Collision-activated dissociation mass spectra of crown ethers,perfluorinated crown ethers and related macrocycles

The collision-activated dissociation (CAD) mass spectra for a series of crown ethers, perfluoro crown ethers, cryptands and several dicyclohexano substituted crown ethers are reported. The CAD spectra were acquired with a triple quadrupole mass spectrometer, and in some cases spectra were recorded as a function of collision energy. In general, the protonated crown ethers dissociate via a series of losses of C₂H₄O units. The perfluoro crown ethers dissociate predominantly via losses of C₂F₄O units. The dicyclohexano ethers fragment in analogous ways in conjunction with cleavage of the cyclohexano rings. CAD spectra are also reported for acyclic ether systems.     

常压下酸催化菊糖水解反应动力学研究

研究了菊芋中菊糖的酸催化水解。通过改变常压下菊糖酸催化水解的反应条件研究了反应动力学 ,得出该反应符合一级串连反应规律的结论     

无处不在的化学——探究生命的时钟

This paper mainly introduces the role of isotopes in exploring the origin of life and related principles. In addition, by reviewing the discovery history of isotopes and summarizing the contributions of major scientists, we hope to show the general process of science developments to the public.     

Non‐natural Photoenzymatic Controlled Radical Polymerization Inspired by DNA Photolyase

Inspired by DNA photolyase, a non‐natural photoenzymatic catalysis of common flavoproteins is developed for controlled radical polymerization under irradiation of visible light. This photoenzymatic polymerization is highly efficient under mild conditions, applicable to various monomer families, suitable for both homogeneous and heterogeneous media, and can be externally modulated by switching light on and off. A unique combination of the natural enzymatic deoxygenation with the non‐natural photoenzymatic process enables an unprecedented oxygen‐tolerant, visible‐light‐controlled radical polymerization using a single enzyme to be developed. Visible light activation of non‐natural catalytic functions of the widely distributed flavoproteins is an exciting conceptual advance and may uncover a hitherto underexplored field of photoenzymatic catalysis.     

Evaluation of three sorbent-phase extraction techniques based on hyper-crosslinked polymer for the extraction of five endocrine disrupters in water

A series of low-cost hyper-crosslinked polymers were prepared by an easy one-step Friedel-Crafts reaction. The synthesized hyper-crosslinked polymers exhibited remarkably porous structure, large surface area, and hydroxyl groups, which can be employed as an ideal adsorbent material for novel sorbent-phase extraction techniques. Based on this, using hyper-crosslinked polymers as sorbent and coating, three novel extraction methods, including micro-solid-phase extraction, dispersive solid-phase extraction, and solid-phase microextraction, were explored and evaluated for simultaneous measurement of five endocrine-disrupting compounds (triclosan and bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A bisallylether, and tetrabromobisphenol A bis(2,3-dibromopropyl ether)) in environment water prior to high-performance liquid chromatography–ultraviolet. The influence of experimental parameters on three extraction techniques such as extraction time, the amount of hyper-crosslinked polymers, extraction temperature, ionic strength, and desorption conditions were optimized. Three previously mentioned methods provided limits of detection ranging from 0.01 to 0.05 μg/L, and high recoveries (85–99%) with relative standard deviations of 1.7–5.6%. This study presented the merits and disadvantages of three proposed extraction methods and their potential for effective monitoring of hazardous pollutants in real water samples.     

Photochemistry and chemometrics—An overview

Photochemistry has made significant contributions to our understanding of many important natural processes as well as the scientific discoveries of the man-made world. The measurements from such studies are often complex and may require advanced data interpretation with the use of multivariate or chemometrics methods. In general, such methods have been applied successfully for data display, classification, multivariate curve resolution and prediction in analytical chemistry, environmental chemistry, engineering, medical research and industry. However, in photochemistry, by comparison, applications of such multivariate approaches were found to be less frequent although a variety of methods have been used, especially with spectroscopic photochemical applications. The methods include Principal Component Analysis (PCA; data display), Partial Least Squares (PLS; prediction), Artificial Neural Networks (ANN; prediction) and several models for multivariate curve resolution related to Parallel Factor Analysis (PARAFAC; decomposition of complex responses). Applications of such methods are discussed in this overview and typical examples include photodegradation of herbicides, prediction of antibiotics in human fluids (fluorescence spectroscopy), non-destructive in- and on-line monitoring (near infrared spectroscopy) and fast-time resolution of spectroscopic signals from photochemical reactions. It is also quite clear from the literature that the scope of spectroscopic photochemistry was enhanced by the application of chemometrics.To highlight and encourage further applications of chemometrics in photochemistry, several additional chemometrics approaches are discussed using data collected by the authors. The use of a PCA biplot is illustrated with an analysis of a matrix containing data on the performance of photocatalysts developed for water splitting and hydrogen production. In addition, the applications of the Multi-Criteria Decision Making (MCDM) ranking methods and Fuzzy Clustering are demonstrated with an analysis of water quality data matrix. Other examples of topics include the application of simultaneous kinetic spectroscopic methods for prediction of pesticides, and the use of response fingerprinting approach for classification of medicinal preparations. In general, the overview endeavours to emphasise the advantages of chemometrics’ interpretation of multivariate photochemical data, and an Appendix of references and summaries of common and less usual chemometrics methods noted in this work, is provided.     

Simultaneous siting and sizing of distribution centers on a plane

The benefits of simultaneous consideration of siting and sizing of distribution centers have been well acknowledged in supply chain design. Most formulations assume that the potential DC sites are known and the decision on location is to select sites from the finite potential DC sites. However, the quality of this discrete version problem depends on the selection of potential DC sites. In this paper we present a planar version of the problem, which assumes that there is no a priori knowledge of DC sites and DCs can be located anywhere in the plane. The goal of the problem is to simultaneously find locations and sizing of DC sites. The solution of the planar problem provides a lower bound for the discrete problem. The objective of the problem is to minimize the total of inbound and outbound transportation costs and distribution center construction costs—which include its fixed charge cost and concave sizing cost. The problem is initially formulated as a nonlinear programming model. We then reformulate it as a set covering problem after establishing certain key properties. A greedy drop heuristic and a column generation heuristic are developed to solve the problem. Computational experiments are provided.     

Oscillatory squeezing flow of a biological material

Large-amplitude oscillatory squeezing flow data are reported for a complex biological material, which is highly shear-thinning in oscillatory shear flow. This soft tissue has a linear viscoelastic limit at a strain of approximately 0.2%. The oscillatory squeezing flow data at large strain are analyzed using two constitutive models: a bi-viscosity Newtonian model, and a non-linear Maxwell model. It is found that although both models may have the same response in shape, the later matches with our non-linear experimental data better. It is also concluded that the non-linear response of the material in large amplitude oscillatory flow is mainly due to the shear thinning of the material. Received: 9 February 2000/Accepted: 22 February 2000