自动顶空固相微萃取气相色谱法同步分析水中17种有机物

采用自动顶空固相微萃取(HS-SPME)技术与气相色谱联用同步分析水中1,4-二氯苯、1,2-二氯苯、1,3,5-三氯苯、1,2,4-三氯苯、1,2,3-三氯苯、六氯苯、硝基苯、对硝基甲苯、α-666、β-666、γ-666、δ-666、七氯、ρ,ρ′-DDE、ρ,ρ′-DDD、o,ρ′-DDT、ρ,ρ′-DDT17种有机物。方法的最低检出浓度为0.001~0.044μg/L,线性相关系数均大于0.999,相对标准偏差为1.4%~8.7%,加标回收率在81.3%~122.9%之间。     

Polymerizable C70 derivatives with acrylate functionality for efficient and stable solar cells

Fullerene-based organic solar cells are generally suffering from severe microstructure evolution occurring in their bulk heterojunction active layers and thus are extremely stable. To address it, four polymerizable C₇₀ fullerene derivatives, [6,6]-phenyl-C₇₁-ethyl acrylate (PC₇₁EA), [6,6]-phenyl-C₇₁-propyl acrylate (PC₇₁PrA), [6,6]-phenyl-C₇₁-butyl acrylate (PC₇₁BA), and [6,6]-phenyl-C₇₁-pentyl acrylate (PC₇₁PeA), have been designed, synthesized, and investigated. These fullerene compounds have a molecular structure, shape and size very like the conventional C₇₀ fullerene acceptor, [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), and have been found no different in their light absorption, redox potentials, and frontier orbital energy levels. Using these fullerene acrylates individually as acceptor and poly(3-hexylthiophene) as donor, organic solar cells have been fabricated and gave optimal efficiencies ranging from 3.32% to 4.16%, comparable to PC₇₁BM-based reference cells (4.06%). Owing to their acrylate functionality, these fullerene derivatives can turn into insoluble upon heating, and thus endow their solar cell devices much better thermostability than PC₇₁BM-based reference cells. The best one, coming from PC₇₁PeA devices, reported an optimal efficiency of 4.16%, and maintained 91.7% efficiency after heat treatment at 150 °C for 35 h. As a sharp contrast, the PC₇₁BM reference cell dropped its optimal efficiency from 4.06% to 0.48% only after 5 h heat treatment. X-ray diffraction, optical and atomic force microscopy, and space-charge-limited current method have been carried out to understand active layer structure, morphology, and charge mobility change during heat treatment.     

Modifications of 5,12-dihydroindolo[3,2-a]carbazole scaffold via its regioselective C2,9-formylation and C2,9-acetylation

The effective approaches for regioselective double formylation and acetylation of 5,12-dialkyl-6,7-diaryl-substituted 5,12-dihydroindolo[3,2-a]carbazoles by their treatment with dichloromethyl methyl ether in the presence of SnCl₄ or with acetyl chloride in the presence of AlCl₃ to afford the 2,9-diformyl or 2,9-diacetyl derivatives, respectively, were developed. Furthermore, new 2,9-bis(2,2-dicyanovinyl) derivatives were synthesized by the Knoevenagel condensation of diformyl-containing substrates with malononitrile, when new 2,9-bis(quinoxaline-2-yl)- and 2,9-bis(benzo[g]quinoxaline-2-yl) derivatives were formed via microwave-promoted oxidation of diacetyl-containing substrates with SeO₂ to the corresponding diglyoxals, followed by the reaction of these intermediates with o-phenylendiamine or 2,3-diaminonaphthalene, respectively. The basic optical and electrochemical properties of some 5,12-dihydroindolo[3,2-a]carbazoles were investigated.     

Laboratory intercomparison study on the analysis of short-chain chlorinated paraffins in an extract of industrial soil

Short-chain chlorinated paraffins (SCCPs) comprise a class of organic pollutants used in many industrial applications and released into the environment. The analytical determination of SCCPs is very challenging. Although there is at present no fully validated measurement procedure that might be applied in routine monitoring, the European Union Water Framework Directive (WFD) has required regular monitoring of this class of compounds at river-basin scale since 2007.To assess the status quo of the analysis of SCCPs in relation to the requirements of the WFD, we organized an interlaboratory comparison on the quantification of SCCPs in an extract of an industrial soil. Six laboratories participated in the exercise using three different techniques [i.e. gas chromatography (GC) coupled to mass spectrometry (MS) in electron-capture negative ionization mode, GC with atomic emission detection, and carbon-skeleton GC-MS]. The results reported were in the range 8.5–3200 mg/L. This confirms that reliable quantification of SCCPs is still very difficult to achieve and that the comparability of SCCP data reported to the European Commission is at least questionable.     

