β-Isothiocyanatoketones: A Convenient Source of Heterocyclic Compounds

Summary. The preparation of -isothiocyanatoketones and their reactions leading to formation of pyrimidine and bicyclic, tricyclic, tetracyclic, and pentacyclic heterocyclic compounds are reviewed. A few references concerning the rearrangement of heterocyclic compounds are also included. Some of the compounds reported have shown good antiinflammatory activity.     

Demonstration of a surface plasmon-coupled emission (SPCE)-based immunoassay in the absence of a spacer layer

The technique of surface plasmon-coupled emission (SPCE) involves the coupling of light which is emitted from a fluorophore into the surface plasmon of an adjacent thin metal film, giving rise to highly directional emission. We have combined the advantages of SPCE with the high light collection efficiency of supercritical angle fluorescence by carrying out an immunoassay on a paraboloid array biochip in the absence of the conventional SPCE spacer layer normally used to minimize metal quenching of the fluorescence. In this work, we have successfully demonstrated an SPCE-based assay by utilizing the protein assay layer as the spacer layer. A novel 3 × 3 injection molded polymer biochip with paraboloid elements was used. The paraboloid elements served to enhance the light collection efficiency while the top surface was coated with a gold layer to use excitation of surface plasmons and detection of SPCE emission. Theoretical modeling of the gold-protein layer structure showed that the surface plasmon resonance angles were located in the detection range of the paraboloid biochip. The polarization dependence of SPCE emission was also demonstrated. Finally, a human IgG sandwich immunoassay was carried out which exhibited a limit of detection of ~10 ng/ml using 3σ. The results demonstrate the potential of the SPCE-based paraboloid array biochip as a novel platform for high-throughput analysis of biomolecular interactions.     

Solvent‐induced crystallization in poly(ethylene terephthalate) during mass transport

Solvent transport in poly(ethylene terephthalate) (PET) and related phase transformation were investigated. The data of mass sorption were analyzed according to Harmon's model for Case I (Fickian), Case II (swelling), and anomalous transport. This transport process in PET is accompanied by the induced crystallization of the original amorphous state. The transformation was examined by wide‐angle X‐ray scattering, small‐angle X‐ray scattering, differential scanning calorimetry, and Fourier transform infrared spectroscopy. During this process, the matrix is under a strain state that causes different kinetic paths of crystallization as compared with that by thermal annealing. This state of strain assists the development of the solvent‐induced crystallization. The model regarding crystallization was proposed in terms of the study of long period L, the crystal thickness l_c, and the thickness of amorphous layer l_a obtained from the one‐dimensional correlation function and interface distribution function. Different kinetic paths were discovered for different crystallization processes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1444–1453, 2002     

Simplified liquid chromatographic determination of glyphosate and metabolite residues in environmental water using post-column fluorogenic labelling

Glyphosate and its metabolite aminomethylphosphonic acid in environmental water can be preconcentrated with an anion-exchange column, eluted with potassium citrate solution and determined directly by liquid chromatography with a post-column reactor and a fluorescence detector. The limit of detection and average recovery are 1 μg 1^?1 and 89.3% for glyphosate and 0.4 μg l^?1 and 86.3% for the metabolite.     

Catalytic Asymmetric 1,6‐Conjugate Addition of para‐Quinone Methides: Formation of All‐Carbon Quaternary Stereocenters

Described herein is a general and mild catalytic asymmetric 1,6‐conjugate addition of para‐quinone methides (p‐QMs), a class of challenging reactions with previous limited success. Benefiting from chiral Brønsted acid catalysis, which allows in situ formation of p‐QMs, our reaction expands the scope to general p‐QMs with various substitution patterns. It also enables efficient intermolecular formation of all‐carbon quaternary stereocenters with high enantioselectivity.     

Asymptotic analysis of growing plane strain tensile cracks in elastic-ideally plastic solids

An exact asymptotic analysis is presented of the stress and deformation fields near the tip of a quasistatically advancing plane strain tensile crack in an elastic-ideally plastic solid. In contrast to previous approximate analyses, no assumptions which reduce the yield condition, a priori, to the form of constant in-plane principal shear stress near the crack tip are made, and the analysis is valid for general Poisson ratio ν. Specific results are given for ν = 0.3 and 0.5, the latter duplicating solutions in previous work by L.I. Slepyan, Y.-C. Gao and the present authors. The crack tip field is shown to divide into five angular sectors of four different types ; in the order in which these sweep across a point in the vicinity of the advancing crack, they are : two plastic sectors which can be described asymptotically (i.e., as r → 0, where r is distance from the crack tip) in slip-line terminology as ‘constant stress’ and ‘centered fan’ sectors, respectively ; a plastic sector of non-constant stress which cannot be described asymptotically in terms of slip lines; an elastic unloading sector; and a trailing plastic sector of the same type as that directly preceding the elastic sector. Further, these four different sector types constitute the full set of asymptotically possible solutions at the crack tip. As is known from prior work, the plastic strain accumulated by a material point passing through such a moving ‘centered fan’ sector is O(ln r) as r → 0 ; it is proved in the present work that the plastic strain accumulated by a material point passing through the ‘constant stress’ sector ahead of a growing crack must be less singular than In r as r → 0. As suggested also in earlier studies, the rate of increase of opening gap δ at a point currently at a distance r behind, but very near, the crack tip is given for crack advance under contained yielding by

$\text{δ}\text{?}\text{=}\text{α}\text{J}\text{?}\text{σ}{}_0\text{+β(}\text{σ}{}_0\text{E}\text{)}\text{a}\text{?}\text{ln(}\text{R}\text{r}\text{)}$

where a is crack length, σ0 is tensile yield strength, E is Young's modulus, J is the value of the J-integral taken in surrounding elastic material, and the parameters α and R are undetermined by the asymptotic analysis. The exact solution for ν = 0.3 gives β = 5.462, which agrees very closely with estimates obtained from finite element solutions. An approximate analysis based on use of slip line representations in all plastic sectors is outlined in the Appendix.     

A new melampolide and other secondary metabolites from <Emphasis Type="Italic">Artemisia baldshuanica</Emphasis>

The composition of secondary metabolites in benzene and alcohol extracts of the epigeal part of Artemisia baldshuanica Krasch. et Zarp. (Asteraceae) collected during the vegetative phase was investigated. A new melampolide, the structure of which was established based on spectral data and an x-ray crystal structure analysis, and known compounds were isolated.