Nanoparticles: scaffolds for molecular recognition

Monolayer and mixed-monolayer protected clusters (MPCs and MMPCs) have great potential to combine molecular functionality with the intrinsic properties of nanometer-sized scaffolds. This synergy can be used to create complex functional devices, including redox-active, electronic, or magnetic storage devices, solution-based sensors, and highly efficient catalysts. This review outlines some of the recent developments in nanoscale receptors based on synthetic and nonbiological recognition elements. In these nanoparticle systems, molecular recognition is achieved by covalent attachment of receptors on the nanoparticles coupled with noncovalent interactions to target substrates. Synthetic host-guest systems, hydrogen bonding, change in redox states, pi-pi stacking, rotaxane formation, and ion recognition are the main topics covered in this review.     

Neighbouring-group Influence on the Ring Opening of Some 2-Alkyl-1,1,2-tribromocyclopropanes under Phase-transfer Conditions

Several 2-alkyl-1,1,2-tribromocyclopropanes were treated with sodium hydroxide and ethanol under phase-transfer conditions. Ring opening gave mixtures of the corresponding acetylenic diethyl ketals and acetals. When the steric bulk of the alkyl substituent was increased acetal formation dominated, and in the case of 1,1,2-tribromo-2-(tert-butyl)cyclopropane, the acetal was formed as the only product.     

Trident Nano-Indexing the Proteomics Table: Next-Version Clustering of Iron Carbide NPs and Protein Corona

Protein corona composition and precise physiological understanding of differentially expressed proteins are key for identifying disease biomarkers. In this report, we presented a distinctive quantitative proteomics table of molecular cell signaling differentially expressed proteins of corona that formed on iron carbide nanoparticles (NPs). High-performance liquid chromatography/electrospray ionization coupled with ion trap mass analyzer (HPLC/ESI-Orbitrap) and MASCOT helped quantify 142 differentially expressed proteins. Among these proteins, 104 proteins showed upregulated behavior and 38 proteins were downregulated with respect to the control, whereas 48, 32 and 24 proteins were upregulated and 8, 9 and 21 were downregulated CW (control with unmodified NPs), CY (control with modified NPs) and WY (modified and unmodified NPs), respectively. These proteins were further categorized on behalf of their regularity, locality, molecular functionality and molecular masses using gene ontology (GO). A STRING analysis was used to target the specific range of proteins involved in metabolic pathways and molecular processing in different kinds of binding functionalities, such as RNA, DNA, ATP, ADP, GTP, GDP and calcium ion bindings. Thus, this study will help develop efficient protocols for the identification of latent biomarkers in early disease detection using protein fingerprints.     

Inclusion complex formation of β-cyclodextrin and Naproxen: a study on exothermic complex formation by differential scanning calorimetry

Inclusion complex formation between β-cyclodextrin and Naproxen was investigated using differential scanning calorimetry (DSC) as a function of the β-cyclodextrin-to-Naproxen molar ratio, ranging from 0:5:1 to 5:1. When these mixtures are heated above the melting temperature of Naproxen, an exothermic peak is observed at a temperature slightly higher than the melting peak of Naproxen. This peak, which has not been previously reported, has been interpreted as an exothermic energy of inclusion complex formation. The magnitude of this complex formation peak was found to be dependent upon the composition of the β-cyclodextrin and Naproxen mixture and increased in magnitude to a maximum value at a β-cyclodextrin:Naproxen molar ratio of 2:1. In addition, Naproxen recrystallization and re-melting peaks seen in the cooling and re-heating scans, respectively, decreased in magnitude with increasing molar ratio and totally disappeared for the mixture with 5:1 of β-cyclodextrin to Naproxen ratio indicative of complete inclusion of Naproxen in the cyclodextrin cavities. Complete inclusion was further reflected by the disappearance of key Naproxen peaks in Fourier transform infrared spectra of samples recovered from DSC experiments. The large excess of β-cyclodextrin needed to fully complex the Naproxen was found to be due to slow kinetics. Increasing the hold time after the initial melting led to inclusion efficiencies up to 95 % even for the 2:1 mixture. These experiments suggest that ratios of β-cyclodextrin:Naproxen 2:1 or greater facilitate the process by increasing the presence of cyclodextrin molecules in the close proximity of the drug molecules and lead to high inclusion efficiencies.     

Polyoxotungstate Archetype {P4W27} and its 3d Derivatives

The propensity of the new, phenylphosphonate-stabilized polyoxotungstate [(C₆H₅P^VO)₂P₄W₂₄O₉₂]¹⁶⁻ to act as a precursor for new 3d metal-functionalized polyanions has been investigated. Reactions with Mn^II and Cu^II induce the formation of the previously unknown polyoxotungstate archetype {P₄W₂₇}, isolated as salts of the polyanions [Na⊂{Mn^II(H₂O)}{WO(H₂O)}P₄W₂₆O₉₈]¹³⁻ ( 1 ) and [K⊂{Cu^II(H₂O)}{W(OH)(H₂O)}P₄W₂₇O₉₉]¹⁴⁻ ( 2 ), which were characterized in the solid state (single-crystal X-ray diffraction, elemental and TG analyses, IR spectroscopy, SQUID magnetometry) and in aqueous solution (UV/Vis spectroscopy, cyclic voltammetry).     

Review of peridynamics for multi-physics coupling modeling

广义来说, 近场动力学(peri-dynamics,PD)是假设每个物质点在承受一定范围内的非接触相互作用下,研究整个物理系统演化过程的理论,为涉及非连续和非局部相互作用的问题提供了一个统一的数学框架,具有广泛的适用性.在简要介绍诸多工程对于多物理场模型和数值计算软件的迫切需求后,针对现有商用软件在处理结构非连续演化问题时遇到的瓶颈,引入近场动力学理论和方法. 概述近场动力学固体力学模型,系统阐述近场动力学扩散模型和近场动力学多物理场耦合建模的研究现状和进展,主要涉及电子元器件、电子封装和岩土工程领域的多物理场耦合建模,包括热--力、湿--热--力、热--氧、热--力--氧、力--电、热--电、力--热--电、多孔介质的水--力流固相互作用等非耦合、半耦合与完全耦合模型,强调发展耦合方程数值解法的重要性.最后对扩散问题和多物理场耦合问题的近场动力学理论模型、数值算法和工程应用做进一步展望.     

A cracked beam or plate transversely loaded by a stamp

In this paper the problem of an infinite elastic beam or a plate containing a crack is considered. The medium is loaded transversely through a stamp which may be rigid or elastic. The problem is a coupled crack-contact problem which cannot be solved by treating the crack and contact problems separately and by using a superposition technique. First the Green's functions for the general case are obtained. Then the integral equations for a cracked infinite strip loaded by a frictionless stamp are obtained. With the question of fracture in mind, the primary interest in the paper has been in calculating the stress intensity factors. The results are given for a rigid flat stamp with sharp edges and for an elastic curved stamp. The effect of friction at the supports on the stress intensity factors is also studied and a numerical example is given.     

A clamped rectangular plate containing a crack

In this paper the general problem of a rectangular plate clamped along two parallel sides and containing a crack parallel to the clamps is considered. The problem is formulated in terms of a system of singular integral equations and the asymptotic behaviour of the stress state near the corners is investigated. Numerical examples are considered for a clamped plate without a crack and with a centrally located crack, and the stress intensity factors and the stresses along the clamps are calculated.