Impact of TiO2 nanoparticles on morphology and performance of crosslinked polyimide organic solvent nanofiltration (OSN) membranes

Chemically crosslinked polyimide organic–inorganic composite nanofiltration membranes suitable for application in harsh organic solvents were successfully prepared by phase inversion of dope solutions. TiO₂ nanoparticles were dispersed in these dope solutions, comprising polyimide (PI) in N,N-dimethylformamide/1,4-dioxane. The impact of TiO₂ on the resulting PI membranes was investigated using SEM, TGA, water contact angle, dope viscosity measurements and mechanical strength. The presence of TiO₂ nanoparticles within the membrane matrix was proved by the detection of a peak characteristic of TiO₂ in the WAXS pattern. SEM pictures of the cross-section of the PI/TiO₂ membranes showed dramatically changed morphology compared to reference membranes with no TiO₂ addition. Macrovoids present in reference membranes were suppressed by increasing loading of TiO₂ nanoparticles, and eventually disappeared completely at a TiO₂ loading above 3 wt.%. Decreasing water contact angle and an increase in ethanol flux indicated that hydrophilicity increased as nanoparticle loading increased. The effect of TiO₂ on the functional performance of the membranes was evaluated by measuring flux and rejection using cross-flow filtration. Perhaps surprisingly, the presence of TiO₂ improved the compaction resistance of the membranes, whereas rejection and steady flux were almost unaltered.     

Relative energy of organic compounds III. Components of the heat of reactions

The relative enthalpies of organic compounds described in Parts I and II of this series made possible to show the contribution of the reactants and products to the heat of reactions. First, the meaning of the relative enthalpies is demonstrated. The components of the heats of reactions are exemplified by a series of reactions: formation of alkyl halides, esters, amides, acid halides, and anhydrides. Further examples are hydrogenation of alkenes, alkynes, benzene, ethylene oxide, aldehydes, and nitriles, and addition of chlorine, water, and hydrogen chloride to ethylene. Acetal and hemiacetal formations and cyclization reactions are also among the examples.     

Chemically bonded assembly and photophysical properties of luminescent hybrid polymeric materials embedded into silicon–oxygen network and carbon unit

Through the reaction between the hydroxyl groups of 2-hydroxyl-3-methylbenzoic acid (HMBA), the glycol (G), the diglycol (DG) or the polyethylene glycol (PEG) and the isocyanate groups of 3-(triethoxysilyl)-propyl isocyanate (TEPIC), the hybrid precursors HMBA-Si, G-Si, DG-Si and PEG-Si were obtained. And then the precursors HMBA-Si and G-Si (DG-Si, PEG-Si) have coordinated to the rare earth ions with the carbonyl group of G-Si (DG-Si, PEG-Si) and the carboxyl group of HMBA-Si to form the hybrid materials HMBA-G-RE-Si (HMBA-DG-RE-Si, HMBA-PEG-RE-Si) through hydrolysis and copolycondensation with the tetraethoxysilane (TEOS) via sol–gel process. Subsequently, the NMR, FT-IR and ultraviolet absorption spectra have indicated that the effective precursors have been obtained successfully and the obtained materials possess the characteristic fluorescent properties, thermal stabilities and regular trunk with hole-like microstructures.     

Structural relaxations in disordered solids below Tg: Study by thermal-cycling single-molecule spectroscopy

Structural relaxation processes in disordered solids on the length scale of nanometers have been studied in a broad temperature range, from 4.5 K up to the glass transition, with single-molecule spectroscopy and thermal cycling experiments. Irreversible changes of single-molecule spectra after thermal cycles were observed and attributed to relaxation processes in the local environment of the probe molecules of tetra-tert-butylterrylene in polyisobutylene (PIB) and terrylene in solid ortho-dichlorobenzene. The effects of the relaxation processes on the individual parameters of low-energy matrix excitations (tunneling two-level systems and low-frequency vibrational modes) were analyzed, as well as the temperature dependence of the efficiency of relaxation processes in PIB. The results prove that the local matrix relaxations are characterized by a spatially varying distribution of activation energies.     

Investigation on growth,optical, thermal,mechanical and dielectric studies of Benzimidazolium L-aspartate NLO crystal

The organic salt of Benzimidazolium L-aspartate (BLA) has been synthesised and single crystals were grown by slow evaporation solution growth technique at room temperature using water as the solvent. The grown crystal was subjected to single crystal X-ray diffraction analysis and confirmed it belongs to monoclinic crystal system with space group P2₁/c. The crystalline perfection was studied using High resolution X-ray diffraction (HRXRD). The functional groups were analysed by FT-IR analysis. The optical transmittance and the lower cut-off wavelength of the BLA crystal have been identified by UV-Vis study. The thermal stability of the title crystal was investigated by TGA/DTA analyses. The Vickers microhardness analysis was carried out to study the mechanical strength of the crystal. The dielectric response of the crystal was studied in the frequency range 100 to 5 MHz at different temperatures. The surface morphology of the grown BLA crystal was studied by scanning electron microscopy (SEM). The second harmonic generation efficiency was measured in comparison with KDP by employing Kurtz Perry Powder method.     

Growth and characterization of a promising nonlinear optical organic crystal

The growth of single crystals of acetoacetanilide using slow evaporation technique is reported. Good-quality crystals up to a size of 20×10×1 mm³ are obtained. The grown crystals are characterized by employing UV-VIS spectrum, IR spectrum, and hardness measurements. Acetoacetanilide shows very good second-harmonic generation (SHG) efficiency.