Sesquiterpenes from Curcuma wenyujin with their inhibitory activities on nitric oxide production in RAW 264.7 cells.

PubMed

Gao, Suyu; Xia, Guiyang; Wang, Liqing; Zhou, Li; Zhao, Feng; Huang, Jian; Chen, Lixia

2017-03-01

One new sesquiterpene, 7α,11-epoxy-6α-hydroxy-carabrane-4,8-dione, along with 10 known ones were isolated from the essential oil of Curcuma wenyujin Y.H. Chen et C. Ling. Their structures were established based on extensive spectroscopic analysis. The absolute configuration of compound 1 was determined by the CD analysis of the insitu formed [Rh 2 (OCOCF 3 ) 4 ] complex, and the CD data analysis based on the octane rule of cyclohexanone. The inhibitory effects of these sesquiterpenes on nitric oxide production in lipopolysaccharide-activated macrophages were also evaluated. Furthermore, the biosynthesis pathway of the isolated compounds was proposed.

Chemical Synthesis and Optical Properties of CdS Poly(Lactic Acid) Nanocomposites and Their Transparent Fluorescent Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Cai-Feng; Cheng, Yu-Peng; Xie, He-Yi

2011-01-01

This paper describes the chemical synthesis of cadmium sulfide (CdS) polymer nanocomposites by covalently grafting poly(lactic acid) (PLA) onto the surfaces of CdS nanocrystals (NCs). Synthesis of the nanocomposites involved two steps. Lactic acid (LA) capped CdS NCs were first prepared by reacting cadmium chloride (CdCl2) with sodium sulfide (Na2S) using LA as the organic ligand in H2O/N,N-dimethylformamide (DMF) solution. Next CdS PLA nanocomposites were formed by in situ ring-opening polymerization of lactide on the surface of modified CdS NCs. Transparent fluorescent films were then successfully prepared by blending as-prepared CdS PLA nanocomposites with high-molecular-weight PLA. The as-prepared CdS NCsmore » and their nanocomposites were studied by transmission electron microscopic imaging, thermogravimetric analyses, and spectroscopic measurements (ultraviolet-visible absorption and photoluminescence). The spectroscopic studies revealed that the CdS polymer nanocomposites exhibited good optical properties in terms of their photoluminescence and transparency.« less

Microstructural and optical properties of CdS nanoparticles synthesized by sol gel method

NASA Astrophysics Data System (ADS)

Mahdi, Hadeel Salih; Parveen, Azra; Agrawal, Shraddha; Azam, Ameer

2018-05-01

Semiconductor nanoparticles of CdS are of great interest for both fundamental research and industrial development due to their unique size-dependent optical and electronic properties and their exciting utilization in the fields of light-emitting diode, electro-chemical cells, laser, hydrogen producing catalyst, biological label. We present a scheme to measure the optical properties of CdS nanoparticles The peaks were indexed by powder-x software. The XRD pattern analysis showed that CdS composition was found to have hexagonal structure with well crystalline nature. the surface morphology and the composition of the samples were investigated by SEM (JEOL, japan). The image shows the presence of large spherical aggregates of smaller individual nanoparticles of various sizes for pure cds. to check the chemical composition of the material, energy dispersive X-ray (EDX) spectroscopic analysis was also performed which further confirmed the presence of cd and s ions in the matrix. The optical absorption spectra of CdS sample was recorded by uv-vis spectrophotometer in the range of 200 to 800 nm.

Correlation Between Bulk Material Defects and Spectroscopic Response in Cadmium Zinc Telluride Detectors

NASA Technical Reports Server (NTRS)

Parker, Bradford H.; Stahle, C. M.; Barthelmy, S. D.; Parsons, A. M.; Tueller, J.; VanSant, J. T.; Munoz, B. F.; Snodgrass, S. J.; Mullinix, R. E.

1999-01-01

One of the critical challenges for large area cadmium zinc telluride (CdZnTe) detector arrays is obtaining material capable of uniform imaging and spectroscopic response. Two complementary nondestructive techniques for characterizing bulk CdZnTe have been developed to identify material with a uniform response. The first technique, infrared transmission imaging, allows for rapid visualization of bulk defects. The second technique, x-ray spectral mapping, provides a map of the material spectroscopic response when it is configured as a planar detector. The two techniques have been used to develop a correlation between bulk defect type and detector performance. The correlation allows for the use of infrared imaging to rapidly develop wafer mining maps. The mining of material free of detrimental defects has the potential to dramatically increase the yield and quality of large area CdZnTe detector arrays.

Biophysical study on the interaction of ceftriaxone sodium with bovine serum albumin using spectroscopic methods.

PubMed

Pan, Jiongwei; Ye, Zaiting; Cai, Xiaoping; Wang, Liangxing; Cao, Zhuo

2012-12-01

The interaction of ceftriaxone sodium (CS), a cephalosporin antibiotic, with the major transport protein, bovine serum albumin (BSA), was investigated using different spectroscopic techniques such as fluorescence, circular dichroism (CD), and UV-vis spectroscopy. Values of binding parameters for BSA-CS interaction in terms of binding constant and number of binding sides were found to be 9.00 × 10(3), 3.24 × 10(3), and 2.30 × 10(3) M(-1) at 281, 301, and 321 K, respectively. Thermodynamic analysis of the binding data obtained at different temperatures showed that the binding process was spontaneous and was primarily mediated by van der Waals force or hydrogen bonding. CS binding to BSA caused secondary structural alterations in the protein as revealed by CD results. The distance between CS and Trp of BSA was determined as 3.23 nm according to the Förster resonance energy transfer theory. © 2012 Wiley Periodicals, Inc.

Sesquiterpenoids from the cultured mycelia of Ganoderma capense.

PubMed

Tan, Zhen; Zhao, Jinlian; Liu, Jimei; Zhang, Min; Chen, Ridao; Xie, Kebo; Dai, Jungui

2017-04-01

Eleven new sesquiterpenoids, including eight cadinane-type sesquiterpenoids, Ganodermanol A-H (1-8), and three eudesmane-type sesquiterpenoids, Ganodermanol I-K (9-11), together with three known compounds (12-14), were isolated from the cultured mycelia of Ganoderma capense. Their structures and absolute configurations were identified through combined extensive spectroscopic analysis, circular dichroism (CD), and Mo 2 (AcO) 4 -induced CD. Compounds 4 and 9 exhibited moderate cytotoxic activity against the human cancer cell line HCT116 with IC 50 values of 16.6 and 12.2μM, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectroscopic profiling and computational study of the binding of tschimgine: A natural monoterpene derivative, with calf thymus DNA

NASA Astrophysics Data System (ADS)

Khajeh, Masoumeh Ashrafi; Dehghan, Gholamreza; Dastmalchi, Siavoush; Shaghaghi, Masoomeh; Iranshahi, Mehrdad

2018-03-01

DNA is a major target for a number of anticancer substances. Interaction studies between small molecules and DNA are essential for rational drug designing to influence main biological processes and also introducing new probes for the assay of DNA. Tschimgine (TMG) is a monoterpene derivative with anticancer properties. In the present study we tried to elucidate the interaction of TMG with calf thymus DNA (CT-DNA) using different spectroscopic methods. UV-visible absorption spectrophotometry, fluorescence and circular dichroism (CD) spectroscopies as well as molecular docking study revealed formation of complex between TMG and CT-DNA. Binding constant (Kb) between TMG and DNA was 2.27 × 104 M- 1, that is comparable to groove binding agents. The fluorescence spectroscopic data revealed that the quenching mechanism of fluorescence of TMG by CT-DNA is static quenching. Thermodynamic parameters (ΔH < 0 and ΔS < 0) at different temperatures indicated that van der Waals forces and hydrogen bonds were involved in the binding process of TMG with CT-DNA. Competitive binding assay with methylene blue (MB) and Hoechst 33258 using fluorescence spectroscopy displayed that TMG possibly binds to the minor groove of CT-DNA. These observations were further confirmed by CD spectral analysis, viscosity measurements and molecular docking.

Five new amicoumacins isolated from a marine-derived bacterium Bacillus subtilis.

PubMed

Li, Yongxin; Xu, Ying; Liu, Lingli; Han, Zhuang; Lai, Pok Yui; Guo, Xiangrong; Zhang, Xixiang; Lin, Wenhan; Qian, Pei-Yuan

2012-02-01

Four novel amicoumacins, namely lipoamicoumacins A-D (1-4), and one new bacilosarcin analog (5) were isolated from culture broth of a marine-derived bacterium Bacillus subtilis, together with six known amicoumacins. Their structures were elucidated on the basis of extensive spectroscopic (2D NNR, IR, CD and MS) analysis and in comparison with data in literature.

Borrelidins C-E: New Antibacterial Macrolides from a Saltern-Derived Halophilic Nocardiopsis sp.

PubMed

Kim, Jungwoo; Shin, Daniel; Kim, Seong-Hwan; Park, Wanki; Shin, Yoonho; Kim, Won Kyung; Lee, Sang Kook; Oh, Ki-Bong; Shin, Jongheon; Oh, Dong-Chan

2017-06-06

Chemical investigation of a halophilic actinomycete strain belonging to the genus Nocardiopsis inhabiting a hypersaline saltern led to the discovery of new 18-membered macrolides with nitrile functionality, borrelidins C-E ( 1 - 3 ), along with a previously reported borrelidin ( 4 ). The planar structures of borrelidins C-E, which are new members of the rare borrelidin class of antibiotics, were elucidated by NMR, mass, IR, and UV spectroscopic analyses. The configurations of borrelidines C-E were determined by the interpretation of ROESY NMR spectra, J-based configuration analysis, a modified Mosher's method, and CD spectroscopic analysis. Borrelidins C and D displayed inhibitory activity, particularly against the Gram-negative pathogen Salmonella enterica , and moderate cytotoxicity against the SNU638 and K562 carcinoma cell lines.

Performance comparison of small-pixel CdZnTe radiation detectors with gold contacts formed by sputter and electroless deposition

NASA Astrophysics Data System (ADS)

Bell, S. J.; Baker, M. A.; Duarte, D. D.; Schneider, A.; Seller, P.; Sellin, P. J.; Veale, M. C.; Wilson, M. D.

2017-06-01

Recent improvements in the growth of wide-bandgap semiconductors, such as cadmium zinc telluride (CdZnTe or CZT), has enabled spectroscopic X/γ-ray imaging detectors to be developed. These detectors have applications covering homeland security, industrial analysis, space science and medical imaging. At the Rutherford Appleton Laboratory (RAL) a promising range of spectroscopic, position sensitive, small-pixel Cd(Zn)Te detectors have been developed. The challenge now is to improve the quality of metal contacts on CdZnTe in order to meet the demanding energy and spatial resolution requirements of these applications. The choice of metal deposition method and fabrication process are of fundamental importance. Presented is a comparison of two CdZnTe detectors with contacts formed by sputter and electroless deposition. The detectors were fabricated with a 74 × 74 array of 200 μm pixels on a 250 μm pitch and bump-bonded to the HEXITEC ASIC. The X/γ-ray emissions from an 241Am source were measured to form energy spectra for comparison. It was found that the detector with contacts formed by electroless deposition produced the best uniformity and energy resolution; the best pixel produced a FWHM of 560 eV at 59.54 keV and 50% of pixels produced a FWHM better than 1.7 keV . This compared with a FWHM of 1.5 keV for the best pixel and 50% of pixels better than 4.4 keV for the detector with sputtered contacts.

Purification of selenium by zone refining

NASA Astrophysics Data System (ADS)

Burger, A.; Henderson, D. O.; Morgan, S. H.; Feng, J.; Silberman, E.

1990-11-01

We studied the purification of Se using zone refining, with emphasis on the efficiency of this technique in removing the Cu impurity, which is known to be related to a trapping center in CdSe. After 78 passes it was found that Cu accumulates at one end section of the ingot, while at the opposite end the level was below the detection limit of the atomic absorption spectroscopic analysis employed. Infrared spectroscopic data, differential solubility and differential scanning calorimetry measurements also indicate that the effective distribution coefficient, k, for the Cu solute, is less than 1. A model for the various phases present during zone melting is presented and the possibility of segregating impurities having k>1 is discussed.

Spithioneines A and B, Two New Bohemamine Derivatives Possessing Ergothioneine Moiety from a Marine-Derived Streptomyces spinoverrucosus

PubMed Central

2015-01-01

Spithioneines A and B (1 and 2), two new bohemamine-type pyrrolizidine alkaloids possessing an unusual ergothioneine moiety, were isolated from a marine-derived Streptomyces spinoverrucosus. Their structures were elucidated by spectroscopic analysis, CD spectra, and chemical degradation and synthesis. Compounds 1 and 2 are rare natural products that incorporate the amino acid ergothioneine. PMID:26024315

Local Electronic Structure Changes in Polycrystalline CdTe with CdCl 2 Treatment and Air Exposure

DOE PAGES

Berg, Morgann; Kephart, Jason M.; Munshi, Amit; ...

