Encapsulation of the interstellar abundant H3+ in a C60 fullerene

The possible encapsulation of the interstellar abundant H₃⁺ ion inside a C₆₀ fullerene cage has been examined by using the Hartree‐Fock (HF) and the second order Møller‐Plesset perturbation (MP2) methods both with the 6‐31G** basis set. It was found that H₃⁺ forms various stable endohedral complexes inside the cage. Six configurations have been examined among which four were stable compared with the separated initial species, the dissociated H₂ + H⁺ inside the cage being the most stable. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Production of monoclonal antibodies against hop-derived (Humulus lupulus L.) prenylflavonoids and the development of immunoassays

Monoclonal antibodies against the hop-derived prenylated chalcone xanthohumol (X) and the prenylated flavonoids isoxanthohumol (IX) and 8-prenylnaringenin (8-PN) were developed. Carboxylic acid haptens of X, IX and 8-PN were synthesized by linking a spacer to their C4′-OH group followed by subsequent coupling to bovine serum albumin (BSA) to form conjugates that were employed as immunogens in BALB/c mice to raise antibodies. The monoclonal antibodies that were secreted from the established hybridoma cell lines proved, in cross-reactivity studies, to possess highly specific binding capacities in an optimized competitive indirect ELISA. The immunoassays make use of immunogen-coated microtiterplates and a peroxidase-labeled anti-mouse IgG₁ secondary antibody with ABTS as a chromogenic substrate. For X the IC₅₀ value derived from the standard curve was 62.91 ng mL⁻¹, and for both IX and 8-PN 37.15 ng mL⁻¹. The assay was validated for the quantitative analysis of X, IX and 8-PN in urine and serum. A simple sample pretreatment procedure using a diethyl ether extraction was optimized and the recoveries and matrix effects were assessed. The validity of the established assay was tested and mean inter- and intra-assay variations in urine were 2.32% and 1.91%, respectively for X, 6.24% and 2.39%, respectively for IX and 7.18% and 0.74%, respectively for 8-PN. In serum, the mean inter- and intra-assay variations were 8.90% and 1.37%, respectively for X, 6.13% and 1.57%, respectively for IX and 6.13% and 2.43%, respectively for 8-PN. Furthermore, the method demonstrated excellent accuracy and significant correlation with measurements by an established and validated HPLC-MS method.     

A systematic approach to assess amino acid conversions in SILAC experiments

SILAC is a widely accepted approach for quantitative proteomics in which proteins are labeled with stable isotopes during cell culture. A major drawback of this technique is the metabolic conversion of labeled amino acids that may hamper accurate quantification. A paradigmatic example of this phenomenon is the generation of labeled proline from arginine, known to occur in a good number of biological models. We propose a novel methodology to identify and quantitate metabolic conversions as well as to evaluate labeling efficiency in SILAC experiments. In this approach, labeled proteins are reduced to amino acids by acid hydrolysis before LC-MS/MS analysis. Since it is carried out at the amino acid level, tracking the fate of the isotope label is straightforward and can be performed for each amino acid independently. After applying this method to mammalian cells, grown in the presence of heavy arginine and lysine, labeling efficiency and amino acid conversions could be accurately evaluated. Only undesirable labeling of proline was found to occur at a significant extent, varying greatly among cell lines. Finally, increasing proline concentration in the growing medium was shown to be effective at preventing arginine conversion without any noticeable side effect.     

Alcaligenes faecalis penicillin G acylase-catalyzed enantioselective acylation of dl-phenylalanine and derivatives in aqueous medium

A new strategy based on enantioselective acylation properties of relatively unknown penicillin G acylase from Alcaligenes faecalis has been developed for the production of pharmacologically interesting enantiomerically pure d-phenylalanine. In order to get high reaction rate and enantioselectivity, two key factors (pH and temperature) and eight different acyl donors were optimized, and the optimal acylation reaction was carried out at pH 10, 35 °C, using phenylacetamide as the acyl donor. This enantioselective acylating method is also illustrated by the effective production of five different p-substituted phenylalanine derivatives in enantiopure.     

Un-catalyzed tandem Knoevenagel–Michael reaction for the synthesis of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ols) in aqueous medium

An environmentally benign un-catalyzed one-pot synthesis of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ols) has been reported via tandem Knoevenagel–Michael reaction of aldehydes with two equivalents of 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one in aqueous medium.     

