Intramolecular hydrogen bond in 3‐imino‐propenylamine isomers: AIM and NBO studies

The molecular structure and intramolecular hydrogen bond energy of 18 conformers of 3‐imino‐propenyl‐amine were investigated at MP2 and B3LYP levels of theory using the standard 6‐311++G** basis set. The atom in molecules or AIM theory of Bader, which is based on the topological properties of the electron density (ρ), was used additionally and the natural bond orbital (NBO) analysis was also carried out. Furthermore calculations for all possible conformations of 3‐imino‐propenyl‐amin in water solution were also carried out at B3LYP/6‐311++G** and MP2/6‐311++G** levels of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the imine–amine conformers of this compound are more stable than the other conformers. B3LYP method predicts the IMA‐1 as global minimum. This stability is mainly due to the formation of a strong N? H···N intramolecular hydrogen bond, which is assisted by π‐electrons resonance, and this π‐electrons are established by NH2 functional group. Hydrogen bond energies for all conformers of 3‐imino‐propenyl‐amine were obtained from the related rotamers methods. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Simultaneous liquid chromatographic assay of amantadine and its four related compounds in phosphate-buffered saline using 4-fluoro-7-nitro-2,1,3-benzoxadiazole as a fluorescent derivatization reagent

Simultaneous HPLC assay of 1-adamantanamine hydrochloride (amantadine) and its four related compounds [2-adamantanamine hydrochloride (2-ADA), 1-adamantanmethylamine (ADAMA), 1-(1-adamantyl)ethylamine hydrochloride (rimantadine) and 3,5-dimethyl-1-adamantanamine hydrochloride (memantine)] in phosphate-buffered saline (pH 7.4) after pre-column derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) was developed. Phosphate-buffered saline samples were mixed with borate buffer and NBD-F solution in acetonitrile at 60 degrees C for 5 min and injected into HPLC. Five derivatives were well separated from each other. The lower limits of detection of amantadine, 2-ADA, ADAMA, rimantadine and memantine were 0.008, 0.001, 0.0008, 0.0015 and 0.01 microg/mL, respectively. The coefficients of variation for intra- and inter-day assay were less than 6.4 and 8.2%, respectively. The method presented was applied to a binding study of these compounds to human alpha(1)-acid glycoprotein. While affinity constants and capacities for ADAMA, rimantadine and memantine were calculated by means of Scatchard plots, those for the others were not determined. ADAMA, rimantadine and memantine were bound with different affinities and capacities. These results indicate that NBD-F is a good candidate as a fluorescent reagent to simultaneously determine amantadine and its four related compounds by HPLC after pre-column derivatization. Our method can be applied to binding studies for protein.     

On σ-algebras related to the measurability of compositions

Given a measurable space (T, F), a set X, and a map ?: T → X, the σ-algebras N _Ф = ?_?∈Φ N _?, and M _Φ = ?_?∈Φ N _?, where G _?(t) = (t, ?(t)) and Φ ? X ^T , are considered. These σ-algebras are used to characterize the (F, B, ?)-measurability of the compositions g ○ ? and f о G _?, where g: X → Y, f: T × X → Y, and (Y, ?) is a measurable space. Their elements are described without using the operations ? ^?1 and G _? ^?1 .     

Detecting and creating oscillations using multifractal methods

By comparing the Hausdorff multifractal spectrum with the large deviations spectrum of a given continuous function f, we find sufficient conditions ensuring that f possesses oscillating singularities. Using a similar approach, we study the nonlinear wavelet threshold operator which associates with any function f = ∑_j ∑_k d_j,k ψ _j,k ∈ L ²(?) the function series f^t whose wavelet coefficients are d ^t _j,k = d_j,k 1 , for some fixed real number γ > 0. This operator creates a context propitious to have oscillating singularities. As a consequence, we prove that the series f^t may have a multifractal spectrum with a support larger than the one of f . We exhibit an example of function f ∈ L ²(?) such that the associated thresholded function series f^t effectively possesses oscillating singularities which were not present in the initial function f . This series f^t is a typical example of function with homogeneous non‐concave multifractal spectrum and which does not satisfy the classical multifractal formalisms. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of Ipratropium Bromide–Related Compounds

Synthesis of ipratropium bromide metabolites is described.     

