Synthesis,crystallographic and spectroscopic studies,evaluation as antimicrobial and cytotoxic agents of a novel mixed-ligand nickel(II) complex

A new mononuclear mixed-ligand complex of Ni(II) has been synthesized and structurally characterized by single-crystal X-ray diffraction as [Ni(4-Cl-pydc)(apym)(H₂O)₂], where 4-Cl-pydc and apym are 4-chloropyridine-26-dicarboxylate and 2-aminopyrimidine, respectively. Spectroscopic studies such as FT-IR, UV-vis, ¹H-NMR, and thermal analysis (TGA/DTA) were carried out. The fluorescence properties were studied in solvents with different dipole moments. Antimicrobial activities of 4-chloropyridine-26-dicarboxylic acid (1), 2-aminopyrimidine (2), complex (3), and nickel(II) nitrate hexahydrate (4) were investigated by disk diffusion and broth microdilution methods against three Gram-positive bacteria, Staphylococcus aureus, Bacillus subtilis, Staphylococcus epidermidis and three Gram-negative bacteria, Escherichia coli, Pseudomonas aeruginosa, S. marcescens; also antifungal effect was evaluated on Aspergillus niger and Saccharomyces cerevisiae in vitro. The highest antibacterial activity of complex was observed nearly equal to gentamicin as a standard drug toward S. epidermids with IZD of 18 mm. The in vitro antiproliferative activity of 1–4 on H1299 (a human non-small cell lung carcinoma), HepG2 (a human liver hepatocellular carcinoma), and β-TC3 (a mouse beta pancreatic) cell lines was evaluated by MTT (3-(45-dimethylthiazol-2-yl)-25-diphenyl-2H-tetrazolium bromide) assay and, effect of complex on depolarization of mitochondrial membrane (MMP) of all three cell lines was measured by rhodamine 123. The highest cytotoxic effect of complex was exhibited toward H1299 cell line with IC₅₀ value equal to 10 μM.     

Analysis of G‐quadruplex conformations using Raman and polarized Raman spectroscopy

G‐quadruplexes (G4s) are four‐stranded DNA structures formed within nucleic acid sequences that are rich in guanines. G4 formation within DNA strands is believed to have significant biological relevance for the control of cell replication and gene expression. Therefore, the development and validation of experimental techniques that can easily and reliably characterize G4 structures under biologically relevant measurement conditions, like Raman spectroscopy, are desirable for G4‐targeted structure based drug design. Here we report Raman and polarized Raman studies of solutions of three oligonucleotides, thrombin binding aptamer (TBA) 5′‐GGTTGGTGTGGTTGG‐3′, human telomeric (HT) 5′‐(TTAGGG)₄‐3′, and a modified c‐Myc NHE‐III₁ sequence (MycL1) 5′‐TGAGGGTGGGTAGGGTGGGTAA‐3′, which were previously reported to form four distinct intramolecular G4 structures in the presence of Na⁺ or K⁺, as determined by NMR. Our results support the previously proposed antiparallel (TBA), antiparallel and hybrid (HT), and parallel with double‐chain reversal (DCR) loop (MycL1) structures. Large sample‐dependent variations in the intensity of bands associated with deoxyribose backbone modes in the 840–930 cm⁻¹ and 1420–1460 cm⁻¹ spectral regions were observed. Most notably, a highly polarized deoxyribose ring symmetric stretch (~930 cm⁻¹) appeared strongly in the solution spectra for HT and TBA, but was very weak or absent in the solution spectrum for MycL1 and the drop deposition (dried sample) spectra for all three oligonucleotides. It is hypothesized that the intensity of this band is likely controlled by furanose ring structure uniformity and/or solvent accessibility to certain nucleotide binding sites. Raman depolarization ratios measured for the G4s in solution were generally very similar to those previously reported for canonical B DNA, with the possible exception of base ring modes that consistently yielded slightly lower depolarization ratios for G4s compared to B DNA. The results further underscore the utility of Raman and polarized Raman spectroscopy for G4 structure elucidation under biologically relevant solution conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

The Chain Segment Motion and Traps in γ‐Irradiation Crystalline Nylon 1010

The chain segment motion, charge trapping and detrapping in γ‐irradiated nylon 1010 films (doses in the range 0–2,000 kGy were used) have been investigated by means of thermally stimulated depolarization current (TSDC). There are three current peaks (named α, ρ₁ and ρ₂, respectively) in the TSDC spectra, corrected by spontaneous current, above room temperature. By analyzing the characteristic parameters of the three peaks, it is found that the chain segment motion in the amorphous regions becomes more difficult at low irradiation dose (<100 kGy) and then becomes easier with further increasing irradiation dose. The stability of the traps at the crystalline‐amorphous interfaces increases at low irradiation dose (<500 kGy) and then decreases with further increasing irradiation dose; the irradiation promotes the creation of traps and the stability of traps in the crystalline regions.     

Investigation of Pendant Group and Chain Segment Motions in P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly(methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M_η ～2×10⁵) with different mass percentages of MMA were synthesized by the method of solution polymerization. Thermally stimulated depolarization current (TSDC) technique was used to investigate the effect of copolymerization on pendant group and chain segment motions. Three TSDC peaks were observed over the temperature range from 310 to 400 K. The highest temperature, ρ peak originates from the detrapping of trapped charge carriers. The lower temperature, α peak corresponds to the glass transition. The activation energy of the α relaxation decreases from 1.2 eV for PMMA to 0.98 eV for MMA(75)/BA(25). In the fitting process, another peak, β′, is separated on the low temperature side. The apparent energy barrier of the β′ for PMMA is 0.80 eV. The β′ relaxation is thought to correspond to the motion of pendant groups including intra‐ and inter‐molecular interactions. All three peaks move to lower temperatures with an increase in BA component, and the activation energy for the α and β′ relaxations also decreases with the increase of BA component in copolymers, indicating that the flexible side groups of BA have an effect of plasticization on the glass transition and motion of pendent groups. The temperatures of the α and β′ peaks of P(MMA/BA) copolymers follow the Fox equation. Fitting results gives the α peak at 238 K and β′ peak at 225 K for polybutyl acrylate (PBA).     

Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues

The Raman depolarization ratios for individual Q₁(J”) branch lines of all diatomic hydrogen isotopologues – H₂, HD, D₂, HT, DT, and T₂ – were measured, for all rotational levels with population larger than 1/100 relative to the Boltzmann maximum at room temperature. For these measurements, the experimental setup normally used for the monitoring of the tritiated hydrogen molecules at KArlsruhe TRItium Neutrino experiment was adapted to optimally control the excitation laser power and polarization, and to precisely define the Raman light collection geometry. The measured Raman depolarization values were compared to theoretical values, which are linked to polarizability tensor quantities. For this, the ‘raw data’ were corrected taking into account distinct aspects affecting Raman depolarization data, including (1) excitation polarization impurities; (2) extended Raman excitation volumes; and (3) Raman light collection over finite solid angles. Our corrected depolarization ratios of the hydrogen isotopologues agree with the theoretical values (based on ab initio quantum calculations by R.J. LeRoy, University of Waterloo, Canada) to better than 5% for nearly all of the measured Q₁(J”) lines, with 1σ confidence level. The results demonstrate that reliable, accurate Raman depolarization ratios can be extracted from experimental measurements, which may be substantially distorted by excitation polarization impurities and by geometrical effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Evaluation method for Raman depolarization measurements including geometrical effects and polarization aberrations

In this article, we address the notoriously difficult problem to quantitatively link measured Raman depolarization values to theoretical polarizability tensor quantities, since quantum calculations do not incorporate experimental parameters. For this, we introduce a numerical model to calculate, for realistic experimental configurations, effective Raman line strength functions, Φ, which find their way into depolarization ratios, ρ. The model is based on interlinked integrations over the angles in the light collection path and a finite Raman source volume along the excitation laser beam. The model deals also with the conditional aperture parameters, associated with more than one optical component in the light collection path. Finally, we also can take into account polarization aberrations introduced by the sample cell windows. The procedure was fully tested for Raman depolarization spectra of selected hydrogen isotopologues. Distinct aspects affecting Raman depolarization data were validated, namely: (1) excitation polarization impurities; (2) extended Raman excitation volumes; (3) Raman light collection over finite solid angles; and (4) polarization aberrations introduced by optics in the light collection path. The correction of the experimental measurement data for the aforementioned effects resulted in depolarization ratios for the Q₁(J " ) Raman lines of H₂ and T₂, which mostly differed by less than 5% from those obtained by quantum‐calculations. Copyright © 2013 John Wiley & Sons, Ltd.     

非偏振分光镜对外差干涉仪非线性误差的影响

除了激光源、偏振分光镜（PBS）和波片等偏振器件之外,非偏振分光镜（NPBS）也是外差干涉仪中重要的非线性误差源。研究了多层介质膜NPBS的退偏效应和方位角对非线性误差的影响。采用p、s分量透射比、反射比、反射相移和透射相移共同表征NPBS的退偏效应,并逐项分析了其非线性误差模型。如果入射光束为理想线偏振光,则只有NPBS的反射相移和透射相移影响测量精度。如果入射光束存在偏振椭圆化和非正交,则NPBS的方位角、透射比和反射比、相移等参数的变化都会引入非线性误差,误差曲线的斜率受椭圆率和非正交角的影响。因此选用不同的激光源,同一个NPBS产生的非线性误差大小不同,一般可达几个纳米量级。为了实现纳米/亚纳米级精度的外差干涉测量,选择性能稳定的NPBS,特别是NPBS退偏效应与激光源输出偏振态之间的匹配非常重要。     

利用CALIPSO卫星数据对大气气溶胶的去偏振度特性分析研究

应用CALIPSO(Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation)卫星数据,对大气中的气溶胶等目标进行了去偏振度计算及分析.结果表明,目标后向散射去偏振度信息,能够很好表征大气气溶胶的构成种类、目标特征、垂直高度分布等特性.气溶胶的去偏振特性,为大气气溶胶的特性与分布情况等研究提供了新的方法与定量化参考参数.CALIPSO数据研究方法和结果,对全球气候变化原因、大气污染、沙尘暴等研究有重要的参考价值.     

无源光接入网单纤三向消偏振截止滤光片的研制

无源光接入网单纤三向技术是实现音频、视频、数据集成传输的关键技术。由于单纤三向滤波要求薄膜器件是大角度入射,因而所造成的偏振分离限制了信道的分离。在单纤三向滤光片的设计中,通过运用消偏振截止设计的方法,经过理论分析,并在莱宝APS1104机上镀膜,研制出了入射角为45°时偏振分量截止位置重合的消偏振截止滤光片,消除了偏振截止分离的影响。     

Electronic Excitation Energy Migration in Partly Ordered Polymeric Films

Multistep intermolecular energy migration between elongated fluorophores (carbocyanines) in uniaxially oriented polymer films is studied based on fluorescence depolarization and Monte-Carlo simulations. Contrary to disordered systems it is found experimentally that the concentration depolarization of fluorescence in uniaxially oriented films is extremely weak despite effective energy migration. Based on the concentration depolarization experiment in the ordered matrix it is possible to estimate the angle between absorption and fluorescence transition moments of carbocyanines. The values of that angle are very close to those obtained from other methods.