Synthesis and structure‐activity relationship of several aromatic ketone‐based two‐photon initiators

Several novel aromatic ketone‐based two‐photon initiators containing triple bonds and dialkylamino groups were synthesized and the structure‐activity relationships were evaluated. Branched alkyl chains were used at the terminal donor groups to improve the solubility in the multifunctional monomers. Because of the long conjugation length and good coplanarity, the evaluated initiators showed large two‐photon cross section values, while their fluorescence lifetimes and quantum yields strongly depend on the solvent polarity. All novel initiators exhibited high activity in terms of two‐photon‐induced microfabrication. This is especially true for fluorenone‐based derivatives, which displayed much broader processing windows than well‐known highly active initiators from the literature and commercially available initiators. While the new photoinitiators gave high reactivity in two‐photon‐induced photopolymerization at concentration as low as 0.1% wt, these compounds are surprisingly stable under one photon condition and nearly no photo initiation activity was found in classical photo DSC experiment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

NMR‐based analysis of structure of heteroleptic triple‐decker (phthalocyaninato) (porphyrinato) lanthanides in solutions

A novel approach for the structural analysis of heteroleptic triple‐decker (porphyrinato)(phthalocyaninato) lanthanides(III) in solutions is developed. The developed approach consists in molecular mechanics (MM+) optimization of the geometry of the complex taking into account the lanthanide‐induced shift (LIS) datasets. LISs of the resonance peaks in ¹H NMR spectra of a series of symmetric complexes [An₄P]Ln[(15C5)₄Pc]Ln[An₄P], where An₄P^2? is 5,10,15,20‐tetrakis(4‐methoxyphenyl)porphyrinato‐dianion, [(15C5)₄Pc]^2? is 2,3,9,10,16,17,24,25‐tetrakis(15‐crown‐5)phthalocyaninato‐dianion and Ln = La, Ce, Pr, Nd, Sm, Eu, are analyzed. Analysis of LISs showed two sets of protons in the molecule with opposite signs of shift. Two‐nuclei analysis of LISs testifies isostructurality of the whole series of investigated complexes in solution despite contraction of the lanthanide ions. Model‐free separation of contact and dipolar contributions of LISs was performed with one‐nucleus technique and did not show changes in contact and dipolar terms within the investigated series. MM+ optimization of the molecular structure allowed the interpretation of features of LIS for each particular group of protons. Parameterization of MM + ‐optimized model of molecule with values of structure‐dependent dipolar contributions of LIS allows the development of the precise structural model of the triple‐decker complex in solution. This approach allows the determination of the geometry and structure of the sandwich macrocyclic tetrapyrrolic complexes together with conformational analysis of flexible peripheral substituents in solutions. The developed method can be applied with minor modifications for the determination of structural parameters of other types of lanthanides(III) complexes with tetrapyrrolic ligands and also supramolecular systems based on them. Copyright © 2010 John Wiley & Sons, Ltd.     

Multielement determination of major elements in polymer additives by microwave induced plasma atomic emission spectrometry after microwave digestion

A method for multielement determination of major elements in polymer additives by microwave induced plasma atomic emission spectrometry (MIP-AES) has been elaborated. Microwave digestion with nitric acid was selected for sample preparation because of its speed and versatility. Sodium nitrate was added to the digestion mixture in order to reduce phosphorus losses. The precision obtained varied between 2 and 4.5% depending on the element determined. The accuracy of the method was studied by analyzing the Spex 5-element oil standard. The method was applied to a variety of commercial and in-house prepared compositions.     

激光表面纹理化过程中的Rayleigh-Taylor不稳定性

用表面纹理化的热模型 ,分析了固体表面的熔化和重固化的物理过程 ,计算了在纹理化过程中的表面温度、穿透深度、熔化深度、相面移动速度等物理量 ,提出了 Rayleigh-Taylor不稳定性形成周期化结构的机理。     

再谈"三维导体"的自感系数

由公式ε＝Ｌ│ｄＩ／ｄｔ│出发，只要求出“三维导体”中的等效自感电动势，即可求得自感系数Ｌ，并以无限长同轴电缆自感系数的求解为例加以证明。     

Optical behavior of antibiofouling additives in environment‐friendly coverglass materials for bio‐sensors and solar panels

Solar panels and bio‐optical sensors play a significant and growing role in a number of applications that are of importance to many organizations. Many of these instruments require a high transmission of radiation into the device for it to work properly. A major issue faced is that harsh marine environments often aid in the growth or development of fouling on the coverglass used to protect the instruments. Over a period of time in an ocean environment, some plant or animal may attach itself to the coverglass, ultimately obscuring the glass and rendering the instrument useless. As such, an antifouling mechanism is needed for these instruments that is inexpensive, long‐lasting, and environment friendly. The approach discussed herein involves the use of known antifouling chemicals which have been incorporated into the polymer matrix. Polymethylmethacrylate (PMMA), bisphenol A polycarbonate (Bis A PC), and a co‐polyterephthalate (CPTE) were examined. The plaques are optically transparent and previous work has shown that, for most samples, the materials display a minimal decrease in mechanical behavior upon the addition of the algaecides. This paper will discuss the effects on the materials' optical properties when exposed to both harsh marine conditions as well as high intensity UV light. Specifically, the decrease in transmission of visible light was examined over a 6 month period of time. Copyright © 2008 John Wiley & Sons, Ltd.     

Luminance and Chromaticity Conditions of a Bichromatic Cross Pattern for Chromatically-Uniform Transparency

We can perceive a surface through another surface. This perception is called transparency. It is known that transparency can be perceived even if the stimulus conditions are not consistent with physical conditions for a real transparent surface. In this study, we measured the ranges of luminance and chromaticity of the overlapping area of two crossed layers at which a surface was perceived as chromatically-uniform transparent. As the results, the luminance range of the overlapping area existed around or near the luminance of the inducing area. The upper and lower limits of the luminance range were higher for the dark background than for the light background. Moreover, the chromatic range existed around the additive colormixture line between two chromaticities of the inducing areas for both dark and light backgrounds. This indicates that the perceptual transparency mechanism would divide the color of an additive color mixture into the original colors that exist in the inducing areas. We noticed that the perceptual appearance of the stimulus changed greatly depending on the luminances of the overlapping area and the background. These differences in perceptual appearance would be a factor explaining individual difference and deciding the luminance conditions for transparency.