Inclusion Complex Formation of Thiacalix[4]arene and Xe in Aqueous Solution Studied by Hyperpolarized 129Xe NMR

The inclusion complex formation of 4-sulfothiacalix[4]arene sodium salt (STCAS) and Xe has been investigated by using hyperpolarized ¹²⁹Xe NMR spectroscopy. Our new continuous-flow type hyperpolarizing system has advantageous capabilities that can supply hyperpolarized gases continuously and directly to a sample solution in a NMR tube. Consequently saturated Xe concentration in the aqueous solution of STCAS is maintained during the NMR experiment, and ¹²⁹Xe NMR spectra can be obtained in remarkably short time. STCAS concentration dependence of ¹²⁹Xe chemical shift has been analyzed in an elaborated way by a computer method as well as a simple graphic method that we have proposed. The association constant K:13.6±0.8 M⁻¹ at 25 °C was obtained, and further analysis of the temperature dependence has successfully given thermodynamic parameters of enthalpy (ΔH) and entropy (ΔS) for the inclusion complex formation: ΔH = −11.9±1.9 kJ mol⁻¹ and ΔS = −17.4±5.8 JK⁻¹ mol⁻¹. The energetic aspects of complex formation are discussed from the size effect and from the molecular theory of standard entropy, and a release of definite number of water molecules from STCAS cavity is suggested in the inclusion complex formation with Xe.     

Long-lived phosphorescence of aqueous solutions of β-cyclodextrin complexes with naphthalene and its derivatives at room temperature

A long-lived phosphorescence at room temperature (lifetime>1 s) of aqueous solutions of β-cyclodextrin complexes with naphthalene and its derivatives was found. The phosphorescence isobserved for aggregated complexes that form in water a light-scattering suspension, and its low intensity is due to predomination of 2∶2 complexes with efficient excimer fluorescence. Complexes containing isolated aromatic molecules are assumed to be the centers of fluorescence. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2022–2024, October, 1999.     

Photopolyaddition of dithiols to bis(alkoxyallene)s

Polyadditions of 1,4-benzenedithiol (BDT) to bis(alkoxyallene)s, such as 1,4-bis(allenyloxy)xylene (3) and 1,4-bis(allenyloxy) benzene (4) , were carried out in benzene at 25°C by irradiation with a high pressure mercury lamp. Thiol groups were added to the terminal double bonds of the allenyloxy groups selectively to afford polymers containing reactive carbon–carbon double bonds in the main chain, similar to the radical polyadditions using azobis(isobutyronitrile) (AIBN). The molecular weight of the polymer obtained from BDT and 3 was 10 times higher than that of the polymer produced in the radical polyaddition with AIBN; whereas the molecular weight of the polymer from BDT and 4 was similar to that in the radical polyaddition, probably because of poor solubility of 4 and the polymer toward benzene. The geometrical structure of carbon–carbon double bonds in the polymer isomerized from an E to Z structure with reaction time by virtue of both the addition elimination of thiyl radical to the double bonds and the UV irradiation. © 1996 John Wiley & Sons, Inc.     

An atom-based explanation for the absence of excimer emission in the fluorescence of dilute solutions of poly(pentafluorostyrene)

The steady-state fluorescence emission spectrum of poly(pentafluorostyrene) in dilute fluid solution shows no excimer emission. An atomic level modeling study explains why this polymer cannot form an excimer. Repulsive Coulombic interactions prohibit the attainment of the extensive overlap of the two rings in the classic face-to-face sandwich conformation of a singlet excimer.     

Photophysics of carbazole-containing systems. 1. Dilute solution behavior of poly(N-vinyl carbazole) and N-vinyl carbazole/methyl acrylate copolymers

