A review of: “Potential Industrial Carcinogens and Mutagens,Studies in Environmental Science 4 by Lawrence Fishbein,Little Rock,Arkansas, 534 pages,many figures and tables,linen, format 250 × 175 mm,printed by Elsevier Scientific Publishing Company,Amsterdam, The Netherlands 1979, 73.25 US$ or 150.-Df1.”

Abstract

The design and calibration of a passive sampler operating according to the diffusion principle and its application to the analysis of indoor air are described. Taking aliphatic and aromatic hydrocarbons as representative pollutants, it is demonstrated that at constant concentration, the amount of substance trapped by the sampler is a linear function of the time of exposure. An equation is given relating this amount of substance to the mean pollutant concentration. The detection limit is of an order of 300μg/(m³.h). For test gas atmospheres variation coefficients of between 5 and 10%, were determined for a 24-hour exposure in an atmosphere with concentrations of the individual hydrocarbons between 150 and 600 μg/m³.     

Determination of diphenylamine in contaminated air of agricultural buildings using active sampling on solid sorbents

This paper reports the results of a study carried out with solid sorbents in order to establish the optimum procedure for sampling and determination of diphenylamine (DPA), the most widely used post-harvest chemical in apples, in the indoor air of apple storage buildings. Different sorbents (Amberlite XAD-2, Amberlite XAD-4, Supelpak 2, Florisil, and the octadecyl silica bonded sorbent, C-18) were evaluated for their capacity to efficiently retain DPA under different air sampling and storage conditions, whereas a desorption study of all sorbents tested was also performed to optimise a simple extraction procedure using low volumes of organic solvents. In general all sorbents produced acceptable results for DPA air sampling whereas DPA was recovered easily by the use of low volumes of both ethyl acetate and acetone from all sorbents studied thus making DPA a suitable analyte to be used in methods of indoor air analysis for multi-organic pollutants. However, the best results (analytical features, recovery results, and stability results during storage) were obtained by the use of Supelpak 2 as a sorbent for DPA active sampling. Limits of Quantification (LOQs) for the GC-NPD system ranged from 1.0 to 2.0?µg?m^?3 for 120 and 60?L air sampled, respectively. The developed air sampling procedure and analytical methodology was applied with success in the field to measure DPA residues in indoor air of two apple storage plants in Greece and results were further used to calculate the occupational inhalation exposure to DPA and consequently risk characterisation. Since DPA was detected in indoor air (at concentrations ranged from 1.6 to 580?µg?m^?3), there is no zero occupational risk for workers. However, the inhalation exposure of workers to DPA estimated in this study is far below the Acceptable Operator Exposure Level recently reviewed by the European Union and far below the critical exposure level for haematotoxicity systemic effect observed in carcinogenicity studies in rats for long-term inhalation exposure to DPA.     

Preparation of Hydrophilic Polystyrene Microspheres with Casein Molecules on the Surface

In this study, suspension polymerization is described to prepare hydrophilic polystyrene microspheres with casein macromolecules on the surface. In the suspension polymerization, casein w as used as an emulsifier and stabilizer instead of synthetic surfactants. The microspheres had spherical shape and the size distribution was narrow, the average size was about 3.5 µm. The microspheres were characterized with a Fourier transform infrared spectroscopy, revealing the existence of hydroxyl, carboxyl and amino groups. XPS analysis was carried out to study the surface composition, it revealed that the nitrogen concentration was 5.04% on the surface of the particles and it remained almost unchanged after the particles were washed by 2% SDS. The microspheres were confirmed to be hydrophilic due to the casein molecules on the surface.     