2018-03-12

Postdeposition CdCl 2 treatment of polycrystalline CdTe is known to increase the photovoltaic device efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this work, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries (GBs). In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl 2 treatment and ambient oxygen exposure. Qualitatively, grain boundaries displayed lower work function and downward band bending relative to grainmore » interiors, but only after air exposure of CdCl 2-treated CdTe. Analysis of numerous space charge regions at grain boundaries showed an average depletion width of 290 nm and an average band bending magnitude of 70 meV, corresponding to a GB trap density of 10 11 cm –2 and a net carrier density of 10 15 cm –3. Finally, these results suggest that both CdCl 2 treatment and oxygen exposure may be independently tuned to enhance the CdTe photovoltaic performance by engineering the interface and bulk electronic structure.« less

Local Electronic Structure Changes in Polycrystalline CdTe with CdCl 2 Treatment and Air Exposure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, Morgann; Kephart, Jason M.; Munshi, Amit

Postdeposition CdCl 2 treatment of polycrystalline CdTe is known to increase the photovoltaic device efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this work, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries (GBs). In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl 2 treatment and ambient oxygen exposure. Qualitatively, grain boundaries displayed lower work function and downward band bending relative to grainmore » interiors, but only after air exposure of CdCl 2-treated CdTe. Analysis of numerous space charge regions at grain boundaries showed an average depletion width of 290 nm and an average band bending magnitude of 70 meV, corresponding to a GB trap density of 10 11 cm –2 and a net carrier density of 10 15 cm –3. Finally, these results suggest that both CdCl 2 treatment and oxygen exposure may be independently tuned to enhance the CdTe photovoltaic performance by engineering the interface and bulk electronic structure.« less

Spectroscopic ellipsometry for analysis of polycrystalline thin-film photovoltaic devices and prediction of external quantum efficiency

NASA Astrophysics Data System (ADS)

Ibdah, Abdel-Rahman; Koirala, Prakash; Aryal, Puruswottam; Pradhan, Puja; Marsillac, Sylvain; Rockett, Angus A.; Podraza, Nikolas J.; Collins, Robert W.

2017-11-01

Complete polycrystalline thin-film photovoltaic (PV) devices employing CuIn1-xGaxSe2/CdS and CdS/CdTe heterojunctions have been studied by ex situ spectroscopic ellipsometry (SE). In this study, layer thicknesses have been extracted along with photon energy independent parameters such as compositions that describe the dielectric function spectra ε(E) of the individual layers. For accurate ex situ SE analysis of these PV devices, a database of ε(E) spectra is required for all thin film component materials used in each of the two absorber technologies. When possible, database measurements are performed by applying SE in situ immediately after deposition of the thin film materials and after cooling to room temperature in order to avoid oxidation and surface contamination. Determination of ε(E) from the resulting in situ SE data requires structural information that can be obtained from analysis of SE data acquired in real time during the deposition process. From the results of ex situ analysis of the complete CuIn1-xGaxSe2 (CIGS) and CdTe PV devices, the deduced layer thicknesses in combination with the parameters describing ε(E) can be employed in further studies that simulate the external quantum efficiency (EQE) spectra of the devices. These simulations have been performed here by assuming that all electron-hole pairs generated within the active layers, i.e. layers incorporating a dominant absorber component (either CIGS or CdTe), are separated and collected. The active layers may include not only the bulk absorber but also window and back contact interface layers, and individual current contributions from these layers have been determined in the simulations. In addition, the ex situ SE analysis results enable calculation of the absorbance spectra for the inactive layers and the overall reflectance spectra, which lead to quantification of all optical losses in terms of a current density deficit. Mapping SE can be performed given the high speed of multichannel ellipsometers employing array detection, and the resulting EQE simulation capability has wide applications in predicting large area PV module output. The ultimate goal is an on-line capability that enables prediction of PV sub-cell current output as early as possible in the production process.

Graphene oxide based CdSe photocatalysts: Synthesis, characterization and comparative photocatalytic efficiency of rhodamine B and industrial dye

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Trisha; Lee, Jeong-Ho; Meng, Ze-Da

Highlights: ► CdSe–graphene is synthesized by hydrothermal method. ► Three molar solutions of CdSe were used making three different composites. ► RhB and Texbrite MST-L were used as sample dye solutions. ► Texbrite MST-L is photo degraded in visible light. ► UV-spectroscopic analysis was done to measure degradation. - Abstract: CdSe–graphene composites were prepared using simple “hydrothermal method” where the graphene surface was modified using different molar solutions of cadmium selenide (CdSe) in aqueous media. The characterization of CdSe–graphene composites were studied by X-ray diffraction (XRD), energy dispersive X-ray (EDX), scanning electron microscope (SEM), and with transmission electron microscope (TEM).more » The catalytic activities of CdSe-composites were evaluated by degradation of rhodamine B (RhB) and commercial industrial dye “Texbrite MST-L (TXT-MST)” with fixed concentration. The degradation was observed by the decrease in the absorbance peak studied by UV spectrophotometer. The decrease in the dye concentration indicated catalytic degradation effect by CdSe–graphene composites.« less

Supramolecular Inclusion in Cyclodextrins: A Pictorial Spectroscopic Demonstration

ERIC Educational Resources Information Center

Haldar, Basudeb; Mallick, Arabinda; Chattopadhyay, Nitin

2008-01-01

A spectroscopic experiment is presented that reveals that the hydrophobically end-modified water-soluble polymeric fluorophore, pyrene end-capped poly(ethylene oxide) (PYPY), interacts differently with [alpha], [beta], and [gamma]-cyclodextrins (CD) to form supramolecular inclusion complexes. The emission spectrum of PYPY in aqueous solution shows…

Spectroscopic profiling and computational study of the binding of tschimgine: A natural monoterpene derivative, with calf thymus DNA.

PubMed

Khajeh, Masoumeh Ashrafi; Dehghan, Gholamreza; Dastmalchi, Siavoush; Shaghaghi, Masoomeh; Iranshahi, Mehrdad

2018-03-05

DNA is a major target for a number of anticancer substances. Interaction studies between small molecules and DNA are essential for rational drug designing to influence main biological processes and also introducing new probes for the assay of DNA. Tschimgine (TMG) is a monoterpene derivative with anticancer properties. In the present study we tried to elucidate the interaction of TMG with calf thymus DNA (CT-DNA) using different spectroscopic methods. UV-visible absorption spectrophotometry, fluorescence and circular dichroism (CD) spectroscopies as well as molecular docking study revealed formation of complex between TMG and CT-DNA. Binding constant (K b ) between TMG and DNA was 2.27×10 4 M -1 , that is comparable to groove binding agents. The fluorescence spectroscopic data revealed that the quenching mechanism of fluorescence of TMG by CT-DNA is static quenching. Thermodynamic parameters (ΔH<0 and ΔS<0) at different temperatures indicated that van der Waals forces and hydrogen bonds were involved in the binding process of TMG with CT-DNA. Competitive binding assay with methylene blue (MB) and Hoechst 33258 using fluorescence spectroscopy displayed that TMG possibly binds to the minor groove of CT-DNA. These observations were further confirmed by CD spectral analysis, viscosity measurements and molecular docking. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectroscopic ellipsometric studies of the dielectric function of Cd1-x-yMnxFeyTe single crystals

NASA Astrophysics Data System (ADS)

Hwang, Younghun; Kim, Hyekyeong; Um, Youngho; Park, Hyoyeol

2004-06-01

Cd1-x-yMnxFeyTe single crystals grown by the vertical Bridgman method have been studied by measuring the complex dielectric function using spectroscopic ellipsometry in the 1.5 5.5 eV photon energy range at room temperature. The CP energy parameters of the E0, E1, E1 + 1, and E2 structures were determined by fitting the second-derivative spectra (d2/d2) with a theoretical model, i.e., the standard critical point (SCP) line shapes. The E1, E1 + 1, and E2 energies decreased with increasing Fe composition y, which is due to the hybridization effect of the valence and conduction bands in Cd1-xMnxTe with Fe 3d levels.

Using circular dichroism collected as a function of temperature to determine the thermodynamics of protein unfolding and binding interactions

PubMed Central

Greenfield, Norma J.

2009-01-01

Circular dichroism (CD) is an excellent spectroscopic technique for following the unfolding and folding of proteins as a function of temperature. One of its principal applications is to determine the effects of mutations and ligands on protein and polypeptide stability If the change in CD as a function of temperature is reversible, analysis of the data may be used to determined the van't Hoff enthalpy (ΔH) and entropy (ΔS) of unfolding, the midpoint of the unfolding transition (TM) and the free energy (ΔG) of unfolding. Binding constants of protein-protein and protein-ligand interactions may also be estimated from the unfolding curves. Analysis of CD spectra obtained as a function of temperature is also useful to determine whether a protein has unfolding intermediates. Measurement of the spectra of five folded proteins and their unfolding curves at a single wavelength takes approximately eight hours. PMID:17406506

Inducamides A–C, Chlorinated Alkaloids from an RNA Polymerase Mutant Strain of Streptomyces sp.

PubMed Central

2015-01-01

Inducamides A–C (1–3), three new chlorinated alkaloids featuring an amide skeleton generated by a tryptophan fragment and a 6-methylsalicylic acid unit, were isolated from a chemically induced mutant strain of Streptomyces sp. with the inducamides only being produced in the mutant strain. Their structures, including stereochemistry, were determined by spectroscopic analysis, Marfey’s method, and CD spectroscopy. PMID:25338006

Two streptothricins with a cis-streptolidine lactam moiety from Streptomyces sp. I08A 1776.

PubMed

Gan, Maoluo; Guan, Yan; Zheng, Xudong; Yang, Yanhui; Hao, Xueqin; Liu, Yishuang; Yu, Liyan; Xiao, Chunling

2012-10-01

Two unique cis-fused streptothricins (1 and 2) were isolated from the culture broth of Streptomyces sp. I08A 1776. Their structures were determined by MS, CD, and 1D and 2D NMR spectroscopic data analysis. Compound 2 showed weak antibacterial activities against Bacillus subtilis and Enterococcus faecalis with MIC values of 32 and 64 μg ml(-1), respectively.

Preparation, characterization and binding behaviors of host-guest inclusion complexes of metoclopramide hydrochloride with α- and β-cyclodextrin molecules

NASA Astrophysics Data System (ADS)

Barman, Siti; Barman, Biraj Kumar; Roy, Mahendra Nath

2018-03-01

The supramolecular interaction of metoclopramide hydrochloride (MP) with α-cyclodextrin (α-CD) and β-cyclodextrin (β-CD) has been inspected by ultraviolet-visible (UV-vis) light, infra-red (IR) light, fluorescence and 1H NMR spectroscopy. The formation of an inclusion complex greatly affects the physical-chemical properties of the guest molecules, such as solubility, chemical reactivity and the spectroscopic and electrochemical properties. Thus the changes in the spectral properties and physico-chemical properties confirm the inclusion complex formation. Surface tension, conductivity studies and Job's plot indicate a 1: 1 stoichiometry of the MP:CD host-guest inclusion complexes. The binding/association constants have been evaluated by both UV-Vis and fluorescence spectroscopic study indicating a higher degree of encapsulation for β-cyclodextrin (β-CD). Furthermore, the negative value of thermodynamic parameter (ΔG°) of the host-guest system suggests that the inclusion process proceeded spontaneously at 298.15 K. Based on the NMR data, the plausible mode of interaction of MP:α-CD and MP:β-CD complexes were proposed, which suggested that lipophilic aromatic ring of the MP entered into the cavity of CDs from the wider side, with the amide (sbnd CONH) and methoxy (-OMe) residues inside the CD cavity.

Effects of sub-bandgap illumination on electrical properties and detector performances of CdZnTe:In

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Lingyan; Jie, Wanqi, E-mail: jwq@nwpu.edu.cn; Zha, Gangqiang, E-mail: zha-gq@hotmail.com

2014-06-09

The effects of sub-bandgap illumination on electrical properties of CdZnTe:In crystals and spectroscopic performances of the fabricated detectors were discussed. The excitation process of charge carriers through thermal and optical transitions at the deep trap could be described by the modified Shockley-Read-Hall model. The ionization probability of the deep donor shows an increase under illumination, which should be responsible for the variation of electrical properties within CdZnTe bulk materials with infrared (IR) irradiation. By applying Ohm's law, diffusion model and interfacial layer-thermionic-diffusion theory, we obtain the decrease of bulk resistivity and the increase of space charge density in the illuminatedmore » crystals. Moreover, the illumination induced ionization will further contribute to improving carrier transport property and charge collection efficiency. Consequently, the application of IR irradiation in the standard working environment is of great significance to improve the spectroscopic characteristics of CdZnTe radiation detectors.« less

Spectroscopic vector analysis for fast pattern quality monitoring

NASA Astrophysics Data System (ADS)

Sohn, Younghoon; Ryu, Sungyoon; Lee, Chihoon; Yang, Yusin

2018-03-01

In semiconductor industry, fast and effective measurement of pattern variation has been key challenge for assuring massproduct quality. Pattern measurement techniques such as conventional CD-SEMs or Optical CDs have been extensively used, but these techniques are increasingly limited in terms of measurement throughput and time spent in modeling. In this paper we propose time effective pattern monitoring method through the direct spectrum-based approach. In this technique, a wavelength band sensitive to a specific pattern change is selected from spectroscopic ellipsometry signal scattered by pattern to be measured, and the amplitude and phase variation in the wavelength band are analyzed as a measurement index of the pattern change. This pattern change measurement technique is applied to several process steps and verified its applicability. Due to its fast and simple analysis, the methods can be adapted to the massive process variation monitoring maximizing measurement throughput.

Three New Highly Oxygenated Germacranolides from Carpesium Divaricatum and Their Cytotoxic Activity.