结合局部一致性和低频振幅探究躯体症状障碍患者大脑自发性活动的改变

躯体症状障碍（somatic symptom disorder,SSD）是一种常见的医学疾病,致病原因涉及生物学、心理学及社会因素.目前关于SSD的神经机制知之甚少.本研究通过静息态功能磁共振成像（functional magnetic resonance imaging,fMRI）,结合低频振幅（amplitudes of low-frequency fluctuation,ALFF）和局部一致性（regional homogeneity,ReHo）分析探究45位SSD患者和43位健康对照自发性脑活动特征的区别.结果发现：与对照组相比,SSD患者右侧扣带回中部的ReHo值显著升高,而右侧楔前叶、左侧颞下回延伸到左侧颞中回和左侧海马旁回、右侧脑桥的ReHo值显著降低.同时,SSD患者扣带回中部延伸至左侧额中回、右侧脑岛延伸至右侧额下回、左侧额中回延伸至左侧前扣带回的ALFF值均显著升高.这些脑区的脑功能与自我加工、情绪处理、身体知觉等有关,与SSD发病机制有重要联系.     

大体积进样气质联用法检测涉水产品浸泡液中的酚类物质

建立了涉水产品浸泡液中酚类物质的柱头大体积进样(OCI-LVI)、串联毛细管柱分离、气相色谱-质谱联用(GC-MS)定性与定量检测方法.样品按相关法规浸泡后,以0.2 g/L的比例立即加入还原剂Na2S2O3,以消除过量余氯.取10 mL浸泡液,加入2,4-二溴酚内标物质.调pH 6.8,Nacl饱和后加1 mL提取溶...     

Characterization of β2‐microglobulin conformational intermediates associated to different fibrillation conditions

β2‐Microglobulin (β2m) is the light chain of the class‐I major histocompatibility complex, being also the causing agent of dialysis‐related amyloidosis, which results from its accumulation as amyloid material in the skeletal joints. This study describes conformational properties of β2m under two distinct, in vitro amyloidogenic conditions: neutral pH in the presence of 20% 2,2,2‐trifluoroethanol (TFE) and acidic pH in the absence of TFE. Species distribution analysis by electrospray ionization–mass spectrometry (ESI‐MS) is combined with information obtained by ion mobility–mass spectrometry (IM‐MS), fluorescence and circular dichroism (CD) spectroscopy. It is shown that β2m populates quite different conformational ensembles under the two conditions, but both ensembles display a minor fraction of the population in a partially folded state. In spite of similar compactness, these two partially folded forms display different conformations: helical secondary structure is predominant in the species at pH 7.4, 20% TFE, while the low‐pH form is mainly random coil. As temperature is increased, the TFE intermediate looses helical structure becoming more similar to the low‐pH intermediate. The existence of different conformational ensembles may rationalize the different aggregation propensity displayed by β2m under the two fibrillation conditions analyzed here. Copyright © 2011 John Wiley & Sons, Ltd.     

An Anti‐angiogenic Reverse Thermal Gel as a Drug‐Delivery System for Age‐Related Wet Macular Degeneration

Reverse thermal gels have numerous biomedical implications, as they undergo physical gelation upon temperature increases and can incorporate biomolecules to promote tissue repair. Such a material is developed for the sustained release of bevacizumab (Avastin), a drug used to treat age‐related macular degeneration. The polymer, poly(ethylene glycol)‐poly(serinol hexamethylene urethane) (ESHU), forms a physical gel when heated to 37 °C and shows good cytocompatibility with ocular cells. ESHU is capable of sustaining bevacizumab release over 17 weeks in vitro, and the release kinetics can be altered by changing the drug dose and the ESHU concentration. These results suggest that ESHU is biologically safe, and suitable for ocular drug delivery.

     

Millimeter wave continuum absorption in moist nitrogen at temperatures 261–328 K

The paper presents results of extensive experimental study of the water related continuum absorption in a mixture of water vapor and nitrogen in 107–143 GHz frequency range at accurately controlled laboratory conditions. Resonator spectrometer and modified method of measurement that minimizes systematic errors related to water adsorption were employed. It allowed investigation in temperature range 261–328 K, including a first-time laboratory study of the continuum at temperatures below freezing. Coefficients of the common empirical parameterization of the continuum including self (H₂O–H₂O) and foreign (H₂O–N₂) parts are derived and compared with results of the most known previous experimental and theoretical studies demonstrating very good qualitative and in some cases quantitative agreement. Dominating types of intermolecular interactions leading to the observed continuum are discussed.