An explanation of the unusual strength of the hydrogen bond in small water clusters

We seek to explain why the hydrogen bond possesses unusual strength in small water clusters that account for many of the complex behaviors of water. We have investigated and visualized the donation of covalent character from covalent (sigma) to hydrogen bonds by calculating the eigenvector coupling properties of quantum theory of atoms in molecules (QTAIM), stress tensor σ ( r ), and Ehrenfest Force F ( r ) on the F ( r ) molecular graph. The next-generation three-dimensional (3-D) bond-path framework sets are presented, and only the F ( r ) bond-path framework sets reproduce the earlier finding on the coupling between covalent (sigma) and hydrogen bonds that possess a degree of covalent character. Exploration of the bond-path between the covalent (sigma) and hydrogen bond's critical points provides an explanation for the previously obtained coupling results. The directional character of the covalent (sigma) and hydrogen bonds' 3-D bond-path framework sets for the F ( r ) explains differences found in the earlier results from QTAIM and the stress tensor σ ( r ).     

A simple,rapid and effective protocol for synthesis of bis(pyrazolyl)methanes using nickel–guanidine complex immobilized on MCM-41

Research on Chemical Intermediates - In this paper, a rapid, easy and very efficient method for the synthesis of bis(pyrazolyl)methanes has been reported in the presence of nickel–guanidine...     

Thermal stability and dynamic mechanical thermal analysis of epoxy thermosets possessing N,N′-disubstituted pyromellitimide units

Abstract

In this work, three epoxy resins including diglycidyl ethers of N,N′-bis(2-hydroxyethyl)pyromellitimide (DIDGE), bisphenol-A (BADGE), and polyethylene glycol (PEDGE) were isothermally cured by an amine curing agent possessing N,N′-disubstituted pyromellitimide units (denoted by DIDAM). DIDGE resin was synthesized from the reaction of N,N′-bis(2-hydroxyethyl)pyromellitimide with an excess of epichlorohydrin. Also, DIDAM curing agent was prepared from the reaction of pyromellitic dianhydride with an excess of ethylene diamine. Completion of the isothermal curing processes was approved by both Fourier transform-infrared spectroscopy and non-isothermal differential scanning calorimetry (DSC). The DSC traces showed only the phase transitions related to the thermal degradation of the resulting thermosets. According to the thermogravimetric analyses, the DIDGE/DIDAM thermoset showed higher thermal stability at temperatures above 425?°C than the other two thermosets. While BADGE/DIDAM and PEDGE/DIDAM thermosets showed about 70% weight loss in the thermal range of 400–850?°C, DIDGE/DIDAM thermoset was encountered with only about 40% weight loss. The glass transition temperatures (T_g ) of the resulting thermosets were determined using tan δ vs temperature plots obtained from dynamic mechanical thermal analysis. The T_g values of BADGE/DIDAM, DIDGE/DIDAM, and PEDGE/DIDAM thermosets were found to be 211?°C, 189?°C, and 81?°C, respectively.     

In Vivo Imaging of the Tumor‐Associated Enzyme NCEH1 with a Covalent PET Probe

Herein, we report the development of an ¹⁸F‐labeled, activity‐based small‐molecule probe targeting the cancer‐associated serine hydrolase NCEH1. We undertook a focused medicinal chemistry campaign to simultaneously preserve potent and specific NCEH1 labeling in live cells and animals, while permitting facile ¹⁸F radionuclide incorporation required for PET imaging. The resulting molecule, [¹⁸F]JW199, labels active NCEH1 in live cells at nanomolar concentrations and greater than 1000‐fold selectivity relative to other serine hydrolases. [¹⁸F]JW199 displays rapid, NCEH1‐dependent accumulation in mouse tissues. Finally, we demonstrate that [¹⁸F]JW199 labels aggressive cancer tumor cells in vivo, which uncovered localized NCEH1 activity at the leading edge of triple‐negative breast cancer tumors, suggesting roles for NCEH1 in tumor aggressiveness and metastasis.     