PubMed

Zhang, Tao; Si, Jin-Guang; Zhang, Qiu-Bo; Chen, Jia-Huan; Ding, Gang; Zhang, Hong-Wu; Jia, Hong-Mei; Zou, Zhong-Mei

2018-05-03

Three new highly oxygenated ( 2 ⁻ 4 ), and two known ( 1 and 5 ) germacranolides, were isolated from the whole plant of Carpesium divaricatum . The planar structures and relative configurations of the new compounds were determined by detailed spectroscopic analysis. The absolute configuration of 1 was established using the circular dichroism (CD) method and X-ray diffraction, and the stereochemistry of the new compounds 2 ⁻ 4 were determined using similar CD spectra with 1 . The new compound 2 and the known compound 5 exhibited potent cytotoxicity against hepatocellular cancer (Hep G2) and human cervical cancer (HeLa) cells, superior to those of the positive control cis -platin.

Evidence for Breakdown of Vibrational Motion in ^110Cd

NASA Astrophysics Data System (ADS)

Bangay, Jack; Garrett, Paul; Bianco, Laura; Leach, Kyle; Finlay, Paul; Green, Katie; Phillips, Andrew; Rand, Evan; Svensson, Carl; Sumithrarachchi, Chandana; Wong, James

2009-10-01

^110Cd has long been considered an excellent example of a vibrational nucleus. However, recent work with other even-even Cadmium isotopes show a breakdown of vibrational motion at the 2 and 3-phonon level, suggesting the need for more precise measurements on ^110Cd. The structure of ^110Cd is studied with the (n,n^'γ) reaction performed at the University of Kentucky, as well as with the high statistics β-decay of ^110In performed at the TRIUMF-ISAC facility using the 8π spectrometer. Excitation funcions and angular distributions from the (n,n^'γ) reaction provide us with spectroscopic information on the level scheme, including level lifetimes and spins. This data is complemented by the γγ coincidences measured in the ^110In β-decay that allows the observation of, or stringent limit on, weak, low-energy branches between levels at high excitation energy. Details of the analysis to date, including candidates for the full octupole-quadrupole coupled quintuplet, will be presented.

Studies on the interaction between 7-(dimethyl amino)-4-(trifluoromethyl)-2H-1-benzopyran-2-one and cadmium sulfide quantum dots

NASA Astrophysics Data System (ADS)

Kuriakose, Alina C.; Pradeep, C.; Nampoori, V. P. N.; Thomas, Sheenu

2018-04-01

Quantum dots (QDs) are well known for their optical properties which differ from those of bulk semiconductors. Herein, we have created an energy transfer platform that combines CdS QDs with a coumarin based dye C485 [7-(dimethyl amino)-4-(trifluoromethyl)-2H-1-benzopyran-2-one]. Spectroscopic studies of energy transfer between the dye donor and CdS QDs as acceptors reveal the occurrence of dynamic quenching. Analysis of the steady-state and time resolved fluorescence measurements of C485 in the presence of CdS QDs infers fluorescence resonance (Förster type) energy transfer (FRET) as responsible for the quenching phenomena. The energy transfer efficiency as well as energy transfer distance for the donor-acceptor pair is calculated using steady-state fluorescence method. Luminescence enhancement of CdS QDs play a critical role in device performance for solar applications and also in the field of biological applications.

High-resolution spectroscopic observations of the new CEMP-s star CD -50°776

NASA Astrophysics Data System (ADS)

Roriz, M.; Pereira, C. B.; Drake, N. A.; Roig, F.; Silva, J. V. Sales

2017-11-01

Carbon enhanced metal-poor (CEMP) stars are a particular class of low-metalicity halo stars whose chemical analysis may provide important contrains to the chemistry evolution of the Galaxy and to the models of mass-transfer and evolution of components in binary systems. Here, we present a detailed analysis of the CEMP star CD -50°776, using high resolution optical spectroscopy. We found that CD -50°776 has a metalicity [Fe/H] = -2.31 and a carbon abundance [C/Fe] = +1.21. Analysing the s-process elements and the europium abundances, we show that this star is actually a CEMP-s star, based on the criteria set in the literature to classify these chemically peculiar objects. We also show that CD -50°776 is a lead star, since it has a ratio [Pb/Ce] = +0.97. In addition, we show that CD -50°776 develops radial velocity variations that may be attributed to the orbital motion in a binary system. The abundance pattern of CD -50°776 is discussed and compared to other CEMP-s stars already reported in the literature to show that this star is a quite exceptional object among the CEMP stars, particularly due to its low nitrogen abundance. Explaining this pattern may require to improve the nucleosynthesis models, and the evolutionary models of mass transfer and binary interaction.

Transparent conducting ZnO-CdO mixed oxide thin films grown by the sol-gel method.

PubMed

Pathak, Trilok K; Rajput, Jeevitesh K; Kumar, Vinod; Purohit, L P; Swart, H C; Kroon, R E

2017-02-01

Mixed oxides of zinc and cadmium with different proportions were deposited on ordinary glass substrates using the sol-gel spin coating method under optimized deposition conditions using zinc acetate dihydrate and cadmium acetate dihydrate as precursors. X-ray diffraction patterns confirmed the polycrystalline nature of the films. A combination of cubic CdO and hexagonal wurtzite ZnO phases was observed. The oxidation states of Zn, Cd and O in the deposited films were determined by X-ray photoelectron spectroscopic studies. Surface morphology was studied by scanning electron microscopy and atomic force microscopy. The compositional analysis of the thin films was studied by secondary ion mass spectroscopy. The transmittance of the thin films was measured in the range 300-800nm and the optical bandgap was calculated using Tauc's plot method. The bandgap decreased from 3.15eV to 2.15eV with increasing CdO content. The light emission properties of the ZnO:CdO thin films were studied by photoluminescence spectra recorded at room temperature. The current-voltage characteristics were also assessed and showed ohmic behaviour. The resistance decreased with increasing CdO content. Copyright © 2016 Elsevier Inc. All rights reserved.

Synthesis, spectral and thermal studies of pyridyl adducts of Zn(II) and Cd(II) dithiocarbamates, and their use as single source precursors for ZnS and CdS nanoparticles.

PubMed

Onwudiwe, Damian C; Strydom, Christien A; Oluwafemi, Oluwatobi S; Hosten, Eric; Jordaan, Anine

2014-06-21

The synthesis, spectroscopic characterisation, and thermal studies of pyridyl adducts of Zn(II) and Cd(II) complexes of N-ethyl-N-phenyl dithiocarbamate, represented as [ZnL2py] and [CdL2py2], are reported. Single-crystal X-ray structural analysis of the Zn compound showed that it is five-coordinate with four sulphurs from dithiocarbamate and one nitrogen from pyridine in a distorted square pyramidal geometry. The thermogravimetric studies indicate that the zinc and cadmium compounds undergo fast weight loss, and the temperature at maximum rate of decomposition is at 277 °C and 265 °C respectively, to give the metal (Zn or Cd) sulphide residues. These compounds were used as single molecule precursors to produce nanocrystalline MS (M = Zn, Cd) after thermolysis in hexadecylamine. The morphological and optical properties of the resulting MS nanocrystallites were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis absorption and photoluminescence (PL) spectroscopy, and powdered X-ray diffraction (XRD). By varying the growth time, the temporal evolution of the optical properties and morphology of the nanocrystals were investigated.

Single-particle states in ^112Cd probed with the ^111Cd(d,p) reaction

NASA Astrophysics Data System (ADS)

Garrett, P. E.; Jamieson, D.; Demand, G. A.; Finlay, P.; Green, K. L.; Leach, K. G.; Phillips, A. A.; Sumithrarachchi, C. S.; Svensson, C. E.; Triambak, S.; Wong, J.; Ball, G. C.; Hertenberger, R.; Wirth, H.-F.; Kr"Ucken, R.; Faestermann, T.

2009-10-01

As part of a program of detailed spectroscopy of the Cd isotopes, the single-particle neutron states in ^112Cd have been probed with the ^111Cd(d,p) reaction. Beams of polarized 22 MeV deuterons, obtained from the LMU/TUM Tandem Accelerator, bombarded a target of ^111Cd. The protons from the reaction, corresponding to excitation energies up to 3 MeV in ^112Cd, were momentum analyzed with the Q3D spectrograph. Cross sections and analyzing powers were fit to results of DWBA calculations, and spectroscopic factors were determined. The results from the experiment, and implications for the structure of ^112Cd, will be presented.

Cascaded systems analysis of charge sharing in cadmium telluride photon-counting x-ray detectors.

PubMed

Tanguay, Jesse; Cunningham, Ian A

2018-05-01

Single-photon-counting (SPC) and spectroscopic x-ray detectors are under development in academic and industry laboratories for medical imaging applications. The spatial resolution of SPC and spectroscopic x-ray detectors is an important design criterion. The purpose of this article was to extend the cascaded systems approach to include a description of the spatial resolution of SPC and spectroscopic x-ray imaging detectors. A cascaded systems approach was used to model reabsorption of characteristic x rays, Coulomb repulsion, and diffusion in SPC and spectroscopic x-ray detectors. In addition to reabsorption, diffusion, and Coulomb repulsion, the model accounted for x-ray conversion to electron-hole (e-h) pairs, integration of e-h pairs in detector elements, electronic noise, and energy thresholding. The probability density function (PDF) describing the number of e-h pairs was propagated through each stage of the model and was used to derive new theoretical expressions for the large-area gain and modulation transfer function (MTF) of CdTe SPC x-ray detectors, and the energy bin sensitivity functions and MTFs of CdTe spectroscopic detectors. Theoretical predictions were compared with the results of MATLAB-based Monte Carlo (MC) simulations and published data. Comparisons were also made with the MTF of energy-integrating systems. Under general radiographic conditions, reabsorption, diffusion, and Coulomb repulsion together artificially inflate count rates by 20% to 50%. For thicker converters (e.g. 1000 μm) and larger detector elements (e.g. 500 μm pixel pitch) these processes result in modest inflation (i.e. ∼10%) in apparent count rates. Our theoretical and MC analyses predict that SPC MTFs will be degraded relative to those of energy-integrating systems for fluoroscopic, general radiographic, and CT imaging conditions. In most cases, this degradation is modest (i.e., ∼10% at the Nyquist frequency). However, for thicker converters, the SPC MTF can be degraded by up to 25% at the Nyquist frequency relative to EI systems. Additionally, unlike EI systems, the MTF of spectroscopic systems is strongly dependent on photon energy, which results in energy-bin-dependent spatial resolution in spectroscopic systems. The PDF-transfer approach to modeling signal transfer through SPC and spectroscopic x-ray imaging systems provides a framework for understanding system performance. Application of this approach demonstrated that charge sharing artificially inflates the SPC image signal and degrades the MTF of SPC and spectroscopic systems relative to energy-integrating systems. These results further motivate the need for anticharge-sharing circuits to mitigate the effects of charge sharing on SPC and spectroscopic x-ray image quality. © 2018 American Association of Physicists in Medicine.

Spectroscopic Factors from the Single Neutron Transfer Reaction 111Cd(d,p)112Cd

NASA Astrophysics Data System (ADS)

Jamieson, D. S.; Garrett, P. E.; Demand, G. A.; Finlay, P.; Green, K. L.; Leach, K. G.; Phillips, A. A.; Svensson, C. E.; Sumithrarachchi, C. S.; Triambak, S.; Wong, J.; Ball, G.; Faestermann, T.; Krücken, R.; Hertenberger, R.; Wirth, H.-F.

2013-03-01

The cadmium isotopes have been cited as excellent examples of vibrational nuclei for decades, with multi-phonon quadrupole, quadrupole-octupole, and mixed-symmetry states proposed. From a variety of experimental studies, a large amount of spectroscopic data has been obtained, recently focused on γ-ray studies. In the present work, the single-particle structure of 112Cd has been investigated using the 111Cd(ěcd, p)112Cd reaction. The investigation was carried out using a 22 MeV beam of polarized deuterons obtained from the Maier-Leibnitz Laboratory at Garching, Germany. The reaction ejectiles were momentum analyzed using a Q3D spectrograph, and 115 levels have been identified up to 4.2 MeV of excitation energy. Spin-parity has been assigned to each analyzed level, and angular distributions for the reaction cross sections and analyzing powers were obtained. Many additional levels have been observed compared with the previous (d,p) study performed with 8 MeV deuterons,1 including strongly populated 5- and 6- states. The former was previously assigned as a member of the quadrupole-octupole quintuplet, based on a strongly enhanced B(E2) value to the 3- state, but is now re-assigned as being predominately s1/2 ⊗ h11/2 configuration.

CN anomalies in extremely metal-deficient red giants

NASA Technical Reports Server (NTRS)

Anthony-Twarog, Barbara J.; Shawl, Stephen J.; Twarog, Bruce A.

1992-01-01

New photometric and UV spectroscopic data for the metal-deficient red giants CD -38 deg 245 and BD -18 deg 5550 are presented and discussed in light of recently noted photometric anomalies. From the IUE spectra it is aparent that the UV excess found in BD -18 deg 5550 is not the result of a hot companion. The IUE spectra, in conjunction with other observations, point to anomalous nitrogen abundances as the source of the discrepancies between the photometric and spectroscopic abundances for these stars. CD -38 deg 245 appears to be exceptionally nitrogen-rich while BD -18 deg 5550 is anomalously nitrogen-poor with respect to stars of comparable metallicities. While BD -18 deg 5550 appears to be an exception to the rule for its metallicity, the confirmation of a similar photometric pattern for CS 22885-96 may be an indication that the nitrogen overabundance in CD -38 deg 245 is typical for giants of extreme metal-deficiency.

