Thermal desorption gas chromatography–mass spectrometry as an enhanced method for the quantification of polycyclic aromatic hydrocarbons from ambient air particulate matter

Polycyclic aromatic hydrocarbons (PAHs) from ambient air particulate matter (PM) were analysed by a two-step thermal desorption (TD) injection system integrated to a gas chromatograph–mass spectrometer (GC/MS). The operational variables of the TD method were optimised and the analytical expanded uncertainties were calculated to vary from 8% to 16% over the operative concentration range (40–4000 pg). The performance of the TD method was validated by the analysis of a standard reference material and by comparison of PAH concentrations in PM samples to those obtained by a conventional liquid extraction (LE) method. The TD method reported lower uncertainties than the LE method for the analysis of similar concentrations in air. The TD method also showed advantages for shorter sampling times in comparison to 24 h for source apportionment applications and for reducing losses of more reactive compounds such as benzo[a]pyrene.     

荒漠土壤全磷含量热红外发射率光谱估算研究

土壤磷素为植物提供营养元素,是评价土壤质量的重要参数之一。传统的土壤全磷含量的测定方法不能实现对荒漠土壤养分有效监测,而运用遥感手段能够弥补传统手段的不足。有学者开展了通过近红外光谱来估算土壤全磷含量的研究,但由于土壤磷素近红外吸收系数小、吸收峰不明显等原因,使得土壤磷素估算的模型精度欠佳。为解决荒漠土壤全磷含量近红外光谱估算存在的不足,提高荒漠土壤全磷含量估算的精度,对准噶尔盆地东部荒漠土壤进行采样、化验分析和发射率光谱测量、处理,分析土壤热红外发射率特征,建立多种荒漠土壤全磷含量热红外发射率估算模型。结果表明:在土壤全磷含量高于0.200g·kg-1的条件下,在8.00~13μm波长范围内,热红外发射率随全磷含量的增加而增加,9.00~9.60μm波段范围内土壤热红外发射率对全磷含量最敏感;多元逐步回归建立的估算模型的估算效果差,不能用于荒漠土壤全磷含量热红外发射率的估算,经过偏最小二乘回归建立的估算模型效果优于多元逐步回归建立的模型;偏最小二乘回归建立的连续去除一阶导数模型最优,校正和验证的R2分别达到了0.97和0.82,校正和验证的RMSE仅有0.010 6和0.015 7,RPD为2.62,模型能够极好的对土壤全磷含量进行估算。该研究的成果为荒漠土壤全磷含量定量遥感估算提供有效支撑,通过有效监测荒漠土壤全磷含量的时空动态变化,为区域生态环境的修复提供依据。     

利用密度泛函理论研究六种多环芳烃的分子结构以及拉曼光谱

利用DFT理论B3LYP/6-31+G(d, p)方法对六种PAHs分子进行理论计算, 可以得到六种多环芳烃分子的分子构型信息, 其中包括具体的键长、键角以及整个分子的长宽信息, 从而为我们能够更加深入地理解稠环芳烃的大小与环糊精内腔的尺寸匹配效应对SERS增强效果的影响提供了理论依据; 还利用Gaussview对这些分子的拉曼光谱给出具体的峰位, 并对计算出的六种多环芳烃的拉曼光谱进行主要峰位的指认。通过与实验测得拉曼光谱的对应关系, 从而对实验所得的拉曼光谱在理论上进行了有力的补充。     

Direct Determination of Total Chromium in Sea Water by Graphite Furnace Atomic Absorption Spectrometry with Multiple Injections

The method of multiple injections coupled with graphite furnace and atomic absorption spectrometry is applied to direct determination of total chromium at extremely small concentrations in samples of open sea water. The method involves the in situ preconcentration of trace chromium in sea water onto a pyrocoated graphite tube by multiple injections (up to 4 × 90 μL) prior to analysis. The selected ashing temperature is up to 1800 °C, and the background signal caused by high sea-salt contents will be markedly reduced when the ashing time is prolonged up to 200 s. A CASS-2 reference sea water has been used as a quality control sample in the analyses of samples of open sea water samples; the results were found to agree with the certified value. Due to the use of a relatively large volume (up to 0.36 mL) of sample for direct determination of trace chromium in sea water, the detection limit for chromium is 0.057 ppb.     