Seed priming with cold plasma improved seedling performance,secondary metabolism,and expression of deacetylvindoline O-acetyltransferase gene in Catharanthus roseus

The plasma-primed seeds of Catharanthus roseus were cultured in a hormone-free culture medium under sterile conditions. Plasma of 30 or 60 s improved root length (mean = 41.4%) and biomass (mean = 47%), whereas plasma of 90 s delayed plant growth. The plasma treatments enhanced concentrations of photosynthetic pigments and soluble phenols. Plasma of 90 s increased the proline level. With a similar trend, plasma priming induced activities of phenylalanine ammonia-lyase, catalase (about twofold) and peroxidase (31%) enzymes. Plasma also upregulated the expressions of deacetylvindoline O-acetyltransferase gene by an average of 7.8 times. Similarly, the plasma-treated seedlings contained higher concentrations of alkaloids (mean = 72%). Here, molecular evidence is provided on the plasma-associated modifications in secondary metabolism.     

The Effect of the Protein Synthesis Entropy Reduction on the Cell Size Regulation and Division Size of Unicellular Organisms

The underlying mechanism determining the size of a particular cell is one of the fundamental unknowns in cell biology. Here, using a new approach that could be used for most of unicellular species, we show that the protein synthesis and cell size are interconnected biophysically and that protein synthesis may be the chief mechanism in establishing size limitations of unicellular organisms. This result is obtained based on the free energy balance equation of protein synthesis and the second law of thermodynamics. Our calculations show that protein synthesis involves a considerable amount of entropy reduction due to polymerization of amino acids depending on the cytoplasmic volume of the cell. The amount of entropy reduction will increase with cell growth and eventually makes the free energy variations of the protein synthesis positive (that is, forbidden thermodynamically). Within the limits of the second law of thermodynamics we propose a framework to estimate the optimal cell size at division.     

Three-Component Reaction of Triphenylphosphine,Acetylenic Esters,and Arylsulfonyl Hydrazides or Aryl Hydrazines: An Efficient One-Pot Synthesis of Stable β-Nitrogen-Substituted Phosphorus Ylides

The three-component reaction between dialkyl acetylenedicarboxylates and triphenylphosphine in the presence of arylsulfonyl hydrazides or aryl hydrazines produces highly functionalized, salt-free phosphorus ylides in excellent yields.     

A non-adapted sparse approximation of PDEs with stochastic inputs

We propose a method for the approximation of solutions of PDEs with stochastic coefficients based on the direct, i.e., non-adapted, sampling of solutions. This sampling can be done by using any legacy code for the deterministic problem as a black box. The method converges in probability (with probabilistic error bounds) as a consequence of sparsity and a concentration of measure phenomenon on the empirical correlation between samples. We show that the method is well suited for truly high-dimensional problems.     

Characterization of a peptide family from the skin secretion of the Middle East Tree Frog Hyla savignyi by composition‐based de novo sequencing

A new tryptophyllin‐like peptide family was found in the skin secretion of the tree frog Hyla savignyi. Peptides were characterized by database‐independent sequencing strategies and specific ion fragmentation features were investigated. Skin secretions from specimens of Hyla savignyi were collected by mild electrical stimulation. Peptides were separated by reversed‐phase nano‐high‐performance liquid chromatography (nanoHPLC) and mass spectra were acquired online by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). Peptides were characterized by manual de novo sequencing and by composition‐based sequencing (CBS), appearing mostly as C‐terminal free acids and as their acid amide analogs. Amide peptides yielded lower intensities of y‐type ions after collision‐induced dissociation (CID) than their acid analogs. A mechanism of internal b‐ion formation (positive ion mode) and of CO₂ elimination (negative ion mode) is proposed. We also exemplified phenomena such as the proline effect and formation of non‐direct sequence ions after sequence rearrangements. The occurrence of rearrangement products, of internal ions and of the proline effect made the CID spectra highly complex. CBS analysis nevertheless resulted in successful and highly reliable sequence analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Three-Component Reaction of Triphenylphosphine,Dimethyl Acetylenedicarboxylate,and Aldehyde Benzoylhydrazones: An Efficient One-Pot Synthesis of Stable Phosphorus Ylides

Protonation of the reactive 1:1 intermediate produced in the reaction between dimethyl acetylenedicarboxylate and triphenylphosphine by benzoylhydrazones leads to vinylphosphonium salts, which undergo Michael addition with the conjugate base of the NH acid to produce highly fanctionalized, salt-free phosphorus ylides in excellent yields.