Synthesis, characterization and spectroscopic properties of the hydrazodye and new hydrazodye-metal complexes

NASA Astrophysics Data System (ADS)

Bouhdada, M.; EL Amane, M.

2017-12-01

The hydrazodye (L) [disodium (7-hydroxyl-8-phenylazo-1,3-naphthalenedisulfonate)] is prepared and characterized by infrared 1H,13C, NMR and UV-visible spectra. The spectral data of the ligand (L) existing predominantly in the hydrazones form. Reaction of the hydrazodye (L) with Cd2+, Ni2+, Cu2+ and Zn2+ chloride gave two series of metal complexes with general formula [ML2 (OH2)2]2Cl and [ML2 (caf)2]2Cl. Their complexes were identified by FTIR, UV-visible spectra, 1H, 13C, NMR, EPR, XRD and molar conductance. The molar conductance reveals that the new series of metal complexes are non-electrolytes. The postulated octahedral structure of the obtained complexes is also proposed on spectroscopic data analysis.

Direct Spectroscopic Detection of ATP Turnover Reveals Mechanistic Divergence of ABC Exporters.

PubMed

Collauto, Alberto; Mishra, Smriti; Litvinov, Aleksei; Mchaourab, Hassane S; Goldfarb, Daniella

2017-08-01

We have applied high-field (W-band) pulse electron-nuclear double resonance (ENDOR) and electron-electron double resonance (ELDOR)-detected nuclear magnetic resonance (EDNMR) to characterize the coordination sphere of the Mn 2+ co-factor in the nucleotide binding sites (NBSs) of ABC transporters. MsbA and BmrCD are two efflux transporters hypothesized to represent divergent catalytic mechanisms. Our results reveal distinct coordination of Mn 2+ to ATP and transporter residues in the consensus and degenerate NBSs of BmrCD. In contrast, the coordination of Mn 2+ at the two NBSs of MsbA is similar, which provides a mechanistic rationale for its higher rate constant of ATP hydrolysis relative to BmrCD. Direct detection of vanadate ion, trapped in a high-energy post-hydrolysis intermediate, further supports the notion of asymmetric hydrolysis by the two NBSs of BmrCD. The integrated spectroscopic approach presented here, which link energy input to conformational dynamics, can be applied to a variety of systems powered by ATP turnover. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of molecular structure, spectroscopic properties (FT-IR, micro-Raman and UV-vis) and quantum chemical calculations of free and ligand 2-thiopheneglyoxylic acid in metal halides (Cd, Co, Cu, Ni and Zn).

PubMed

Gökce, Halil; Bahçeli, Semiha

2013-12-01

In this study, molecular geometries, experimental vibrational wavenumbers, electronic properties and quantum chemical calculations of 2-thiopheneglyoxylic acid molecule, (C6H4O3S), and its metal halides (Cd, Co, Cu, Ni and Zn) which are used as pharmacologic agents have been investigated experimentally by FT-IR, micro-Raman and UV-visible spectroscopies and elemental analysis. Meanwhile the vibrational calculations were verified by DFT/B3LYP method with 6-311++G(d,p) and LANL2DZ basis sets in the ground state, for free TPGA molecule and its metal halide complexes, respectively, for the first time. The calculated fundamental vibrational frequencies for the title compounds are in a good agreement with the experimental data. Copyright © 2013 Elsevier B.V. All rights reserved.

Simple and green synthesis of protein-conjugated CdS nanoparticles and spectroscopic study on the interaction between CdS and zein

NASA Astrophysics Data System (ADS)

Qin, Dezhi; Zhang, Li; Du, Xian; Wang, Yabo; Zhang, Qiuxia

2016-09-01

The present study demonstrates the role of zein molecules in synthesizing CdS nanoassemblies through protein-directed, green synthetic approach. Zein molecules can as capping ligand and stabilizing agent to regulate the nucleation and growth of CdS nanocrystals, and the obtained products are organic-inorganic nanocomposites. The analysis of surface charge and conductivity indicates that strong electrostatic force restricts mobility of ions, which creates a local supersaturation surrounding the binding sites of zein and reduces the activated energy of nucleation. The interaction between Cd2+/CdS and zein molecules was systematically investigated through spectroscopy techniques. Fourier transform infrared (FT-IR) spectra were used to envisage the binding of the functional groups of zein with the surface of CdS nanoparticles. Ultraviolet visible (UV-Vis) and photoluminescence (PL) spectra results show that Cd2+/CdS might interact with the aromatic amino acids of protein molecules and change its chemical microenvironment. The quantum-confined effect of nanocrystals is confirmed by optical absorption spectrum due to the small size (3-5 nm) of CdS particles. The data of circular dichroism (CD) spectra indicate that the formation of CdS nanocrystals could lead to the conformational change of zein molecules. Moreover, the possible mechanism of CdS nanocrystals growth in zein solution was also discussed. The weak interactions such as Van der Waals, hydrophobic forces and hydrogen bonds in zein molecules should play a crucial factor in the self-assembly of small nanoparticles.

The E3Σ1+ (63S1)←A3Π0+(53P1) transition in CdAr revisited: The spectrum and new analysis of the E3Σ1+ Rydberg state interatomic potential.

PubMed

Urbańczyk, T; Krośnicki, M; Kędziorski, A; Koperski, J

2018-05-05

Revisited study of the E 3 Σ 1 + (6 3 S 1 )←A 3 Π 0+ (5 3 P 1 ) transition in CdAr using both theoretical and experimental approach is presented. Systematic detection of the E 3 Σ 1 + in ,υ'←A 3 Π 0+ ,υ″=6 transition frequencies with higher accuracy and spectrally narrower laser extended and improved analysis and simulation of the LIF excitation spectrum. More consistent characterization of the E 3 Σ 1 + in -Rydberg state inner well using inversed perturbation approach methodology was achieved. Free←bound transitions in the E 3 Σ 1 + in ←A 3 Π 0+ ,υ″=6 excitation were taken into account in the analysis and simulation of the recorded spectrum. The updated spectroscopic characterization of the A 3 Π 0+ state was also revisited. Copyright © 2018 Elsevier B.V. All rights reserved.

The E3Σ1+ (63S1) ← A3Π0+(53P1) transition in CdAr revisited: The spectrum and new analysis of the E3Σ1+ Rydberg state interatomic potential

NASA Astrophysics Data System (ADS)

Urbańczyk, T.; Krośnicki, M.; Kędziorski, A.; Koperski, J.

2018-05-01

Revisited study of the E3Σ1+ (63S1) ← A3Π0+(53P1) transition in CdAr using both theoretical and experimental approach is presented. Systematic detection of the E3Σ1+in,υ' ← A3Π0+,υ″ = 6 transition frequencies with higher accuracy and spectrally narrower laser extended and improved analysis and simulation of the LIF excitation spectrum. More consistent characterization of the E3Σ1+in-Rydberg state inner well using inversed perturbation approach methodology was achieved. Free ← bound transitions in the E3Σ1+in ← A3Π0+,υ″ = 6 excitation were taken into account in the analysis and simulation of the recorded spectrum. The updated spectroscopic characterization of the A3Π0+ state was also revisited.

Three New Cytotoxic Withanolides from the Chinese Folk Medicine Physalis angulata.

PubMed

Gao, Cai-Yun; Ma, Ting; Luo, Jun; Kong, Ling-Yi

2015-12-01

Physagulides M-O, three new withanolides (1-3), were isolated from the aerial parts of Physalis angulata L. Their structures were elucidated through extensive spectroscopic techniques, including 1D and 2D NMR, and HRESIMS. The absolute configurations (22-R) of these new compounds were determined by CD analysis. Compounds 1 and 3 showed significant selective cytotoxic activities on the MG-63 cell line, with IC50 values of 4.28 and 5.44 μM, respectively.

Dye sensitized solar cell applications of CdTiO3-TiO2 composite thin films deposited from single molecular complex

NASA Astrophysics Data System (ADS)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy; Huang, Nay Ming; Arifin, Zainudin; Mazhar, Muhammad

2015-10-01

A heterobimetallic complex [Cd2Ti4(μ-O)6(TFA)8(THF)6]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO3-TiO2 composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity, phase identification and chemical composition of microspherical architectured CdTiO3-TiO2 composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application.

On the Role of High Amounts of Mn Element in CdS Structure

NASA Astrophysics Data System (ADS)

Gonullu, Meryem Polat; Kose, Salih

2017-03-01

CdS and MnS are technologically important semiconducting materials. In this work, due to the limited ability of these materials separately, a detailed characterization of the new samples formed by the combined use of them has been reported. CdS films, with the incorporation of Mn in a wide range of concentrations, have been produced by a low-cost Ultrasonic Spray Pyrolysis set-up. Spectroscopic Ellipsometry (SE) has been used to determine the thicknesses and optical constants ( n, k) of the samples. It has been determined that samples with high amounts of Mn have lower refractive index values. Absorbance spectra have shown additional band edges along with the one belonging to CdS, for samples with Mn concentrations higher than 50 pct. This has been attributed to a phase separation above this limit. Raman spectroscopy analysis which shows additional Raman peaks belonging to MnS phase also supports these findings. Depending on this phase separation, crystalline structure has been deteriorated. Surface properties of the samples have been investigated by SEM and AFM. Elemental analysis has been performed by EDS. Resistivity measurements performed by a four-probe set-up have shown that samples containing high amount of Mn have lower electrical resistivity values.

Anion-cation charge-transfer properties and spectral studies of [M(phen)3][Cd4(SPh)10] (M = Ru, Fe, and Ni).

PubMed

Jiang, Jian-Bing; Bian, Guo-Qing; Zhang, Ya-Ping; Luo, Wen; Zhu, Qin-Yu; Dai, Jie

2011-10-07

Three anion-cation compounds 1-3 with formula [M(phen)(3)][Cd(4)(SPh)(10)]·Sol (M = Ru(2+), Fe(2+), and Ni(2+), Sol = MeCN and H(2)O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π···π stacking and C-H···π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion-cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)(3)](2+) is enhanced when the cation interacts with the [Cd(4)(SPh)(10)](2-) anion. The mechanism for the enhancement of photoluminescence has been proposed.

Dynamics of cD Clusters of Galaxies. 4; Conclusion of a Survey of 25 Abell Clusters

NASA Technical Reports Server (NTRS)

Oegerle, William R.; Hill, John M.; Fisher, Richard R. (Technical Monitor)

2001-01-01

We present the final results of a spectroscopic study of a sample of cD galaxy clusters. The goal of this program has been to study the dynamics of the clusters, with emphasis on determining the nature and frequency of cD galaxies with peculiar velocities. Redshifts measured with the MX Spectrometer have been combined with those obtained from the literature to obtain typically 50 - 150 observed velocities in each of 25 galaxy clusters containing a central cD galaxy. We present a dynamical analysis of the final 11 clusters to be observed in this sample. All 25 clusters are analyzed in a uniform manner to test for the presence of substructure, and to determine peculiar velocities and their statistical significance for the central cD galaxy. These peculiar velocities were used to determine whether or not the central cD galaxy is at rest in the cluster potential well. We find that 30 - 50% of the clusters in our sample possess significant subclustering (depending on the cluster radius used in the analysis), which is in agreement with other studies of non-cD clusters. Hence, the dynamical state of cD clusters is not different than other present-day clusters. After careful study, four of the clusters appear to have a cD galaxy with a significant peculiar velocity. Dressler-Shectman tests indicate that three of these four clusters have statistically significant substructure within 1.5/h(sub 75) Mpc of the cluster center. The dispersion 75 of the cD peculiar velocities is 164 +41/-34 km/s around the mean cluster velocity. This represents a significant detection of peculiar cD velocities, but at a level which is far below the mean velocity dispersion for this sample of clusters. The picture that emerges is one in which cD galaxies are nearly at rest with respect to the cluster potential well, but have small residual velocities due to subcluster mergers.

Spectroscopic characterization of metal bound phytochelatin analogue (Glu-Cys)4-Gly.

PubMed

Cheng, Yongsheng; Yan, Yong-Bin; Liu, Jinyuan

2005-10-01

The metal ion binding properties of a phytochelatin (PC) analogue, (Glu-Cys)4-Gly (named as EC4), have been studied by a divalent metal ion binding assay monitored by UV-visible spectroscopy, circular dichroism and NMR spectroscopy. Spectro- photometric titration with different divalent metal ions have revealed that the stiochoimetry of metal-bound EC4 was 1:1, and its metal binding affinities with different divalent metal ions in the order of Cd(II)>Cu(II)>Zn(II)>Pb(II)>Ni(II)>Co(II). UV-visible spectroscopic analysis of metal complexes indicated that four sulfur atoms in cysteine residues are attributable to ligand-to-metal charge transfer (LMCT) between divalent metal ions and EC4, and further confirmed by 1D H1 NMR study and Circular Dichroism. In addition, Circular Dichroism spectra of both free and metal-bound forms of EC4 revealed that metal coordination drives the nonapeptide chain to fold into a turned conformation. The comprehensive analysis of spectroscopic properties of the nonapeptide complexed with metal ions not only provides a fundamental description of the metal ion binding properties of PC analogue, but also shows a correlation between metal binding affinity of PC analogue and the induction activity of metal ions.

