Fluorescence studies and semiempirical calculations on alkali ion indicators

Two newly synthesized cryptands act as sensitive Na⁺- and K⁺-selective indicators for cation concentrations above 20 M. The fluorescence properties change markedly upon cation binding. In addition, the free ligands exhibit a pronounced sensitivity to pH, which is considerably lower for the cation complexes. Time resolved fluorescence is characterized by a decay time of about 5 ns that is attributed to the diprotonated protolytic state of the uncomplexed ligands. Semiempirical calculations show the systematic influence of the nitrogen lone pairs or the N–H bond on the stability of the system. The cause of the strong fluorescence intensity increase observed upon protonation of the fluorescent cryptands may be attributed to an increase in the S₁–T _x energy gap as a consequence of bridgehead nitrogen protonation.This is a peer-reviewed conference proceeding article from the Third Conference on Methods and Applications of Fluorescence Spectroscopy, Prague, Czech Republic, October 18–21, 1993.     

pH‐sensing nanostar probe using surface‐enhanced Raman scattering (SERS): theoretical and experimental studies

Local pH environment has been considered to be a potential biomarker for tumor diagnosis because solid tumors contain highly acidic environments. A pH‐sensing nanoprobe based on surface‐enhanced Raman scattering (SERS) using nanostars under near‐infrared excitation has been developed for potential biomedical applications. To theoretically investigate the effect of protonation state on SERS spectra of p‐mercaptobenzoic acid (pMBA), we used the density functional theory (DFT) with the B3LYP functional to calculate Raman vibrational spectra of pMBA‐Au/Ag complex in both protonated and deprotonated states. Vibrational spectral bands were assigned with DFT calculation and used to investigate SERS spectral changes observed from experiment when varying pH value between five and nine. The SERS peak position of pMBA at ~1580 cm⁻¹ was identified to be a novel pH‐sensing index, which has small but noticeable downshift with pH increase. This phenomenon is confirmed and well‐explained with theoretical simulation. The study demonstrates that SERS is a sensitive tool to monitor minor structural changes due to local pH environment, and DFT calculations can be used to investigate Raman spectra changes associated with minor differences in molecular structure. Copyright © 2013 John Wiley & Sons, Ltd.     

有机掺杂溶胶-凝胶法制备pH敏感膜及其光谱响应的研究

使用四甲氧基硅烷（TMOS）和二甲基二甲氧基硅烷（DiMe-DMOS)为共先驱体，采用溶胶－凝胶的有机掺杂，制备对pH具有宽程响应的敏感膜。详细考察了包埋溴酚蓝和溴酚绿的敏感膜对pH的响应值、响应时间、泄漏和可逆性等响应性能指标，并进行了溴酚蓝和溴酚绿在水相与膜内吸收光谱的研究。     

激光诱导法制备SERS光纤pH传感器

利用光化学法在光纤尖端快速沉积银纳米粒子构建活性层,通过银纳米粒子与探针分子4-巯基吡啶分子中的巯基吸附作用,将探针分子组装在银膜上制备SERS光纤传感器。检测光纤活性端在不同pH缓冲液中探针分子的SERS光谱,对比分析其SERS光谱特征峰强度及拉曼频移的差异,讨论探针分子在不同pH值下结构的变化、与银膜之间夹角的变化,并通过重复实验证明这种SERS光纤pH传感器在实际检测中的应用价值。     

Space tests of relativistic gravity with precision clocks and atom interferometers

Precision clocks and interferometers in space can test relativistic gravity with extremely high sensitivity. Yet, only a single such test has been performed, namely the celebrated flight of a hydrogen maser in a sub-orbital trajectory in 1976 (GP-A mission). This paper suggests some of the obstacles to space flight of precision instruments, and describes how the emergence of new technology might offer a pathway for removing those obstacles. A brief review of emerging technologies is made, and new mission concepts based on them are described. Some of the technologies that can impact more tests of relativistic gravity in space at a more distant future are also described.     

咪唑类氮氧自由基的ESR波谱的酸度相关性-pH自旋探针应用研究之一

根据咪唑类氮氧自由基的结构特性合成了一系列的pH自旅探针,其ESR波谱参数均在一定范围内与介质的酸性呈明显的相关性.可望为较精确地测量化学胶束、细胞等微观体系的pH值开辟一个新的途径.本文研究了灵敏变化的pH范围与取代基的关系,得到了5种自旅探针的ESR参数-pH曲线、pKa值以及Hanmmett相关图,分析了如何通过改变取代基合成出不同pH变化范围并适用于不同生物和化学体系的pH自旅探针,最终达到付诸应用的目的.     

Enhanced Ratiometric pH Sensing Using SNAFL-2 on Silver Island Films: Metal-enhanced Fluorescence Sensing

We have explored the opportunities for enhanced ratiometric pH sensing using the well-known carboxy seminaphthofluorescein (SNAFL-2) and silver island films (SiFs). Our results show that the metallic surfaces can provide up to a 40-fold increase in probe fluorescence intensity as compared to nonmetallic surfaces with the same probe coverage. However, while the S/N is significantly better for pH sensing, the emission wavelength ratiometric values are similar to that obtained in solution, due to the fact that the emission of both the acidic and basic forms of the probe are enhanced to similar extents. To the best of our knowledge this is the first report of enhanced ratiometric fluorescence sensing on metallic surfaces.     

Growth and magnetic properties of single crystalline Ni nanowire arrays prepared by pulse DC electrodeposition

Highly textured Ni nanowire arrays were fabricated into anodic aluminum oxide(AAO) templates by pulse DC electrodeposition.The applied voltage and pH value of electrolytes were found strongly affecting the microstructure and magnetic properties of Ni nanowire arrays.Low applied potential and pH value both prefer to form polycrystalline fcc Ni nanowires.Increasing the applied potential or pH value favors the Ni [220] texture and even eventually forms the [220] oriented single crystal Ni wires,while exorbitan...     

An optical fibre pH sensor based on dye doped mesostructured silica

This paper describes the synthesis and optical pH sensing properties of a pH indicator dye activated mesostructured silica coated optical fibre. The pH-sensitive dye bromothymol blue was incorporated into the mesostructure sol precursor and thin films/coatings were used for pH-sensing applications without prior removal of the surfactant. The pH sensitivity range and operating wavelength were analysed by absorption measurements on layer dip-coated on glass slides. The pH sensing properties of coated optical fibre were tested by evanescent wave method. Experiments were carried out by using a series of solutions of known pH. No leaching was observed (except at very high pH) and an excellent reversibility was obtained between pH=2 and 5.     

CdTe/CdO nH2O核壳纳米复合粒子的水相合成及光学特性.

"研究了CdTe/CdO?nH2O核壳纳米复合物的水相合成及其光学特性． 以巯基乙酸为稳定剂通过氯化镉和碲氢化钠反应制备了碲化镉纳米晶． 在反应过程中, 反应前驱溶液中镉离子与碲离子的摩尔浓度比对最终制备的碲化镉纳米晶的荧光强度起到了极其重要的作用． 在pH值为8.2, 镉离子与碲离子摩尔浓度比为4.0的情况下,制备出了具有最强荧光强度的碲化镉量子点．之后,CdTe/CdO?nH2O核壳纳米复合物在水相中制备出来．在适当的氢氧化镉沉积在碲化镉纳米粒子表面后,碲化镉量子点的荧光大大增强．所制备的CdTe/C