Synthesis and optical properties of poly(aryl ether ketone)s incorporating porphyrins in the backbones

A series of novel soluble poly(aryl ether ketone)s (PAEKs) based on 5,10‐bis(4‐hydroxyphenyl)?15,20‐diphenylporphyrin (cis‐DHTPP), 4,4′‐(hexafluoroisopropylidene) diphenol (6FBPA) and 4,4′‐difluorobenzophenone (DFB) were synthesized and characterized by FT‐IR, ¹H‐NMR, UV–vis and fluorescence spectroscopies. The intrinsic photophysical properties of porphyrins were preserved because of the absence of photoinduced electron transfer in the polymer chains. Investigation of the copolymers thermal properties indicated that these polymers had high glass transition temperatures and excellent thermal stabilities. The results of Z‐scan and optical limiting measurements manifested that incorporation of the porphyrin chromophore into the main chain engendered the novel PAEKs with superior nonlinear optical properties and optical limiting function, which could be effectively tuned by varying the molar ratio of porphyrin monomers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1282–1290     

The study of wave motion in the Talbot interferometer with a lens

We present the study of the wave motion in the Talbot interferometer with an additional element such as a lens for all related audiences. Our solutions are in the analytic form. A general principle of the Talbot effect, which is the optical near-field effect, is the Fresnel diffraction. The Fresnel integral is rather complicated. We therefore introduce an alternative method which is based on the wave propagation through the transmission functions of the grating and the lens. Our method has been proved by a simple experimental setup.     

Prediction of 195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

¹⁹⁵Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO₃)_n(OH)_{6 ? n}]^2?, [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 1–6), and [Pt(NO₃)_{6 ? n ? m}(OH)_m(OH₂)_n]^{?2 + n ? m} formed by dissolution of platinic acid, H₂[Pt(OH)₆], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge‐including atomic orbitals (GIAO)‐PBE0/segmented all‐electron relativistically contracted–zeroth‐order regular approximation (SARC–ZORA)(Pt) ∪ 6–31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second‐order polynomial plots of δ_calcd(¹⁹⁵Pt) versus δ_exptl(¹⁹⁵Pt) chemical shifts and δ_calcd(¹⁹⁵Pt) versus the natural atomic charge Q_Pt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ ¹⁹⁵Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σ^{iso 195}Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ ¹⁹⁵Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter‐ion effects on the ¹⁹⁵Pt NMR chemical shifts of the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? and cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 0–3) complexes we calculated the ¹⁹⁵Pt NMR chemical shifts of the neutral (PyH)₂[Pt(NO₃)_n(OH)_{6 ? n}] (n = 1–6; PyH = pyridinium cation, C₅H₅NH⁺) and [Pt(NO₃)_n(H₂O)_{6 ? n}](NO₃)_{4 ? n} (n = 0–3) complexes. Counter‐anion effects are very important for the accurate prediction of the ¹⁹⁵Pt NMR chemical shifts of the cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} complexes, while counter‐cation effects are less important for the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd.     

润滑油膜光纤干涉仪测量的原理探讨

高速流体动压滑动轴承被广泛应用在许多大型或高速旋转机械中,而其产生的润滑油膜特性直接影响这些轴承的工作性能,所以如何测量油膜厚度一直是一个重要的研究领域.为了实现对油膜厚度的准确测量,介绍了一种新的基于光纤迈克尔逊干涉仪测量方法.     

Strong optical nonlinearities of self-assembled polymorphic microstructures of phenylethynyl functionalized fluorenones

The polymorphs of a phenylethynyl functionalized fluorenone derivative, and their controlled self-assembly for microstructures with different morphologies have been studied. These polymorphic microcrystals exhibit very distinctive NLO properties, which are highly correlated to their electronic and supramolecular structures.     

Two Histidines in an α‐Helix: A Rigid Co2+‐Binding Motif for PCS Measurements by NMR Spectroscopy

Pseudocontact shifts (PCS) generated by paramagnetic metal ions present valuable long‐range information in the study of protein structural biology by nuclear magnetic resonance (NMR) spectroscopy. Faithful interpretation of PCSs, however, requires complete immobilization of the metal ion relative to the protein, which is difficult to achieve with synthetic metal tags. We show that two histidine residues in sequential turns of an α‐helix provide a binding site for a Co²⁺ ion, which positions the metal ion in a uniquely well‐defined and predictable location. Exchange between the bound and free cobalt is slow on the timescale defined by chemical shifts, but the NMR resonance assignments are nonetheless readily transferred from the diamagnetic to the paramagnetic NMR spectrum by an I_zS_z‐exchange experiment. The double‐histidine‐Co²⁺ motif offers a straightforward, inexpensive, and convenient way of generating precision PCSs in proteins.     

光栅刻划机刻划系统光机电集成优化方法研究

针对大面积衍射光栅刻划机在宏观尺度下进行微纳加工的工作特点以及纳米级刻线检测困难的问题,提出了一种光机电集成优化方法.此方法采用计算傅里叶光学和弦振动理论进行光栅刻线误差分析,结合振动实验及光学测量进行验证,最后采用智能优化方法对刻划系统进行结构参数优化.虚拟样机仿真结果表明,刻划系统的振动幅度降低了30%,验证了该集成优化方法的有效性.     

掺镱光学频率梳噪声抑制与载波包络相位锁定

本文研究了泵浦源功率稳定性、环境温度和机械振动等因素对掺镱光纤光学频率梳自由运转下的载波包络偏移相位的影响,基于锁相环伺服反馈系统实现了光学频率梳的载波包络相位锁定.实验中采用重复频率为60 MHz的掺镱光纤飞秒激光器,经过两级功率放大、光谱展宽和f-2f拍频探测系统,获得了信噪比为25 dB的拍频信号.在此基础上,由伺服反馈系统对载波包络相位信号进行控制,锁定后的载波包络相位信号的频率抖动标准方差为283 mHz(计数时间为0.5 h).     

An extraction system for low-energy hydrogen ions formed by electron impact

A system has been developed for extracting near-zero kinetic energy H⁻ and D⁻ ions formed by dissociative electron attachment. It is the essential part of a new set-up for vibrational spectroscopy of hydrogen molecules. A magnetic field is used to collimate the probing electron beam. Ions produced by electron collision with the target molecules are collected by the combined action of this field and an electrostatic field penetrating into the interaction region. Highly effective extraction is achieved by taking into account the correct out-of plane displacement of ion trajectories which is usually neglected in similar arrangements. The extraction conditions are mass dependent so that by proper tuning, mass selection of detected ions is achieved. The new system is also used for detecting positive ions created by electron collisions with hydrogen atoms and molecules.