Novel Process Applications Using PHI-TEC II Adiabatic Calorimeter

This paper presents several applications of the PHI-TEC II that are not commonly associated with adiabatic calorimeters but which have proved to be extremely valuable. These include simulation of a deep oil well for enhanced oil recovery, isothermal calorimetry of a semibatch reaction, catalyst research using flow through reactors (both plug flow and CSTR) with controlled feeds of high pressure liquid and gas.This revised version was published online in November 2005 with corrections to the Cover Date.     

Vanadium Chloroperoxidases: The Missing Link in the Formation of Chlorinated Compounds and Chloroform in the Terrestrial Environment?

It is well established that the majority of chlorinated organic substances found in the terrestrial environment are produced naturally. The presence of these compounds in soils is not limited to a single ecosystem. Natural chlorination is also a widespread phenomenon in grasslands and agricultural soils typical for unforested areas. These chlorinated compounds are formed from chlorination of natural organic matter consisting of very complex chemical structures, such as lignin. Chlorination of several lignin model compounds results in the intermediate formation of trichloroacetyl‐containing compounds, which are also found in soils. These decay, in general, through a haloform‐type reaction mechanism to CHCl₃. Upon release into the atmosphere, CHCl₃ will produce chlorine radicals through photolysis, which will, in turn, lead to natural depletion of ozone. There is evidence that fungal chloroperoxidases able to produce HOCl are involved in the chlorination of natural organic matter. The objective of this review is to clarify the role and source of the various chloroperoxidases involved in the natural formation of CHCl₃.     

Introducing nonlinear,multivariate ‘Predictor Surfaces’ for quantitative modeling of chemical systems with higher-order,coupled predictor variables

Innovations in chemometrics are required for studies of chemical systems which are governed by nonlinear responses to chemical parameters and/or interdependencies (coupling) among these parameters. Conventional and linear multivariate models have limited use for quantitative and qualitative investigations of such systems because they are based on the assumption that the measured data are simple superpositions of several input parameters. ‘Predictor Surfaces’ were developed for studies of more chemically complex systems such as biological materials in order to ensure accurate quantitative analyses and proper chemical modeling for in-depth studies of such systems. Predictor Surfaces are based on approximating nonlinear multivariate model functions by multivariate Taylor expansions which inherently introduce the required coupled and higher-order predictor variables.     

Ordered long‐helical conformation of isotactic polypropylene obtained in constrained environment of nanoclay

Special crystallization event of isotactic polypropylene (iPP) in a constrained environment, a layered clay network, was followed by in situ Fourier transform infrared (FTIR) spectroscopy during the cooling process. Before occurrence of nucleation/crystallization, a conformationally ordered phase, which consists of significant amounts of long 3₁ helices with 14 monomeric units, has been identified for the first time. More importantly, it was found that the long‐ordering helices could play a more important role than short ones for the confined crystallization. It could be tentatively explained as due to the existence of constrained regions in the proximity of the nanoclay platelets or tactoids and the heterogeneous nucleation capability of the surface of nanoclay. Copyright © 2011 John Wiley & Sons, Ltd.     

考虑环境因素的中国城市经济效率评价研究

在考虑环境因素情形下,实证考察中国城市经济效率水平.引入环境因素,构建中国城市经济效率评价指标体系;运用DEA-BCC模型对中国31个省会城市和计划单列市的经济效率进行评价,计算得出各决策单元的DEA评价值,并进行效率分析、投入冗余产出不足分析和区域比较分析.考虑环境因素情形下,中国城市经济效率总体上较好,综合效率、纯技术效率和规模效率平均值分别达0.912、0.855和0.940,但个体差异较大,存在个体间的非均衡发展;从规模报酬来看,太原、福州、南昌等10个决策单元的经济规模应适当增加;长春、哈尔滨、南京等9个决策单元的经济规模应适当减少;太原、长春、哈尔滨等16个决策单元存在不同程度的投入冗余和产出不足,亟待改进;中国城市经济效率存在区域间的非均衡发展,综合效率平均值呈现东部地区最高,中部地区次之,西部地区最低的格局.     

基于盲数理论和随机模拟的河流水环境容量计算

针对水环境系统的不确定性,将延拓盲数引入到水环境容量计算模型中,并运用随机模拟方法对盲参数进行模拟,把盲数之间的运算转化为普通实数之间的运算,从而建立了水环境容量的延拓盲数与随机模拟的耦合模型.经实例研究,得到研究对象的水环境容量随机模拟分布以及在不同保证率下的水环境容量值,为研究对象当地的水环境规划和保护提供丰富可靠的依据.     

More efficient estimators for marginal additive hazards model in case-cohort studies with multiple outcomes

Case-cohort study designs are widely used to reduce the cost of large cohort studies. When several diseases are of interest, we can use the same subcohort. In this paper, we will study the casecohort design of marginal additive hazards model for multiple outcomes by a more efficient version. Instead of analyzing each disease separately, ignoring the additional exposure measurements collected on subjects with other diseases, we propose a new weighted estimating equation approach to improve the efficiency by utilizing as much information collected as possible. The consistency and asymptotic normality of the resulting estimator are established. Simulation studies are conducted to examine the finite sample performance of the proposed estimator, which confirm the efficiency gains.     

A Tensile Strain Hardening Test Indicator of Environmental Stress Cracking Resistance

Environmental stress cracking resistance (ESCR) is an important indicator of performance for high density polyethylene (HDPE) in structural and polymer pipe applications. The commonly used test for determining ESCR of HDPE can be time consuming and rather imprecise. A tensile strain hardening test was recently proposed to offer a faster way to characterize ESCR of polyethylene. In this paper, a practical approach is adopted whereby the test is extended to room temperature and shown to relate reliably to the ESCR of HDPE. Several HDPE resins (including pipe‐grade resins) are analyzed at strain rates of 0.5 mm/min and 7 mm/min to compare the effect of strain rate. Comparisons between the conventional ESCR test method and the strain hardening test show that strain hardening can be used to rank ESCR of HDPE in a reliable fashion. In our study the more direct measure of “hardening stiffness” is used to compare resins instead of strain hardening modulus. Because no true stress‐strain measurement is needed, this is a much simpler test method than other methods previously suggested. In addition, the use of the natural drawing ratio (NDR) as ESCR ranking indicator is examined. Results show that NDR can also be employed as a strain rate‐independent indicator of ESCR of HDPE. The test proposed herein is practical, simple and precise, and hence a more reliable indicator of ESCR performance of HDPE.     

Single-drop microextraction technique for the determination of antibiotics in environmental water

Growing concerns related to antibiotic residues in environmental water have encouraged the development of rapid, sensitive, and accurate analytical methods. Single-drop microextraction has been recognized as an efficient approach for the isolation and preconcentration of several analytes from a complex sample matrix. Thus, single-drop microextraction techniques are cost-effective and less harmful to the environment, subscribing to green analytical chemistry principles. Herein, an overview and the current advances in single-drop microextraction for the determination of antibiotics in environmental water are presented were included. In particular, two main approaches used to perform single-drop microextraction (direct immersion-single-drop microextraction and headspace-single-drop microextraction) are reviewed. Furthermore, the impressive analytical features and future perspectives of single-drop microextraction are discussed in this review.