Molecular dynamics simulation study of the structural features and inclusion capacities of cucurbit[6]uril derivatives in aqueous solutions

Molecular dynamics (MD) simulations were performed for cucurbit[6]uril (CB6) methyl and cyclohexyl derivatives in aqueous solutions. Furthermore, MD simulations have been conducted to study the inclusion complexes between each CB6 derivative with α,ω-pentane diammonium ion (NH₃⁺(CH₂)₅NH₃⁺) to estimate the binding free energies, the complex geometries and the intermolecular forces responsible for complex formation. Results show a complete inclusion of the guest molecule in the cavity of the host for all complexes. Results also indicate that the guest dynamics inside the cavity of the substituted host is similar to that for the unsubstituted host. This demonstrates that the molecular recognition of the host is not affected by the alkyl substitution at the equator. Also, there is an insignificant conformational change of the macrocyclic structure upon inclusion of the guest. Molecular mechanics/Poisson Boltzmann surface area method was used to estimate the binding free energy of each complex. Results indicate that host–guest electrostatic interactions make the largest contribution to the complex binding free energy. Moreover, van der Waals interactions add significantly to the complex stability. The guest molecules show more or less similar binding free energies with the substituted CB6 that exhibits slightly more negative values than unsubstituted CB6 which is proved also by umbrella sampling.     

Fe3O4/壳聚糖季铵盐磁共振造影剂的制备及肝造影性能

采用季铵盐化壳聚糖(HTCC)对Fe₃O₄进行表面改性, 成功制备在模拟生理环境中悬浮稳定的超顺磁性Fe₃O₄/HTCC复合纳米粒。通过动态光散射、透射电镜、振动样品磁强计、磁共振等手段对材料的性能进行表征, 并考察了其细胞相容性及磁共振造影性能。结果表明: 该方法所制备的超顺磁性复合纳米粒粒径均一, 模拟生理环境中具有良好的分散稳定性;体外实验表明该磁性纳米粒具有良好的细胞相容性;大鼠体内肝脏磁共振造影实验表明Fe₃O₄/HTCC纳米粒注入后, 大鼠肝实质信号强度明显下降, 因此Fe₃O₄/HTCC纳米粒有望作为潜在的阴性造影剂应用于肝磁共振造影检测。     

Electrochemical Detection of Gunshot Residue for Forensic Analysis: A Review

Current demands for detection of Gunshot Residue (GSR) require a reliable and rapid decentralized detection system with high sensitivity and specificity. This article reviews the use of electrochemical devices for GSR detection over the last 35 years and highlights recent advances associated with the demands of GSR field detection such as portability, speed, cost and power. Anodic stripping voltammetry (ASV) has been widely implemented for the detection of the metallic components of GSR at a variety of working electrodes. Efforts toward the detection of the organic components of GSR have also been reported using cyclic‐ and square‐wave voltammetry. The simultaneous detection of both organic and inorganic GSR constituents has recently been examined to increase the overall information content in a single voltammetric scan. As well as this, exploitation of screen‐printing fabrication allows replacement of conventional electrochemical cells with easy‐to‐use sensor strips Sampling methods for electrochemical GSR analysis are also advancing from acid washes or swabs to simpler abrasive methods which integrate sampling and analysis obviating the need for intermediate processing steps. The latest direction of electrochemical detection of GSR involves chemometric treatment to evaluate data allowing for more objective conclusions and increasing the automation of the system. These advances indicate great promise for investigating firearm‐related crimes, and bring significant changes to the detection of GSR making electroanalysis a powerful tool for decentralized forensic analysis.     

PDMS extraction bars for the determination of volatile aromatic hydrocarbons in water and wastewater

In this study, the preparation and application of extraction bars of PDMS were investigated to preconcentrate and determine benzene, toluene, ethylbenzene, and xylene in water and wastewater by means of HPLC with fluorescence detection. Aliquot samples from hospital wastewater were used as the model effluent. The independent variables for the sorptive extraction were as follows: ionic strength (added amounts of NaCl); pH; temperature and time of absorption; temperature and time of desorption. Under optimized conditions, by using a factorial design, the suspended extraction bars could allow the determination of benzene, toluene, ethylbenzene, and xylene (1.20 ± 0.05 μg/L; 10.40 ± 0.02 μg/L; 1.80 ± 0.04 μg/L; 15.9 ± 0.04 μg/L, respectively) in hospital effluent (fortified samples), by recoveries of 71.9 ± 4.9 to 74.8 ± 5.6%. This procedure represents an innovation that eliminates the time‐consuming stage of vacuum microfiltration, and allows the determination of volatile organic compounds by HPLC. As far as we know, this procedure is original and represents an important contribution to the field.     