Classification of inflammatory bowel diseases by means of Raman spectroscopic imaging of epithelium cells

NASA Astrophysics Data System (ADS)

Bielecki, Christiane; Bocklitz, Thomas W.; Schmitt, Michael; Krafft, Christoph; Marquardt, Claudio; Gharbi, Akram; Knösel, Thomas; Stallmach, Andreas; Popp, Juergen

2012-07-01

We report on a Raman microspectroscopic characterization of the inflammatory bowel diseases (IBD) Crohn's disease (CD) and ulcerative colitis (UC). Therefore, Raman maps of human colon tissue sections were analyzed by utilizing innovative chemometric approaches. First, support vector machines were applied to highlight the tissue morphology (=Raman spectroscopic histopathology). In a second step, the biochemical tissue composition has been studied by analyzing the epithelium Raman spectra of sections of healthy control subjects (n=11), subjects with CD (n=14), and subjects with UC (n=13). These three groups exhibit significantly different molecular specific Raman signatures, allowing establishment of a classifier (support-vector-machine). By utilizing this classifier it was possible to separate between healthy control patients, patients with CD, and patients with UC with an accuracy of 98.90%. The automatic design of both classification steps (visualization of the tissue morphology and molecular classification of IBD) paves the way for an objective clinical diagnosis of IBD by means of Raman spectroscopy in combination with chemometric approaches.

"Reagent-free" L-asparaginase activity assay based on CD spectroscopy and conductometry.

PubMed

Kudryashova, Elena V; Sukhoverkov, Kirill V

2016-02-01

A new method to determine the catalytic parameters of L-asparaginase using circular dichroism spectroscopy (CD spectroscopy) has been developed. The assay is based on the difference in CD signal between the substrate (L-asparagine) and the product (L-aspartic acid) of enzymatic reaction. CD spectroscopy, being a direct method, enables continuous measurement, and thus differentiates from multistage and laborious approach based on Nessler's method, and overcomes limitations of conjugated enzymatic reaction methods. In this work, we show robust measurements of L-asparaginase activity in conjugates with PEG-chitosan copolymers, which otherwise would not have been possible. The main limitation associated with the CD method is that the analysis should be performed at substrate saturation conditions (V max regime). For K M measurement, the conductometry method is suggested, which can serve as a complimentary method to CD spectroscopy. The activity assay based on CD spectroscopy and conductometry was successfully implicated to examine the catalytic parameters of L-asparaginase conjugates with chitosan and its derivatives, and for optimization of the molecular architecture and composition of such conjugates for improving biocatalytic properties of the enzyme in the physiological conditions. The approach developed is potentially applicable to other enzymatic reactions where the spectroscopic properties of substrate and product do not enable direct measurement with absorption or fluorescence spectroscopy. This may include a number of amino acid or glycoside-transforming enzymes.

Subgap time of flight: A spectroscopic study of deep levels in semi-insulating CdTe:Cl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pousset, J.; Farella, I.; Cola, A., E-mail: adriano.cola@le.imm.cnr.it

2016-03-14

We report on a study of deep levels in semi-insulating CdTe:Cl by means of a time-of-flight spectral approach. By varying the wavelength of a pulsed optical source within the CdTe energy gap, transitions to/from localized levels generate free carriers which are analysed through the induced photocurrent transients. Both acceptor-like centers, related to the A-center, and a midgap level, 0.725 eV from the valence band, have been detected. The midgap level is close to the Fermi level and is possibly a recombination center responsible for the compensation mechanism. When the irradiance is varied, either linear or quadratic dependence of the electron andmore » hole collected charge are observed, depending on the dominant optical transitions. The analysis discloses the potentiality of such a novel approach exploitable in the field of photorefractive materials as well as for deep levels spectroscopy.« less

A /sup 1/Pi--X /sup 1/. sigma. /sup +/ band system in CH/sup +/ and CD/sup +/: theoretical spectroscopic constants and lifetimes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elander, N.; Oddershede, J.; Beebe, N.H.F.

1977-08-15

Polarization propagator calculation of spectroscopic constants and radiative lifetimes for the A /sup 1/Pi--X /sup 1/..sigma../sup +/ band system are presented. The spectroscopic constants agree well with experimental and other theoretical values. We have also performed an iterative Rydberg-Klein-Rees (RKR) calculation of B/sub e/, ..omega../sub e/, and ..omega../sub e/x/sub e/ for the experimental X /sup 1/..sigma../sup +/ state.The calculated radiative lifetime for the A /sup 1/Pi state (v'=0) is 660 ns and 598 ns, with theoretical and experimental potential energy curves, respectively. This difference (about 60 ns) indicates the inaccuracy in the present calculation. Experimentally the most recent estimate ofmore » the A /sup 1/Pi (v'=0) state is 630 +- 50 ns, and theoretically the Yoshimine et al. transition moment gives tau (A /sup 1/Pi, v'=0) =722 ns.The radiative lifetimes calculated for CD/sup +/ are between 1.3% and 3.9% larger than the corresponding CH/sup +/ lifetimes.« less

Position sensitive detection of neutrons in high radiation background field.

PubMed

Vavrik, D; Jakubek, J; Pospisil, S; Vacik, J

2014-01-01

We present the development of a high-resolution position sensitive device for detection of slow neutrons in the environment of extremely high γ and e(-) radiation background. We make use of a planar silicon pixelated (pixel size: 55 × 55 μm(2)) spectroscopic Timepix detector adapted for neutron detection utilizing very thin (10)B converter placed onto detector surface. We demonstrate that electromagnetic radiation background can be discriminated from the neutron signal utilizing the fact that each particle type produces characteristic ionization tracks in the pixelated detector. Particular tracks can be distinguished by their 2D shape (in the detector plane) and spectroscopic response using single event analysis. A Cd sheet served as thermal neutron stopper as well as intensive source of gamma rays and energetic electrons. Highly efficient discrimination was successful even at very low neutron to electromagnetic background ratio about 10(-4).

Position sensitive detection of neutrons in high radiation background field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vavrik, D., E-mail: vavrik@itam.cas.cz; Institute of Theoretical and Applied Mechanics, Academy of Sciences of the Czech Republic, Prosecka 76, 190 00 Prague 9; Jakubek, J.

We present the development of a high-resolution position sensitive device for detection of slow neutrons in the environment of extremely high γ and e{sup −} radiation background. We make use of a planar silicon pixelated (pixel size: 55 × 55 μm{sup 2}) spectroscopic Timepix detector adapted for neutron detection utilizing very thin {sup 10}B converter placed onto detector surface. We demonstrate that electromagnetic radiation background can be discriminated from the neutron signal utilizing the fact that each particle type produces characteristic ionization tracks in the pixelated detector. Particular tracks can be distinguished by their 2D shape (in the detector plane)more » and spectroscopic response using single event analysis. A Cd sheet served as thermal neutron stopper as well as intensive source of gamma rays and energetic electrons. Highly efficient discrimination was successful even at very low neutron to electromagnetic background ratio about 10{sup −4}.« less

Spectroscopic manifestations of hybrid association of CdS colloidal quantum dots with J-aggregates of a thiatrimethine cyanine dye

NASA Astrophysics Data System (ADS)

Ovchinnikov, O. V.; Smirnov, M. S.; Shapiro, B. I.; Dedikova, A. O.; Shatskikh, T. S.

2015-11-01

We have found spectroscopic manifestations of hybrid association in mixtures of CdS colloidal quantum dots with an average size of 2.5-4.2 nm with J-aggregates of pyridinium salt of the 3,3'-di-(γ- sulfopropyl)-9-ethyl-4,5,4',5'-dibenzo-thiacarbocyanine betaine dye that were prepared by the sol-gel method in gelatin. Observed changes of the spectral properties of J-aggregates of dye molecules due to their hybrid association with CdS quantum dots are ensured by steric transformations of dye molecules, which lead to the formation of luminescent trans-J-aggregates. The hybrid association is accompanied by the quenching of the recombination luminescence band of CdS quantum dots (540-640 nm) and by an increase in the luminescence intensity of J-aggregates of dye molecules (670-680 nm). This regularity becomes enhanced with an increase in the ratio of the number of dye molecules to the number of quantum dots [ n dye]: [ n QD] and in the degree of overlap between the luminescence spectrum of quantum dots and the absorption spectrum of J-aggregates, which indicates that there is a resonant nonradiative transfer of the electronic excitation energy from recombination luminescence centers in CdS quantum dots to trans-J-aggregates of dye molecules conjugated to them.

Spectroscopic and microscopic investigation of MBE-grown CdTe (211)B epitaxial thin films on GaAs (211)B substrates

NASA Astrophysics Data System (ADS)

Özden, Selin; Koc, Mumin Mehmet

2018-03-01

CdTe epitaxial thin films, for use as a buffer layer for HgCdTe defectors, were grown on GaAs (211)B using the molecular beam epitaxy method. Wet chemical etching (Everson method) was applied to the epitaxial films using various concentrations and application times to quantify the crystal quality and dislocation density. Surface characterization of the epitaxial films was achieved using Atomic force microscopy and Scanning electron microscopy (SEM) before and after each treatment. The Energy Dispersive X-Ray apparatus of SEM was used to characterize the chemical composition. Untreated CdTe films show smooth surface characteristics with root mean square (RMS) roughnesses of 1.18-3.89 nm. The thicknesses of the CdTe layers formed were calculated via FTIR spectrometry and obtained by ex situ spectroscopic ellipsometry. Raman spectra were obtained for various temperatures. Etch pit densities (EPD) were measured, from which it could be seen that EPD changes between 1.7 × 108 and 9.2 × 108 cm-2 depending on the concentration of the Everson etch solution and treatment time. Structure, shape and depth of pits resulting from each etch pit implementation were also evaluated. Pit widths varying between 0.15 and 0.71 µm with heights varying between 2 and 80 nm were observed. RMS roughness was found to vary by anything from 1.56 to 26 nm.

Enhanced anticancer effect of fabricated gallic acid/CdS on the rGO nanosheets on human glomerular mesangial (IP15) and epithelial proximal (HK2) kidney cell lines - Cytotoxicity investigations.

PubMed

Peng, Wei; Luo, Pengcheng; Gui, Dingwen; Jiang, Weidong; Wu, Haixia; Zhang, Jie

2018-01-01

In spite of the technological innovation in the biomedical science, cancer remains a critical disease. In this study, we designed a gallic acid/cadmium sulfide (GA/CdS) nanocomposite fabricated on the reduced graphene oxide (GA/CdS-rGO) nanosheets for the treatment system of human kidney cancer cells. The GA/CdS-rGO nanosheets have been prepared using gallic acid as a reducing agent. The characterization of nanocomposites was studied using UV-Vis spectroscope, FT-IR, XRD, SEM and TEM. The microscopic images showed the spherical shape and nano-scaled CdS nanoparticles on the sheet like rGO nanomaterials. These structural and morphology investigations show that excellent properties of as-prepared GA/CdS-rGO has ability to treat the human glomerular mesangial (IP15) cancer cells at 50μg/ml as an IC 50 value, without affecting the epithelial proximal (HK-2) normal cells. In vitro cytotoxicity results showed that the variability of toxic effects after CdS exposure was strongly associated to the cellular Cd content. Release of Cd 2+ from nanocomposites depended to solubility and particle degradation of CdS nanoparticles were considered to be the main cause of these cytotoxicity. The in vitro analysis results indicated that heterogeneity of Cd and gallic acid toxicity that was highly dependent on the physico-chemical properties of the nanocomposites. The cytotoxicity results suggested that the prepared nanomaterials were toxic and inhibitory efficiency to human kidney cancer cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigating the Electron-Phonon Coupling of Molecular Beam Epitaxy-Grown Hg1-x Cd x Se Semiconductor Alloys

NASA Astrophysics Data System (ADS)

Peiris, F. C.; Lewis, M. V.; Brill, G.; Doyle, Kevin; Myers, T. H.

2018-03-01

Using spectroscopic ellipsometry, the temperature-dependence of the dielectric functions of a series of Hg1-x Cd x Se thin films deposited on both ZnTe/Si(112) and GaSb(112) substrates were investigated. Initially, for each sample, room-temperature ellipsometric spectra were obtained from 35 meV to 6 eV using two different ellipsometers. Subsequently, ellipsometry spectra were obtained from 10 K to 300 K by incorporating a cryostat to the ellipsometer. Using a standard inversion technique, the spectroscopic ellipsometric data were modeled in order to obtain the temperature-dependent dielectric functions of each of the Hg1-x Cd x Se thin films. The results indicate that the E 1 critical point blue-shifts as a function of Cd-alloy concentration. The temperature-dependence of E 1 was fitted to a Bose-Einstein occupation distribution function, which consequently allowed us to determine the electron-phonon coupling of Hg1-x Cd x Se alloys. From the fitting results, we obtain a value of 17 ± 2 meV for the strength of the electron-phonon coupling for Hg1-x Cd x Se alloy system, which compares nominally with the binary systems, such as CdSe and CdTe, which have values around 38 meV and 16 meV, respectively. This implies that the addition of Hg into the CdSe binary system does not significantly alter its electron-phonon coupling strength. Raman spectroscopy measurements performed on all the samples show the HgSe-like transverse optic (TO) and longitudinal optic (LO) phonons (˜ 130 cm-1 and ˜ 160 cm-1, respectively) for all the samples. While there is a slight red-shift of the HgSe-like TO peak as a function of the Cd-concentration, HgSe-like LO peak does not significantly change with the alloy concentration.

Immunomodulatory Polyketides from a Phoma-like Fungus Isolated from a Soft Coral.