An Efficient Synthesis of N‐Substituted‐3‐aryl‐3‐(2‐hydroxy‐4,4‐dimethyl‐6‐oxocyclohex‐1‐enyl)propanamides by Four‐component Reaction in Aqueous Medium

A mild and efficient synthesis of N‐substituted‐3‐aryl‐3‐(2‐hydroxy‐4,4‐dimethyl‐6‐oxocyclohex‐1‐enyl)propanamides via four‐component reaction of an aldehyde, amine, Meldrum's acid and 5,5‐dimethylcyclo‐hexane‐1,3‐dione in the presence of benzyltriethylammonium chloride (TEBAC) in aqueous medium is described. This method has the advantages of accessible starting materials, good yields, mild reaction conditions and eco‐friendliness.     

采用光谱技术研究[C4mim][BF4]的传压和测压性能

金刚石压腔是一种在实验室被频繁使用的高压产生装置,它在高压领域占据着重要地位。当金刚石压腔内传压介质只能提供非静水压环境时,利用传统的红宝石荧光光谱测压方法将很难准确测量样品压强,这也是目前超高压实验面临的普遍困难。若有一种兼具“传压”和“测压”双重功能的物质,根据“相邻位置、相近压强”原则,将能够解决在非静水压环境中测不准样品压强问题。显然,探寻兼具“传压”和“测压”双重功能的物质是一项非常重要的工作。本文将红宝石微粒与离子液体[C₄mim][BF₄]装入金刚石压腔,然后利用金刚石压腔压缩[C₄mim][BF₄]使其提供高压环境,同时采集红宝石的荧光光谱及其附近[C₄mim][BF₄]的拉曼光谱。通过分析红宝石特征荧光峰R₁的峰位,得到了[C₄mim][BF₄]在加压过程中提供的一系列高压环境的压强值。通过分析红宝石特征荧光峰R₁的峰宽,发现[C₄mim][BF₄]在0~6.26和6.26~21.43 GPa两个压强范围内可分别提供静水压环境和准静水压环境,表明[C₄mim][BF₄]在0~21.43 GPa范围内可以作为传压介质使用。此外,还发现[C₄mim][BF₄]在0~2.28,2.28~6.26,6.26~14.39和14.39~21.43 GPa四个压强范围内分别为“液相Ⅰ”、“液相Ⅱ”、“非晶相Ⅰ”和“非晶相Ⅱ”。通过分析[C₄mim][BF₄]中特征拉曼峰ν_(B-F)和ν_(ring)的峰位,发现在[C₄mim][BF₄]四个相态内ν_(B-F)和ν_(ring)的峰位随压强增加均满足线性变化关系,并给出了相应的压强与峰位关系函数,这些函数是[C₄mim][BF₄]用作压标物质的重要依据。综上所述,[C₄mim][BF₄]不仅具有“传压”功能,同时还具有“测压”功能,可同时用作“传压介质”和“压标物质”。研究结果为在非静水压环境中准确测量样品压强提供了重要依据,也为超高压条件下样品压强测量不准确问题提供了新的解决思路。     

Physical aspects of magnetized Jeffrey nanomaterial flow with irreversibility analysis

This research presents the applications of entropy generation phenomenon in incompressible flow of Jeffrey nanofluid in the presence of distinct thermal features. The novel aspects of various features, such as Joule heating, porous medium, dissipation features, and radiative mechanism are addressed. In order to improve thermal transportation systems based on nanomaterials, convective boundary conditions are introduced. The thermal viscoelastic nanofluid model is expressed in terms of differential equations. The problem is presented via nonlinear differential equations for which analytical expressions are obtained by using the homotopy analysis method (HAM). The accuracy of solution is ensured. The effective outcomes of all physical parameters associated with the flow model are carefully examined and underlined through various curves. The observations summarized from current analysis reveal that the presence of a permeability parameter offers resistance to the flow. A monotonic decrement in local Nusselt number is noted with Hartmann number and Prandtl number. Moreover, entropy generation and Bejan number increases with radiation parameter and fluid parameter.     

Total synthesis of (+)-davidiin

Quite strained: The total synthesis of (+)-davidiin, an ellagitannin with more substituents in axial than in equatorial positions, requires a conformational lock of the glucose, induced by steric repulsion between adjacent bulky silyloxy groups. This conformational lock played a pivotal role in 1)?the β-selective formation of the glycosyl ester at the anomeric position, 2)?the formation of the 1,6-HHDP bridge, and 3)?the complete control of axial chirality in the aryl-aryl coupling.