically modified precursors. Microstructural differences, for example, porosity changes due to the different precursor backbone structures, are interrogated by monitoring oxygen gas and aqueous-phase sensor response. Oxygen sensing using these films is enabled by incorporating in the films an oxygen-sensitive ruthenium dye whose fluorescence is quenched in the presence of oxygen. Film properties such as thickness, thickness stabilization time, as well as sensor response, are discussed in terms of relative hydrolysis and condensation behavior for the different precursors. Film hydrophobicity, an issue which has been identified as being of crucial importance for optimum dissolved oxygen sensor response, is discussed and contact angle measurements are used to investigate the degree of hydrophobicity for different film types. The main motivation for this work is film optimization for optical gas-phase and dissolved oxygen sensors.     

Hydrophobic Molecular Similarity from MST Fractional Contributions to the Octanol/water Partition Coefficient

Summary The use of a recently proposed hydrophobic similarity index for the alignment of molecules and the prediction of their differences in biological activity is described. The hydrophobic similarity index exploits atomic contributions to the octanol/water transfer free energy, which are evaluated by means of the fractional partitioning scheme developed within the framework of the Miertus-Scrocco-Tomasi continuum model. Those contributions are used to define global and local measures of hydrophobic similarity. The suitability of this computational strategy is examined for two series of compounds (ACAT inhibitors and 5-HT₃ receptor agonists), which are aligned to maximize the global hydrophobic similarity using a Monte Carlo-simulated protocol. Indeed, the concept of local hydrophobic similarity is used to explore structure–activity relationships in a series of COX-2 inhibitors. Inspection of the 3D distribution of hydrophobic/hydrophilic contributions in the aligned molecules is valuable to identify regions of very similar hydrophobicity, which can define pharmacophoric recognition patterns. Moreover, low similar regions permit to identify structural elements that modulate the differences in activity between molecules. Finally, the quantitative relationships found between the pharmacological activity and the hydrophobic similarity index points out that not only the global hydrophobicity, but its 3D distribution, is important to gain insight into the activity of molecules. J.M.M. and S.P. have contributed equally to this study.     

Lipophilicity in PK design: methyl, ethyl, futile

Lipophilicity, often expressed as distribution coefficients (log D) in octanol/water, is an important physicochemical parameter influencing processes such as oral absorption, brain uptake and various pharmacokinetic (PK) properties. Increasing log D values increases oral absorption, plasma protein binding and volume of distribution. However, more lipophilic compounds also become more vulnerable to P450 metabolism, leading to higher clearance. Molecular size and hydrogen bonding capacity are two other properties often considered as important for membrane permeation and pharmacokinetics. Interrelationships among these physicochemical properties are discussed. Increasing size (molecular weight) often gives higher potency, but inevitably also leads to either higher lipophilicity, and hence poorer dissolution/solubility, or to more hydrogen bonding capacity, which limits oral absorption. Differences in optimal properties between gastrointestinal absorption and uptake into the brain are addressed. Special attention is given to the desired lipophilicity of CNS drugs. In examples using -blockers, Ca channel antagonists and peptidic renin inhibitors we will demonstrate how potency and pharmacokinetic properties need to be balanced.