Monitoring of an esterification reaction by on-line direct liquid sampling mass spectrometry and in-line mid infrared spectrometry with an attenuated total reflectance probe

A specially designed thermal vaporiser was used with a process mass spectrometer designed for gas analysis to monitor the esterification of butan-1-ol and acetic anhydride. The reaction was conducted at two scales: in a 150 mL flask and a 1 L jacketed batch reactor, with liquid delivery flow rates to the vaporiser of 0.1 and 1.0 mL min⁻¹, respectively. Mass spectrometry measurements were made at selected ion masses, and classical least squares multivariate linear regression was used to produce concentration profiles for the reactants, products and catalyst. The extent of reaction was obtained from the butyl acetate profile and found to be 83% and 76% at 40 °C and 20 °C, respectively, at the 1 L scale. Reactions in the 1 L reactor were also monitored by in-line mid-infrared (MIR) spectrometry; off-line gas chromatography (GC) was used as a reference technique when building partial least squares (PLS) multivariate calibration models for prediction of butyl acetate concentrations from the MIR spectra. In validation experiments, good agreement was achieved between the concentration of butyl acetate obtained from in-line MIR spectra and off-line GC. In the initial few minutes of the reaction the profiles for butyl acetate derived from on-line direct liquid sampling mass spectrometry (DLSMS) differed from those of in-line MIR spectrometry owing to the 2 min transfer time between the reactor and mass spectrometer. As the reaction proceeded, however, the difference between the concentration profiles became less noticeable. DLSMS had advantages over in-line MIR spectrometry as it was easier to generate concentration profiles for all the components in the reaction. Also, it was possible to detect the presence of a simulated impurity of ethanol (at levels of 2.6 and 9.1% mol/mol) in butan-1-ol, and the resulting production of ethyl acetate, by DLSMS, but not by in-line MIR spectrometry.     

Reaction mechanism of Ru(II) piano‐stool complexes: Umbrella sampling QM/MM MD study

Biologically relevant interactions of piano‐stool ruthenium(II) complexes with ds‐DNA are studied in this article by hybrid quantum mechanics—molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru^II(η⁶‐benzene)(en)Cl]⁺ complex, (ii) monoadduct formation between the resulting aqua‐Ru(II) complex and N7 position of one of the guanines in the ds‐DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross‐link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)‐N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross‐link formation. One feasible pathway leading to Ru(II) guanine‐guanine cross‐link with synchronous releasing of the benzene ligand is predicted. The cross‐linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds‐DNA. © 2014 Wiley Periodicals, Inc.     

Small molecule‐mediated control of hydroxyapatite growth: Free energy calculations benchmarked to density functional theory

The unique, plate‐like morphology of hydroxyapatite (HAP) nanocrystals in bone lends to the hierarchical structure and functions of bone. Proteins enriched in phosphoserine (Ser‐OPO₃) and glutamic acid (Glu) residues have been proposed to regulate crystal morphology; however, the atomic‐level mechanisms remain unclear. Previous molecular dynamics studies addressing biomineralization have used force fields with limited benchmarking, especially at the water/mineral interface, and often limited sampling for the binding free energy profile. Here, we use the umbrella sampling/weighted histogram analysis method to obtain the adsorption free energy of Ser‐OPO₃ and Glu on HAP (100) and (001) surfaces to understand organic‐mediated crystal growth. The calculated organic‐water–mineral interfacial energies are carefully benchmarked to density functional theory calculations, with explicit inclusion of solvating water molecules around the adsorbate plus the Poisson–Boltzmann continuum model for long‐range solvation effects. Both amino acids adsorb more strongly on the HAP (100) face than the (001) face. Growth rate along the [100] direction should then be slower than in the [001] direction, resulting in plate‐like crystal morphology with greater surface area for the (100) than the (001) face, consistent with bone HAP crystal morphology. Thus, even small molecules are capable of regulating bone crystal growth by preferential adsorption in specific directions. Furthermore, Ser‐OPO₃ is a more effective growth modifier by adsorbing more strongly than Glu on the (100) face, providing one possible explanation for the energetically expensive process of phosphorylation of some proteins involved in bone biomineralization. The current results have broader implications for designing routes for biomimetic crystal synthesis. © 2013 Wiley Periodicals, Inc.