PubMed

Sun, Yi-Zhe; Kurtán, Tibor; Mándi, Attila; Tang, Hua; Chou, Yalan; Soong, Keryea; Su, Li; Sun, Peng; Zhuang, Chun-Lin; Zhang, Wen

2017-11-22

Fourteen new polyketides with a trans-fused decalin ring system, libertalides A-N (3-16), together with two known analogues, aspermytin A and its acetate (1, 2), were isolated from the fermentation extract of a coral-derived Libertasomyces sp. fungus. Their relative configurations were elucidated on the basis of detailed spectroscopic analysis, and the absolute configurations were determined by TDDFT-ECD and optical rotation (OR) calculations. The OR of 1 and 2 were found to have opposite signs in CH 3 CN and CHCl 3 , which was in agreement with the OR calculations producing alternating signs for the optical rotation depending on the applied conditions. Because the signs of the OR for 1 and 2 showed high solvent dependence, they may not be used alone to correlate the absolute configurations. Compound 16 displayed structural novelty characterized by an α-enol ether bridge conjugated with an aldehyde group. In in vitro immunomodulatory screening, compounds 1, 4, and 10 significantly induced the proliferation of CD3 + T cells, while compounds 2, 7, 11, and 14 significantly increased the CD4 + /CD8 + ratio at 3 μM. A preliminary structure-activity analysis revealed a crucial role of Δ 7 and a terminal OH group in the regulation of CD3 + T cell proliferation. This is the first report of immunoregulatory activity for metabolites of this kind.

The multi-mode polarization modulation spectrometer: part 1: simultaneous detection of absorption, turbidity, and optical activity.

PubMed

Arvinte, Tudor; Bui, Tam T T; Dahab, Ali A; Demeule, Barthélemy; Drake, Alex F; Elhag, Dhia; King, Peter

2004-09-01

Circular dichroism (CD) is an important spectroscopic technique for monitoring chirality and biological macromolecule conformation. However, during a CD measurement, absorbance, light scattering/turbidity, and fluorescence can also be detected. The simultaneous measurement of these different spectral features for a single sample is the basis of a multi-mode optical spectrometer. This allows time-efficient gathering of complementary information and provides a scheme to ensure that CD measurements are reliable. Aspects of circular polarization differential light scattering, pH, and temperature variation of a protein (antibody) solution are described. A procedure to help ensure that CD measurements are reliable is described.

2D polymeric cadmium(II) complexes containing 1,3-imidazolidine-2-thione (Imt) ligand, [Cd(Imt)(H2O)2(SO4)]n and [Cd(Imt)2(N3)2]n

NASA Astrophysics Data System (ADS)

Mahmood, Rashid; Ahmad, Saeed; Fettouhi, Mohammed; Roisnel, Thierry; Gilani, Mazhar Amjad; Mehmood, Kashif; Murtaza, Ghulam; Isab, Anvarhusein A.

2018-03-01

The present study aims at preparing and carrying out the structural investigation of two polymeric cadmium(II) complexes of imidazolidine-2-thione (Imt) based on sulfate or azide ions, [Cd(Imt)(H2O)2(SO4)]n (1) and [Cd(Imt)2(N3)2]n (2). The structures of the complexes were determined by single crystal X-ray analysis. Both compounds, 1 and 2 crystallize in the form of 2D coordination polymers and the cadmium(II) ion is six-coordinate having a distorted octahedral geometry in each compound. In 1, the metal ion is bonded to one sulfur atom of Imt and five oxygen atoms with two from water and three of bridging sulfate ions. In 2, the cadmium coordination sphere is completed by two Imt molecules binding through the sulfur atoms and four nitrogen atoms of bridging azide ions. The crystal structures are stabilized by intra and intermolecular hydrogen bonding interactions. The complexes were also characterized by IR and NMR spectroscopy and the spectroscopic data is consistent with the binding of the ligands.

Compound semiconductor detectors for X-ray astronomy: Spectroscopic measurements and material characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bavdaz, M.; Kraft, S.; Peacock, A.

1998-12-31

The use of some specific compound semiconductors in the fabrication of high energy X-ray detectors shows significant potential for X-ray astrophysics space missions. The authors are currently investigating three high purity crystals--CdZnTe, GaAs and TlBr--as the basis for future hard X-ray detectors (above 10 keV). In this paper the authors present the first results on CdZnTe and GaAs based detectors and evaluate the factors currently still constraining the performance. Energy resolutions (FWHM) of 0.9 keV and 1.1 keV at 14 keV and 60 keV, respectively, have been obtained with an epitaxial GaAs detector, while 0.7 keV and 1.5 keV FWHMmore » were measured at the same energies with a CdZnTe detector. Based on these results it is clear, that the next generation of X-ray astrophysics missions now in the planning phase may well consider extending the photon energy range up to {approximately} 100 keV by use of efficient detectors with reasonable spectroscopic capabilities.« less

Studies on the interactions of SAP-1 (an N-terminal truncated form of cystatin S) with its binding partners by CD-spectroscopic and molecular docking methods.

PubMed

Yadav, Vikash Kumar; Mandal, Rahul Shubhra; Puniya, Bhanwar Lal; Singh, Sarman; Yadav, Savita

2015-01-01

SAP-1 is a 113 amino acid long single-chain protein which belongs to the type 2 cystatin gene family. In our previous study, we have purified SAP-1 from human seminal plasma and observed its cross-class inhibitory property. At this time, we report the interaction of SAP-1 with diverse proteases and its binding partners by CD-spectroscopic and molecular docking methods. The circular dichroism (CD) spectroscopic studies demonstrate that the conformation of SAP-1 is changed after its complexation with proteases, and the alterations in protein secondary structure are quantitatively calculated with increase of α-helices and reduction of β-strand content. To get insight into the interactions between SAP-1 and proteases, we make an effort to model the three-dimensional structure of SAP-1 by molecular modeling and verify its stability and viability through molecular dynamics simulations and finally complexed with different proteases using ClusPro 2.0 Server. A high degree of shape complementarity is examined within the complexes, stabilized by a number of hydrogen bonds (HBs) and hydrophobic interactions. Using HB analyses in different protein complexes, we have identified a series of key residues that may be involved in the interactions between SAP-1 and proteases. These findings will assist to understand the mechanism of inhibition of SAP-1 for different proteases and provide intimation for further research.

Optical spectroscopic methods for probing the conformational stability of immobilised enzymes.

PubMed

Ganesan, Ashok; Moore, Barry D; Kelly, Sharon M; Price, Nicholas C; Rolinski, Olaf J; Birch, David J S; Dunkin, Ian R; Halling, Peter J

2009-07-13

We report the development of biophysical techniques based on circular dichroism (CD), diffuse reflectance infrared Fourier transform (DRIFT) and tryptophan (Trp) fluorescence to investigate in situ the structure of enzymes immobilised on solid particles. Their applicability is demonstrated using subtilisin Carlsberg (SC) immobilised on silica gel and Candida antartica lipase B immobilised on Lewatit VP.OC 1600 (Novozyme 435). SC shows nearly identical secondary structure in solution and in the immobilised state as evident from far UV CD spectra and amide I vibration bands. Increased near UV CD intensity and reduced Trp fluorescence suggest a more rigid tertiary structure on the silica surface. After immobilised SC is inactivated, these techniques reveal: a) almost complete loss of near UV CD signal, suggesting loss of tertiary structure; b) a shift in the amide I vibrational band from 1658 cm(-1) to 1632 cm(-1), indicating a shift from alpha-helical structure to beta-sheet; c) a substantial blue shift and reduced dichroism in the far UV CD, supporting a shift to beta-sheet structure; d) strong increase in Trp fluorescence intensity, which reflects reduced intramolecular quenching with loss of tertiary structure; and e) major change in fluorescence lifetime distribution, confirming a substantial change in Trp environment. DRIFT measurements suggest that pressing KBr discs may perturb protein structure. With the enzyme on organic polymer it was possible to obtain near UV CD spectra free of interference by the carrier material. However, far UV CD, DRIFT and fluorescence measurements showed strong signals from the organic support. In conclusion, the spectroscopic methods described here provide structural information hitherto inaccessible, with their applicability limited by interference from, rather than the particulate nature of, the support material.

Deuterated fatty acids as Raman spectroscopic probes of membrane structure.

PubMed

Mendelsohn, R; Sunder, S; Bernstein, H J

1976-09-07

Raman spectra are reported for the C-D stretching region of stearic acid-d35 bound in egg lecithin multilayers. The temperature dependence of the spectra shows that the linewidth of the C-D stretching bands is a sensitive and non-perturbative probe of membrane hydrocarbon chain conformation. The utility of this approach for studying lipid conformation in membranes containing a significant fraction of non-lipid component is discussed.

The interactions between CdSe quantum dots and yeast Saccharomyces cerevisiae: adhesion of quantum dots to the cell surface and the protection effect of ZnS shell.

PubMed

Mei, Jie; Yang, Li-Yun; Lai, Lu; Xu, Zi-Qiang; Wang, Can; Zhao, Jie; Jin, Jian-Cheng; Jiang, Feng-Lei; Liu, Yi

2014-10-01

The interactions between quantum dots (QDs) and biological systems have attracted increasing attention due to concerns on possible toxicity of the nanoscale materials. The biological effects of CdSe QDs and CdSe/ZnS QDs with nearly identical hydrodynamic size on Saccharomyces cerevisiae were investigated via microcalorimetric, spectroscopic and microscopic methods, demonstrating a toxic order CdSe>CdSe/ZnS QDs. CdSe QDs damaged yeast cell wall and reduced the mitochondrial membrane potential. Noteworthy, adhesion of QDs to the yeast cell surface renders this work a good example of interaction site at cell surface, and the epitaxial coating of ZnS could greatly reduce the toxicity of Cd-containing QDs. These results will contribute to the safety evaluation of quantum dots, and provide valuable information for design of nanomaterials. Copyright © 2014 Elsevier Ltd. All rights reserved.

The relationship between Cho/NAA and glioma metabolism: implementation for margin delineation of cerebral gliomas.

PubMed

Guo, Jun; Yao, Chengjun; Chen, Hong; Zhuang, Dongxiao; Tang, Weijun; Ren, Guang; Wang, Yin; Wu, Jinsong; Huang, Fengping; Zhou, Liangfu

2012-08-01

The marginal delineation of gliomas cannot be defined by conventional imaging due to their infiltrative growth pattern. Here we investigate the relationship between changes in glioma metabolism by proton magnetic resonance spectroscopic imaging ((1)H-MRSI) and histopathological findings in order to determine an optimal threshold value of choline/N-acetyl-aspartate (Cho/NAA) that can be used to define the extent of glioma spread. Eighteen patients with different grades of glioma were examined using (1)H-MRSI. Needle biopsies were performed under the guidance of neuronavigation prior to craniotomy. Intraoperative magnetic resonance imaging (MRI) was performed to evaluate the accuracy of sampling. Haematoxylin and eosin, and immunohistochemical staining with IDH1, MIB-1, p53, CD34 and glial fibrillary acidic protein (GFAP) antibodies were performed on all samples. Logistic regression analysis was used to determine the relationship between Cho/NAA and MIB-1, p53, CD34, and the degree of tumour infiltration. The clinical threshold ratio distinguishing tumour tissue in high-grade (grades III and IV) glioma (HGG) and low-grade (grade II) glioma (LGG) was calculated. In HGG, higher Cho/NAA ratios were associated with a greater probability of higher MIB-1 counts, stronger CD34 expression, and tumour infiltration. Ratio threshold values of 0.5, 1.0, 1.5 and 2.0 appeared to predict the specimens containing the tumour with respective probabilities of 0.38, 0.60, 0.79, 0.90 in HGG and 0.16, 0.39, 0.67, 0.87 in LGG. HGG and LGG exhibit different spectroscopic patterns. Using (1)H-MRSI to guide the extent of resection has the potential to improve the clinical outcome of glioma surgery.

Fatty acid modulated human serum albumin binding of the β-carboline alkaloids norharmane and harmane.

PubMed

Domonkos, Celesztina; Fitos, Ilona; Visy, Júlia; Zsila, Ferenc

2013-12-02

Harmane and norharmane are representative members of the large group of natural β-carboline alkaloids featured with diverse pharmacological activities. In blood, these agents are transported by human serum albumin (HSA) which has a profound impact on the pharmacokinetic and pharmacodynamic properties of many therapeutic drugs and xenobiotics. By combination of various spectroscopic methods, the present contribution is aimed to elucidate how nonesterified fatty acids (FAs), the primary endogenous ligands of HSA, affect the binding properties of harmane and norharmane. Analysis of induced circular dichroism (CD) and fluorescence spectroscopic data indicates the inclusion of the neutral form of both molecules into the binding pocket of subdomain IIIA, which hosts two FA binding sites, too. The induced CD and UV absorption spectra of harmane and norharmane exhibit peculiar changes upon addition of FAs, suggesting the formation of ternary complexes in which the lipid ligands significantly alter the binding mode of the alkaloids via cooperative allosteric mechanism. To our knowledge, it is the first instance of the demonstration of drug-FA cobinding at site IIIA. In line with these results, molecular docking calculations showed two distinct binding positions of norharmane within subdomain IIIA. The profound increase in the affinity constants of β-carbolines estimated in the presence of FAs predicts that the unbound, pharmacologically active serum fraction of these compounds strongly depends on the actual lipid binding profile of HSA.

Photovoltaic and Impedance Spectroscopy Study of Screen-Printed TiO₂ Based CdS Quantum Dot Sensitized Solar Cells.

