Theoretical study of14N pure quadrupole resonance in amino acids

The theoretical hybridization model of Vega is adapted to the tetrahedral environment around the nitrogen nucleus in eleven amino acids to estimate the orbital occupation numbers using the experimental values of the quadrupole coupling constant and asymmetry parameter of¹⁴N quadrupole resonance and the results are discussed.     

几种N-取代马来酰胺酸辅酶模型的核磁共振研究

我们对8种N-取代马来酰胺酸辅酶模型与不同类型的亲核试剂反应后生成的产物进行了¹H、¹³C NMR的研究, 测得¹H、¹³C谱化学位移,研 究探讨其规律性, 并测试了IR谱和元素分析.     

15N/14N Analysis of Amino Acids with GC-C-IRMS - Methodical Investigations and Ecotoxicological Applications

Abstract

In order to perform the ¹⁵N/¹⁴N analysis of amino acids using a gas chromatograph and isotope ratio mass spectrometer linked up via a combustion interface (GC-C-IRMS), the amino acids must be derivatized. Tert-butyldimethylsilylation is examined using various techniques (direct conversion to nitrogen gas, ConFlo-IRMS [1], GC-C-IRMS [2]) and subsequently applied to isotopic characterization of amino acids from wheat protein hydrolyzate obtained from plants exposed to ozone. The method provides a reliable tool for studying ecotoxicological effects on plants at a molecular level in addition to the investigation of the natural variations of different N fractions.     

Relationship between experimental pKa values in aqueous solution and a gas phase bond length in bicyclo[2.2.2]octane and cubane carboxylic acids

Linear correlations were established between the calculated bond lengths and the pK_a or σ_I values for a series of 4‐substituted bicyclo[2.2.2]octane‐1‐carboxylic acid and 4‐cubane‐1‐carboxylic acid derivatives. The bond lengths have been calculated at a modest computational level, HF/6‐31G(d), both in the gas phase and with the continuum solvation model, polarisable continuum model (PCM). In general, the best correlations are obtained when the PCM model is taken into account, especially when neutral and charged molecules are considered together. The best models in each case show square correlation coefficients (R²) larger than 0.9 and indicate that they can be used as predictive tools. These results expand previous results that indicate the possibility of a relationship between gas phase bond length and pK_a values in aqueous solution and indicate that such relationships are more general than hitherto expected. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

以光散射技术研究啶虫脒的测定及其与DNA的相互作用

研究了啶虫脒与脱氧核糖核酸(DNA)之间的共振光散射(RLS)增强作用。加入啶虫脒导致DNA的共振光散射增强,在316.0 nm处,存在一处共振光散射增强峰。由此建立了一种以DNA为探针检测农药啶虫脒的新方法。体系的最佳条件为,实验选择了pH 1.73为适宜酸度;加入10 μg·mL-1浓度的DNA溶液的体积为 2 mL;在室温条件下,体系的反应需要30 min达到稳定;“啶虫脒-DNA-H₂SO₄”的加药顺序为最佳。该方法适用的线性范围为0～2.25 μg·mL-1,检出限为0.2 μg·mL-1,啶虫脒在河水样品中的回收率为98.0%～102.0%,并探讨了DNA与啶虫脒的相互作用机理：啶虫脒与核酸间的相互作用包含有静电引力,啶虫脒的吡啶基与DNA碱基之间的π—π堆积作用。     

Hepatic lipid composition analysis using 3.0-T MR spectroscopy in a steatotic rat model

Purpose

To investigate the feasibility of in vivo assessment of hepatic lipid composition using 3.0-T proton magnetic resonance spectroscopy (¹H-MRS) in a steatotic rat model and compare it to histopathological and biochemical assessment.

Materials and Methods

Hepatic steatosis was induced by feeding rats with a methionine/choline-deficient (MCD) diet for 1, 2, 3, 5 or 7 weeks (n=5 per group). At the end of the diet period, ¹H-MRS of the liver was performed, and rats were sacrificed for histopathological and biochemical assessment of the liver. Spectra were acquired in a single voxel (1.2 cc) using a point-resolved spectroscopic sequence with TE/TR=35/2000 ms and 64 signal acquisitions. From the MR spectra, peak area ratios were calculated to estimate hepatic lipid composition.