From S,N‐Heteroacene to Large Discotic Polycyclic Aromatic Hydrocarbons (PAHs): Liquid Crystal versus Plastic Crystalline Materials with Tunable Mechanochromic Fluorescence

A novel type of discotic polycyclic aromatic hydrocarbon (PAH) based on an enlarged dibenzo[a,c]phenazine core has been developed. The large conjugated mesogenic core with increased dipole moment derived from S,N heteroatoms facilitates the formation of highly ordered columnar superstructures both in solution and bulk. Columnar mesophases, including liquid crystal (LC) and plastic crystal (PC) assemblies could form unprecedentedly based on the same PAH core. The cores are delicately modulated by the peripherical alkoxy chains. Both mesogens have mechanochromic fluorescent (MCF) character, which is also structure dependent and correlated with the different mesophase formation. For the first time, MCF properties can be realized in such a large conjugated mesogenic system.     

Total syntheses of (+)- and (−)-1,3,4,5-tetragalloylapiitol and revision of absolute configuration of naturally occurring (−)-1,3,4,5-tetragalloylapiitol

The total syntheses of (+)- and (−)-1,3,4,5-tetragalloylapiitol were achieved in seven steps from d- and l-ribose, respectively. By comparing the optical rotations of both enantiomers with those of the natural product, the absolute configuration at C-3 in the naturally occurring 1,3,4,5-tetragalloylapiitol has been revised to R. The absolute configurations at C-3 in the synthetic (+)- and (−)-1,3,4,5-tetragalloylapiitol were further confirmed by the circular dichroism exciton chirality method.     

Development and study of zeolite catalytic systems for the transformation of lower hydrocarbons into valuable chemicals

The results of studies aimed at the development of highly efficient catalysts based on zeolites of the pentasil family for synthesis of aliphatic and aromatic hydrocarbons from C₂−C₅ olefins and paraffins are summarized. Dedicated to the memory of Academician M. E. Vol'pin timed to his 75th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1071–1080, June, 1998.     

Sequential injection system for on-line analysis of total nitrogen with UV-mineralization

An automatic method for the determination of total nitrogen in wastewater by sequential injection analysis and mineralization with UV radiation has been developed. The method is based on the mineralization of the samples with sodium persulphate in basic medium under UV radiation. Small volumes of sample and reagents are firstly aspirated into a single channel and then propelled by flow reversal to the UV reactor and then to the detector. The organic and inorganic nitrogen compounds are oxidized to nitrate that is then measured at 226 nm. The sequential injection procedure has been optimized and the factors affecting the efficiency of the oxidation have been studied with a number of test substances with different chemical structures and properties. Solutions in the concentration range 1-56 g l⁻¹ of nitrogen can be analyzed with the described procedure. The sample rate is of 30-40 samples h⁻¹. The LOD is 0.6 mg l⁻¹ N and the reproducibility is 1.8% (28 mg l⁻¹ N). Organic carbon in the form of glucose was added to a number of test solutions to study the potential interference of organic matter.The method was compared with the Kjeldahl digestion method by analyzing 15 wastewater samples with both methods. The nitrate and nitrite content of the non-oxidized samples were subtracted from the corresponding nitrogen content determined after photo-oxidation and the value compared with the Kjeldahl nitrogen content.     

羟基取代的多环芳烃与一氧化氮的反应研究

内源性的一氧化氮(NO)是多种生理过程中必不可少的信使分子,它在神经系统递质传导、神经发育、脑血流调节以及免疫调节等过程中具有十分重要的作用。为揭示NO生理功能的化学本质,NO成为化学家近年来研究的重要课题之一。     

Switching between Local and Global Aromaticity in a Conjugated Macrocycle for High‐Performance Organic Sodium‐Ion Battery Anodes

Aromatic organic compounds can be used as electrode materials in rechargeable batteries and are expected to advance the development of both anode and cathode materials for sodium‐ion batteries (SIBs). However, most aromatic organic compounds assessed as anode materials in SIBs to date exhibit significant degradation issues under fast‐charge/discharge conditions and unsatisfying long‐term cycling performance. Now, a molecular design concept is presented for improving the stability of organic compounds for battery electrodes. The molecular design of the investigated compound, [2.2.2.2]paracyclophane‐1,9,17,25‐tetraene (PCT), can stabilize the neutral state by local aromaticity and the doubly reduced state by global aromaticity, resulting in an anode material with extraordinarily stable cycling performance and outstanding performance under fast‐charge/discharge conditions, demonstrating an exciting new path for the development of electrode materials for SIBs and other types of batteries.