PubMed

Atif, M; Farooq, W A; Fatehmulla, Amanullah; Aslam, M; Ali, Syed Mansoor

2015-01-19

Cadmium sulphide (CdS) quantum dot sensitized solar cells (QDSSCs) based on screen-printed TiO₂ were assembled using a screen-printing technique. The CdS quantum dots (QDs) were grown by using the Successive Ionic Layer Adsorption and Reaction (SILAR) method. The optical properties were studied by UV-Vis absorbance spectroscopy. Photovoltaic characteristics and impedance spectroscopic measurements of CdS QDSSCs were carried out under air mass 1.5 illuminations. The experimental results of capacitance against voltage indicate a trend from positive to negative capacitance because of the injection of electrons from the Fluorine doped tin oxide (FTO) electrode into TiO₂.

The immune adjuvant response of polysaccharides from Atractylodis macrocephalae Koidz in chickens vaccinated against Newcastle disease (ND).

PubMed

Zhao, Xiaona; Sun, Wenjing; Zhang, Shijie; Meng, Guangju; Qi, Chunhua; Fan, Wentao; Wang, Yuge; Liu, Jianzhu

2016-05-05

Build on our previous research, polysaccharides from the rhizome of Atractylodis macrocephalae Koidz (RAMPS), RAMPStp and RAMPS60c were prepared and the structural characterization and immune response of ND vaccine in chicken were investigated. Immune organ index, Lymphocyte proliferation, antibody titers, cell cycle distribution, and percentages of CD4(+) and CD8(+) cells were determined. GPC analysis showed that the Mn of RAMPS with two peaks were 1.29×10(5) and 1.74×10(3), respectively. GC-MS analysis revealed that RAMPS was composed of glucose, mannose, arabinose, galactose, xylose, d-Ribose and rhamnose, with mass percentages of 66.39%, 21.24%, 5.64%, 2.65%, 2.30%, 1.15% and 0.64%, respectively. NMR spectroscopic analysis demonstrated that a preliminary structure of RAMPS was proposed as 1,3-linked β-d-Galp and 1,6-linked β-d-Galpresidues. In vivo test showed that RAMPStp and RAMPS60c could promote peripheral lymphocytes proliferation and entering into S and G2/M phases, enhance serum HI antibody titer and effectively improve the percentages of CD4(+) and CD8(+) T cells in chickens vaccinated with ND vaccine at most time points. The actions of RAMPStp and RAMPS60c were stronger than that of Lev, and RAMPStp presented the best efficacy. These results indicated that RAMPStp and RAMPS60c characterize of the immune-enhancing activity and RAMPStp possessed the strongest activity. It would be anticipated as a component of new-type immunopotentiator. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electronic structures and spectroscopic properties of CdI: MRCI+Q study including spin-orbit coupling

NASA Astrophysics Data System (ADS)

Li, Rui; Zhang, Hua; Liu, Xiaohua; Zhao, Shutao; Liu, Yadong; Yan, Bing

2018-01-01

Cadmium iodide (CdI), which is a candidate for laser material in chemical lasing, has attracted considerable scientific interest. While the complete picture for electronic structure of CdI is still unclear, particularly for the interactions of excited states. In this paper, high-level configuration interaction method is applied to compute the low-lying electronic states of the lowest two dissociation limits (Cd(1S) + I(2P) and Cd(3P) + I(2P)). To ensure the accuracy, the Davidson correction, core-valence electronic correlations and spin-orbit coupling effects are also taken into account. The potential energy curves of the 14 Λ-S states and 30 Ω states obtained from those Λ-S states are calculated. On the basis of the computed potential energy curves, the spectroscopic constants of bound and quasibound states are determined, most of which have not been reported in existing studies. The calculated values of spin-orbit coupling matrix elements demonstrate that the B2Σ+1/2 state imposes a strong perturbation on ν‧> 0 vibrational level of C2Π1/2, which can explain the weak spectral intensity of C2Π1/2-X2Σ+1/2 observed in previous experiment. The transition dipole moments as well as the lifetimes are evaluated to predict the transition properties of B2Σ+1/2, C2Π1/2 and 22Π3/2 states.

Four New Flavonoids with α-Glucosidase Inhibitory Activities from Morus alba var. tatarica.

PubMed

Zhang, Ya-Long; Luo, Jian-Guang; Wan, Chuan-Xing; Zhou, Zhong-Bo; Kong, Ling-Yi

2015-11-01

Four new flavonoids, mortatarins A-D (1-4, resp.), along with eight known flavonoids (5-12) were isolated from the root bark of Morus alba var. tatarica. Their structures were established on the basis of spectroscopic data analysis, and the absolute configuration of 4 was determined by analysis of its CD spectrum. All isolates were tested for inhibitory activities against α-glucosidase. Compounds 4, 7, and 8 exhibited a significant degree of inhibition with IC50 values of 5.0 ± 0.3, 7.5 ± 0.5, and 5.9 ± 0.2 μM, respectively. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

Three new amino acid derivatives from edible mushroom Pleurotus ostreatus.

PubMed

Lu, Xiao-Jie; Feng, Bao-Min; Chen, Shao-Fei; Zhao, Dan; Chen, Gang; Wang, Hai-Feng; Pei, Yue-Hu

2017-12-01

Three new amino acid derivatives, oxalamido-L-phenylalanine methyl ester (1), oxalamido-L-leucine methyl ester (2), and lumichrome hydrolyzate (3), together with nine known compounds (4-12), were isolated from the solid culture of edible mushroom Pleurotus ostreatus. Their structures were elucidated on the basis of extensive spectroscopic analysis. The absolute configurations of 1 and 2 were established by the chiral synthesis and confirmed by circular dichroism (CD) analysis of their total synthesis products and natural isolates. All new compounds were evaluated for their antioxidant effects, antimicrobial activities, and cytotoxic activity. Compounds 1-3 showed weak antifungal activities against Candida albicans with minimum inhibitory concentration (MIC) value of 500 μg/ml.

1D helical cadmium coordination polymers containing hydrazide ligand: The role of solvent and molar ratio

NASA Astrophysics Data System (ADS)

Notash, Behrouz

2018-03-01

Three new cadmium coordination polymers, [Cd(L)(NO3)2CH3OH]n, 1, {[Cd(L)2(NO3)]NO3}n, 2 and {[Cd(L)2(NO3)]NO3.H2O}n3, which L is nicotinohydrazide have been synthesized and characterized by spectroscopic methods as well as single crystal X-ray diffraction. Compounds 1-3 have been synthesized by changing solvent and metal-to-ligand ratio. X-ray crystallography showed that compounds 1-3 have different 1D helical structural motif. Semi-flexible nature of L ligand causes to syn-syn conformation which leading to form 1D helical chains coordination polymers. Compounds 2 and 3 were synthesized under the same reaction conditions with similar molar ratio, but using different solvent system. These compounds are pseudopolymorph which differs in the presence or absence of water molecule in their crystal packing. Hirshfeld surface analysis of the structures 1-3 have been performed and find the percent of participation of intermolecular interactions in the crystal packing of compounds.

Preparation, spectroscopic, thermal, antihepatotoxicity, hematological parameters and liver antioxidant capacity characterizations of Cd(II), Hg(II), and Pb(II) mononuclear complexes of paracetamol anti-inflammatory drug

NASA Astrophysics Data System (ADS)

El-Megharbel, Samy M.; Hamza, Reham Z.; Refat, Moamen S.

2014-10-01

Keeping in view that some metal complexes are found to be more potent than their parent drugs, therefore, our present paper aimed to synthesized Cd(II), Hg(II) and Pb(II) complexes of paracetamol (Para) anti-inflammatory drug. Paracetamol complexes with general formula [M(Para)2(H2O)2]·nH2O have been synthesized and characterized on the basis of elemental analysis, conductivity, IR and thermal (TG/DTG), 1H NMR, electronic spectral studies. The conductivity data of these complexes have non-electrolytic nature. Comparative antimicrobial (bacteria and fungi) behaviors and molecular weights of paracetamol with their complexes have been studied. In vivo the antihepatotoxicity effect and some liver function parameters levels (serum total protein, ALT, AST, and LDH) were measured. Hematological parameters and liver antioxidant capacities of both Para and their complexes were performed. The Cd2+ + Para complex was recorded amelioration of antioxidant capacities in liver homogenates compared to other Para complexes treated groups.

Antioxidant and quinone reductase-inducing constituents of black chokeberry (Aronia melanocarpa) fruits.

PubMed

Li, Jie; Deng, Ye; Yuan, Chunhua; Pan, Li; Chai, Heebyung; Keller, William J; Kinghorn, A Douglas

2012-11-21

Using in vitro hydroxyl radical-scavenging and quinone reductase-inducing assays, bioactivity-guided fractionation of an ethyl acetate-soluble extract of the fruits of the botanical dietary supplement, black chokeberry (Aronia melanocarpa), led to the isolation of 27 compounds, including a new depside, ethyl 2-[(3,4-dihydroxybenzoyloxy)-4,6-dihydroxyphenyl] acetate (1), along with 26 known compounds (2-27). The structures of the isolated compounds were identified by analysis of their physical and spectroscopic data ([α](D), NMR, IR, UV, and MS). Altogether, 17 compounds (1-4, 9, 15-17, and 19-27) showed significant antioxidant activity in the hydroxyl radical-scavenging assay, with hyperin (24, ED(50) = 0.17 μM) being the most potent. The new compound (1, ED(50) = 0.44 μM) also exhibited potent antioxidant activity in this assay. Three constituents of black chokeberry fruits doubled quinone reductase activity at concentrations <20 μM, namely, protocatechuic acid [9, concentration required to double quinone reductase activity (CD) = 4.3 μM], neochlorogenic acid methyl ester (22, CD = 6.7 μM), and quercetin (23, CD = 3.1 μM).

Four-wave mixing in CdMnTeSe: In crystals

NASA Astrophysics Data System (ADS)

Koziarska-Glinka, B.; Wojtowicz, T.; Miotkowski, I.; Furdyna, J. K.; Suchocki, A.

1998-02-01

It is shown that the four-wave mixing technique can be used as a spectroscopic tool for studying the properties of bistable centers in semiconductors. Two metastable centers with different lattice relaxation energy have been identified in the Cd 1- xMn xTe 1- ySe x: In crystal. The power dependence of the FWM signal provides additional support for the "negative-U" model of metastable centers in this material.

Cytotoxic prenylated flavones from the stem and root bark of Daphne giraldii.

PubMed

Sun, Qian; Wang, Di; Li, Fei-Fei; Yao, Guo-Dong; Li, Xue; Li, Ling-Zhi; Huang, Xiao-Xiao; Song, Shao-Jiang

2016-08-15

Three new prenylated flavones (1-3), along with three known analogues (4-6), were isolated from the stem and root bark of Daphne giraldii. Their structures were determined by comprehensive NMR and HRESIMS spectroscopic data analyses. The absolute configurations of compounds 2 and 3 were assigned by optical rotation comparison, CD and [Rh2(OCOCF3)4]-induced CD spectral methods. The in vitro cytotoxicity experiments carried out involving five cancer cell lines (U251, A549, HepG2, MCF-7 and Bcap37) showed that 2 markedly inhibited the proliferation of all tested cells with IC50 values ranging from 4.26 to 20.82μM. The preliminary structure-activity relationships of these flavones are discussed. In addition, compound 2 was found to effectively induce apoptosis in HepG2 cells according to a flow cytometry analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quadrupole-octupole coupled states in 112Cd populated in the 111Cd(d ⃗,p ) reaction

NASA Astrophysics Data System (ADS)

Jamieson, D. S.; Garrett, P. E.; Bildstein, V.; Demand, G. A.; Finlay, P.; Green, K. L.; Leach, K. G.; Phillips, A. A.; Sumithrarachchi, C. S.; Svensson, C. E.; Triambak, S.; Ball, G. C.; Faestermann, T.; Hertenberger, R.; Wirth, H.-F.

2014-11-01

States in 112Cd have been studied with the 111Cd(d ⃗,p ) 12Cd reaction using 22 MeV polarized deuterons. The protons from the reaction were momentum analyzed with a Q3D magnetic spectrograph, and spectra have been recorded with a position-sensitive detector located on the focal plane. Angular distributions of cross sections and analyzing powers have been constructed for the low-lying negative-parity states observed, including the 3-,4-, and 5- members of the previously assigned quadrupole-octupole quintuplet. The 5- member at 2373-keV possess the second largest spectroscopic strength observed, and is reassigned as having the s1/2⊗h11/2 two-quasineutron configuration as the dominate component of its wave function.

Very early reaction intermediates detected by microsecond time scale kinetics of cytochrome cd1-catalyzed reduction of nitrite.

PubMed

Sam, Katharine A; Strampraad, Marc J F; de Vries, Simon; Ferguson, Stuart J

2008-10-10

Paracoccus pantotrophus cytochrome cd(1) is a nitrite reductase found in the periplasm of many denitrifying bacteria. It catalyzes the reduction of nitrite to nitric oxide during the denitrification part of the biological nitrogen cycle. Previous studies of early millisecond intermediates in the nitrite reduction reaction have shown, by comparison with pH 7.0, that at the optimum pH, approximately pH 6, the earliest intermediates were lost in the dead time of the instrument. Access to early time points (approximately 100 micros) through use of an ultra-rapid mixing device has identified a spectroscopically novel intermediate, assigned as the Michaelis complex, formed from reaction of fully reduced enzyme with nitrite. Spectroscopic observation of the subsequent transformation of this species has provided data that demand reappraisal of the general belief that the two subunits of the enzyme function independently.