Results

During MCD diet periods, hepatic steatosis significantly increased on histopathology (P<.001). The ¹H-MRS measurements of total hepatic fat content [1.3/(1.3+4.65) ppm] correlated strongly with histological macrovesicular hepatic steatosis (r=0.93, P<.001) and with the biochemical total hepatic fatty acids (r=0.94, P<.001). Total unsaturated fatty acids [TUFA, 5.4/(1.3+4.65) ppm] estimated with ¹H-MRS strongly correlated with the biochemical unsaturated fatty acids (r=0.90, P<.001). Polyunsaturated fatty acids [PUFA, 2.8/(1.3+4.65) ppm] estimated with ¹H-MRS strongly correlated with biochemical PUFA (r=0.91, P<.001). The proportion of total unsaturated fatty acids relative to the amount of total fatty acids (rTUFA, 5.4/1.3ppm) measured with ¹H-MRS strongly correlated with the biochemical amount of unsaturated relative to total hepatic fatty acids (r=0.81, P<.001). The proportion of PUFA relative to the amount of total fatty acids (rPUFA, 2.8/1.3 ppm) measured with ¹H-MRS correlated with the biochemical amount of PUFA relative to total fatty acids (r=0.59, P=0.005,) and with the biochemical amount of omega-6 PUFA relative to total fatty acids (r=0.73, P<.001).PUFA at ¹H-MRS correlated with the histopathologically assessed degree of lobular inflammation in the liver (r=0.57, P=.001).

Conclusion

3.0T ¹H-MRS is able to measure poly- and unsaturated hepatic fatty acids and this strongly correlates with biochemical assessment. This study provides evidence that 3.0-T ¹H-MRS is a noninvasive technique to assess hepatic lipid composition.     

Ultrasound irradiation promoted enzymatic alcoholysis for synthesis of monoglyceryl phenolic acids in a solvent-free system

Monoglyceryl phenolic acids (MPAs) were known as the natural hydrophilic antioxidants which could be used in different fields such as food, pharmaceutical, cosmetic etc. A novel enzymatic route of MPAs synthesis by the alcoholysis of phenolic acid ethyl esters with glycerol under ultrasound irradiation in solvent free system was developed. Optimization of reaction parameters shows that a high conversion of above 97.4% can be obtained under the following conditions: phenolic acid ethyl esters to glycerol molar ratio of 1:10, with 6% catalyst (Novozym 435), at 60 °C and 200 rpm, with ultrasound input of 250 W, at 20 kHz frequency. Compared to the conventional stirring method, the activation energy for phenolic acid ethyl esters conversion was decreased from 65.0 kJ/mol to 32.1 kJ/mol under ultrasound promotion; the apparent kinetic constant (V_m/K_m) increased above 1.2-folds; the lipase amount decreased to 50%; the time required for the maximum conversion reduced up to 3-folds without damaging the lipase activity, which is the fastest report for enzymatic synthesis of MPAs.     

新疆野生黑加仑与马林果实的营养成分分析

通过对新疆野生黑加仑和野生马林的脂肪油，8种微量元素，17种氨基酸以及维生素C的含量进行测定得出：黑加仑脂肪油含量为17．9％，马林的脂肪油含量为22．3％，其中，黑加仑脂肪油中，r－亚麻酸的含量为19．02％，而马林中，其含量为9．40％，黑加仑中K，Na,Ca,Cu,Zn,Fe的含量比马林中的含量高，而Mn,Mg元素的含量却比马林含量低；马林的维生素C含量为16．22mg/g，黑加仑的含量为108mg/g，黑加仑的氨基酸的总量为1．63％，马林为1．14％。     

Partial molar adiabatic compressibilities of transfer of some amino acids from water to aqueous lactose solutions at different temperatures

Apparent molar adiabatic compressibilities (K_{?, s}) of glycine, L-alanine, L-valine, and L-leucine have been determined in aqueous and mixed aqueous solutions of lactose (2 to 6 mass%) at T = (293.15, 298.15, 303.15, and 308.15) K. From these data partial molar adiabatic compressibilities at infinite dilution (K_{?, s}⁰) have been evaluated to calculate corresponding transfer function. The transfer partial molar adiabatic compressibilities at infinite dilution (ΔK_{?, s}⁰) are found to be positive. The decrease in the magnitude of transfer partial molar adiabatic compressibilities from glycine to L-leucine indicates the dominance of hydrophobic-hydrophobic interactions between the increasing side chains of amino acids. Also, the contributions of NH₃⁺COO⁻ , and CH₂ groups have been calculated by the linear correlation of K_{?, s}⁰ with number of carbon atoms in the alkyl chain of amino acids.