Steady-state and time-resolved fluorescence techniques have been used to study the photophysical behaviors of poly(N-vinyl carbazole), PNVCz and a series of N-vinyl carbazole-methyl acrylate (NVCz-co-MA) copolymers in dilute solution as a function of both NVCz composition and temperature. A kinetic scheme, intended to describe intramolecular excimer formation across the entire NVCz composition range, is proposed. In low aromatic content copolymers, two monomer species (unquenched and quenched monomer) and two excimer species (the sandwich-like excimer and a higher energy excimer) exist. The contribution from monomer emission to the overall fluorescence decreases with increasing NVCz content through increased excimer formation: this is likely to be consequent upon (1) an increase in the number of excimer forming sites, and (2) increasing efficiency of energy transfer from the excited monomers to the excimer forming sites. In the homopolymer, PNVCz, the only emission that can be observed on a nanosecond timescale is excimeric. This fluorescence appears to originate from three excimer species (the sandwich-like excimer, and two higher energy forms). For the homopolymer, the current observations are consistent with the model proposed by Vandendriessche and De Schryver [Polym. Photochem. 7 , 153 (1986)]. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 963–978, 1997     

Comparison of the Structural Information on Sol-Gel Systems Provided by Pyrene Labeled Fluorescent Probes

The influence of the acid catalyst concentration on the structural evolution of a sol-gel system was studied by doping TEOS based starting solutions with two fluorescent probes: a polystyrene chain (M _n =1700) and a much shorter alkane chain (M=172), both of them labeled at both ends with 1-pyrenyl. For this purpose, each probe was incorporated in two TEOS∶H₂O∶C₂H₅OH mixtures (molar ratios 1∶4∶1), one at pH 1.2 and the other at pH 2.5 (respectively below and above the isoelectric point of silica). Very low concentrations of the probes were used (≤10⁻⁶ M), so the pyrene dimmers and excimers were formed only intramolecularly. The ratios of excimer to monomer fluorescence intensities at excitation wavelength of 360 nm (where mainly the ground state pyrene dimmers are excited) were studied as a function of time. Different evolutions of these ratios were observed, which allowed us to predict that the silica structure developsvia the formation of primary particles, even at pH values below the isoelectric point of silica, where it is not possible to directly detect their formation.     

波长校准用低压石英汞灯驱动电源的研制

研制波长校准用低压石英汞灯电源,用于驱动汞灯起辉并维持稳态发光。电路由EMI滤波电路、桥式整流电路、LCC半桥谐振逆变电路、控制电路和保护电路5部分组成。采用系统建模与仿真验证电路的可行性并计算电路参数理论值,利用示波器和功率表验证电源输出参数,功率输出稳定性不大于0.03 W。根据紫外可见近红外分光光度计国防最高计量标准对研制的电源驱动汞灯的工作效果进行评价。结果表明,汞灯能够输出系列特征谱线,谱线相对强度稳定性不大于5.16%;汞灯工作3 h后,灯管外壳表面温度为43℃。该驱动电源的性能参数满足JJG112–2015《低压石英汞灯波长标准器检定规程》的要求。     

Surface analysis of ripple pattern on PS and PEN induced with ring‐shaped mask due to KrF laser treatment

The approach for ripple nanopattern construction on surface of two polymer substrates [polyethylene naphthalate (PEN) and polystyrene (PS)] exposed by a KrF pulse excimer UV laser through a contact lithographic mask with circular slit was proposed in this paper. Thin layer of gold was deposited on samples after the laser treatment. Changes in the morphology of the surface of both the shielded and exposed areas of the substrates, as well as the dimensions of the laser‐induced periodic surface structures, were determined (by atomic force microscopy, laser confocal microscopy and scanning electron microscopy), compared with observations and measurements made on samples treated directly (without a contact mask) under the same conditions. The morphology of the interface between the treated and untreated regions was also closely studied. Surface chemistry of treated samples was studied in detail by X‐ray Photoelectron Spectroscopy. The detailed study of surface chemistry of modified PEN and PS revealed a significant increase of oxygen concentration for laser treated PS and increase of carboxyl groups in case of PEN. The potential application of this research can be found in biotechnology, micro technology and several other fields. Copyright © 2016 John Wiley & Sons, Ltd.     

真空紫外光电离质谱技术进展及其在快速分析中的应用

真空紫外光电离源(VUV-PI)是一种普适性的质谱软电离源,真空紫外光电离质谱谱图无碎片、易解析、灵敏度高,适合于在线快速分析.真空紫外光电离质谱根据分析对象不同可以直接采用单光子电离或添加掺杂剂实现化学电离,能实现气、液、固体分析,也可实现成像分析.该文介绍了真空紫外光电离源的电离原理、光源类型,分析了光电离质谱灵敏...