Structure and spectroscopic investigations of a bi-dentate N‧-[(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide and its Co(II), Ni(II), Cu(II) and Cd(II) complexes: Insights relevant to biological properties

NASA Astrophysics Data System (ADS)

Gopal Reddy, N. B.; Krishna, P. Murali; Shantha Kumar, S. S.; Patil, Yogesh P.; Nethaji, Munirathinam

2017-06-01

The present paper describes the synthesis of novel ligand, N‧-[(4-ethylphenyl)methylidene]-4-hydroxy benzohydrazide (HL) and its Co(II), Ni(II), Cu(II) and Cd(II) complexes. The ligand (HL) crystallizes in orthorhombic lattice in P212121 space group with a = 7.9941 (7) Å, b = 11.6154 (10) Å, c = 15.2278 (13) Å, α = β = γ = 90°. Spectroscopic data gives the strong evidence that ligand is coordinated through azomethine nitrogen and enolic oxygen with metal ion. The DNA binding studies revealed that the complexes bind to CT-DNA via intercalation/electrostatic interaction. All the targeted compounds showed more pronounced DNA cleavage activity in the presence of H2O2 and also inhibit the growth of in vitro antibacterial activity against Gram-positive and Gram-negative bacteria.

Study of the interaction of deoxynivalenol with human serum albumin by spectroscopic technique and molecular modelling.

PubMed

Li, Yuqin; Wang, Hao; Jia, Baoxiu; Liu, Caihong; Liu, Ke; Qi, Yongxiu; Hu, Zhide

2013-01-01

The mechanism of interaction between deoxynivalenol (DON) and human serum albumin (HSA) was studied using spectroscopic methods including fluorescence spectra, UV-VIS, Fourier transform infrared (FT-IR) and circular dichroism (CD). The quenching mechanism was investigated in terms of the association constants, number of binding sites and basic thermodynamic parameters. The distance between the HSA donor and the acceptor DON was 2.80 nm as derived from fluorescence resonance energy transfer. The secondary structure compositions of free HSA and its DON complexes were estimated by the FT-IR spectra. Alteration of the secondary protein structure in the presence of DON was confirmed by UV-VIS and CD spectroscopy. Molecular modelling revealed that a DON-protein complex was stabilised by hydrophobic forces and hydrogen bonding. It was potentially useful for elucidating the toxigenicity of DON when combined with biomolecular function effect, transmembrane transport, toxicological testing and the other experiments.

(d ,n ) proton-transfer reactions on 9Be, 11B, 13C, N,1514, and 19F and spectroscopic factors at Ed=16 MeV

NASA Astrophysics Data System (ADS)

Febbraro, M.; Becchetti, F. D.; Torres-Isea, R. O.; Riggins, J.; Lawrence, C. C.; Kolata, J. J.; Howard, A. M.

2017-08-01

The (d ,n ) reaction has been studied with targets of 9Be, 11B, 13C, N,1514, and 19F at Ed=16 MeV using a deuterated liquid-scintillator array. Advanced spectral unfolding techniques with accurately measured scintillator response functions were employed to extract neutron energy spectra without the need for long-path neutron time-of-flight. An analysis of the proton-transfer data at forward angles to the ground states of the final nuclei, using finite-range distorted-wave Born approximation analysis with common bound-state, global, and local optical-model parameter sets, yields a set of self-consistent spectroscopic factors. These are compared with the results of several previous time-of-flight measurements, most done many years ago for individual nuclei at lower energy and often analyzed using zero-range transfer codes. In contrast to some of the earlier published data, our data generally compare well with simple shell-model predictions, with little evidence for uniform quenching (reduction from shell-model values) that has previously been reported from analysis of nucleon knock-out reactions. Data for low-lying excited states in 14N from 13C(d ,n ) also is analyzed and spectroscopic information relevant to nuclear astrophysics obtained. A preliminary study of the radioactive ion beam induced reaction 7Be(d ,n ) , E (7Be)=30 MeV was carried out and indicates further improvements are needed for such measurements, which require detection of neutrons with En<2 MeV .

Preparation, characterization, and in vitro anti-inflammatory evaluation of novel water soluble kamebakaurin/hydroxypropyl-β-cyclodextrin inclusion complex

NASA Astrophysics Data System (ADS)

Raza, Aun; Sun, Huifang; Bano, Shumaila; Zhao, Yingying; Xu, Xiuquan; Tang, Jian

2017-02-01

To enhance the aqueous solubility of kamebakaurin (KA), it was complexed with hydroxypropyl-β-cyclodextrin (HP-β-CD). In this study, the interaction KA with HP-β-CD and their inclusion complex behavior were determined by different characterization techniques such as UV-vis, 1H NMR, FT-IR, PXRD and SEM. All the characterization information proved the development of inclusion complex KA/HP-β-CD, and this inclusion complex demonstrated discriminable spectroscopic characteristics and properties from free compound KA. The results demonstrated that the water solubility of KA was remarkably increased in the presence of HP-β-CD. Furthermore, in vitro anti-inflammatory study showed that inclusion complex KA/HP-β-CD maintained the anti-inflammatory effect of KA. These results demonstrate that HP-β-CD will be promisingly employed in the application of water-insoluble anti-inflammatory phytochemicals such as KA.

Effect of osmolytes on the conformation and aggregation of some amyloid peptides: CD spectroscopic data.

PubMed

Inayathullah, Mohammed; Rajadas, Jayakumar

2016-06-01

Protein misfolding and aggregation are responsible for a large number of diseases called protein conformational diseases or disorders that include Alzheimer׳s disease, Huntington׳s diseases, Prion related encephalopathies and type-II diabetes (http://dx.doi.org/10.1038/35041139) (Kopito and Ron, 2000) [1]. A variety of studies have shown that some small organic molecules, known as osmolytes have the ability to stabilize native conformation of proteins and prevent misfolding and aggregation (http://www.la-press.com/article.php?article_id=447) (Zhao et al., 2008) [2]. It has been shown that certain short segment or fragment of respective proteins can also form amyloids, and the segments also promote the aggregation in the full-length protein (http://dx.doi.org/10.2174/0929867023369187) (Gazit, 2002) [3]. This article presents circular dichroism spectroscopic data on conformational analysis and effect of osmolytes on Aβ peptide fragments, different lengths of polyglutamine peptide and the amyloidogenic segment of islet amyloid polypeptide.

Interaction of Lysozyme with Rhodamine B: A combined analysis of spectroscopic & molecular docking.

PubMed

Millan, Sabera; Satish, Lakkoji; Kesh, Sandeep; Chaudhary, Yatendra S; Sahoo, Harekrushna

2016-09-01

The interaction of Rhodamine B (RB) with Lysozyme (Lys) was investigated by different optical spectroscopic techniques such as absorption, fluorescence, and circular-dichroism (CD), along with molecular docking studies. The fluorescence results (including steady-state and time-resolved mode) revealed that the addition of RB effectively causes strong quenching of intrinsic fluorescence in Lysozyme and mostly, by the static quenching mechanism. Different binding and thermodynamic parameters were calculated at different temperatures and the binding constant value was found to be 2963.54Lmol(-1) at 25°C. The average distance (r0) was found to be 3.31nm according to Förster's theory of non-radiative energy transfer between Lysozyme and RB. The conformational change in Lysozyme during interaction with RB was confirmed from absorbance, synchronous fluorescence, and circular dichroism measurements. Finally, molecular docking studies were done to confirm that the dye binds with Lysozyme. Copyright © 2016 Elsevier B.V. All rights reserved.

Spectroscopic and thermodynamic studies on ferulic acid - Alpha-2-macroglobulin interaction

NASA Astrophysics Data System (ADS)

Rehman, Ahmed Abdur; Sarwar, Tarique; Arif, Hussain; Ali, Syed Saqib; Ahsan, Haseeb; Tabish, Mohammad; Khan, Fahim Halim

2017-09-01

Ferulic acid is a major phenolic acid found in numerous plant species in conjugated form. It binds to enzymes and oligomeric proteins and modifies their structure and function. This study was designed to examine the interaction of ferulic acid, an active ingredient of some important medicines, with α2M, a key serum proteinase, under physiological conditions. The mechanism of interaction was studied by spectroscopic techniques such as, UV-visible absorption, fluorescence spectroscopy, circular dichroism along with isothermal titration calorimetry. Fluorescence quenching of α2M by ferulic acid demonstrated the formation of α2M-ferulic acid complex by static quenching mechanism. Binding parameters calculated by Stern-Volmer method showed that ferulic acid binds to α2M with moderate affinity of the order of ∼104 M-1. The thermodynamic signatures reveal that binding was enthalpy driven and hydrogen bonding played a major role in ferulic acid-α2M binding. CD spectra analysis suggests very little conformational changes in α2M on ferulic acid binding.

Binding of mitomycin C to blood proteins: A spectroscopic analysis and molecular docking

NASA Astrophysics Data System (ADS)

Jang, Jongchol; Liu, Hui; Chen, Wei; Zou, Guolin

2009-06-01

Mitomycin C (MMC) was the first recognized bioreductive alkylating agent, and has been widely used clinically for antitumor therapy. The binding of MMC to two human blood proteins, human serum albumin (HSA) and human hemoglobin (HHb), have been investigated by fluorescence quenching, synchronous fluorescence, circular dichroism (CD) spectroscopy and molecular docking methods. The fluorescence data showed that binding of MMC to proteins caused strong fluorescence quenching of proteins through a static quenching way, and each protein had only one binding site for the drug. The binding constants of MMC to HSA and HHb at 298 K were 2.71 × 10 4 and 2.56 × 10 4 L mol -1, respectively. Thermodynamic analysis suggested that both hydrophobic interaction and hydrogen bonding played major roles in the binding of MMC to HSA or HHb. The CD spectroscopy indicated that the secondary structures of the two proteins were not changed in the presence of MMC. The study of molecular docking showed that MMC was located in the entrance of site I of HSA, and in the central cavity of HHb.

Dielectric relaxation studies in Se{sub 90}Cd{sub 8}Sb{sub 2} glassy alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Nitesh; Rao, Vandita; Dwivedi, D. K.

2016-05-06

Se{sub 90}Cd{sub 8}Sb{sub 2} chalcogenide semiconducting alloy was prepared by melt quench technique. The prepared glassy alloy has been characterized by techniques such as scanning electron microscopy (SEM) and energy dispersive X-ray (EDAX).Dielectric properties of Se{sub 90}Cd{sub 8}Sb{sub 2} chalcogenide semiconductor have been studied using impedance spectroscopic technique in the frequency range 5×10{sup 2}Hz - 1×10{sup 5}Hz and in temperature range 303-318K. It is found that dielectric constant ε′ and dielectric loss factor ε″ are dependent on frequency and temperature.

Interaction of Flavonoids from Woodwardia unigemmata with Bovine Serum Albumin (BSA): Application of Spectroscopic Techniques and Molecular Modeling Methods.

PubMed

Ma, Rui; Pan, Hong; Shen, Tao; Li, Peng; Chen, Yanan; Li, Zhenyu; Di, Xiaxia; Wang, Shuqi

2017-08-09

Phytochemical investigation on the methanol extract of Woodwardia unigemmata resulted in the isolation of seven flavonoids, including one new flavonol acylglycoside ( 1 ). The structures of these compounds were elucidated on the basis of extensive spectroscopic analysis and comparison of literature data. The multidrug resistance (MDR) reversing activity was evaluated for the isolated compounds using doxorubicin-resistant K562/A02 cells model. Compound 6 showed comparable MDR reversing effect to verapamil. Furthermore, the interaction between compounds and bovine serum albumin (BSA) was investigated by spectroscopic methods, including steady-state fluorescence, synchronous fluorescence, circular dichroism (CD) spectroscopies, and molecular docking approach. The experimental results indicated that the seven flavonoids bind to BSA by static quenching mechanisms. The negative ΔH and ΔS values indicated that van der Waals interactions and hydrogen bonds contributed in the binding of compounds 2 - 6 to BSA. In the case of compounds 1 and 7 systems, the hydrophobic interactions play a major role. The binding of compounds to BSA causes slight changes in the secondary structure of BSA. There are two binding sites of compound 6 on BSA and site I is the main site according to the molecular docking studies and the site marker competitive binding assay.

Identification of new diterpene esters from green Arabica coffee beans, and their platelet aggregation accelerating activities.

PubMed

Wang, Xia; Meng, QianQian; Peng, XingRong; Hu, GuiLin; Qiu, MingHua

2018-10-15

Eight new ent-kaurane diterpene fatty acid esters, namely caffarolides A-H (1-8), were isolated from green beans of Coffea arabica. Their chemical structures were confirmed by extensive spectroscopic analysis including 1D, 2D NMR (HSQC, HMBC, 1 H- 1 H COSY, and ROESY), HRMS, IR and CD spectra and by GC-FID analysis. Interestingly, the diterpene moiety of these new compounds first occurred in genus Coffea. All the isolates were evaluated for platelet aggregation activity in vitro. As the results, caffarolides C, D and F (3, 4 and 6) showed induction effect for platelet aggregation and the possible structure-activity relationships have been discussed briefly. Copyright © 2018 Elsevier Ltd. All rights reserved.

Physical Chemistry of Sol-Gel Materials Symposium Held during the 213th National Meeting of the American Chemical Society Held in Anaheim, California on March 21-25, 1999

DTIC Science & Technology

2000-05-01

conditions allow us to correlate framework structure and synthesis conditions with hydrothermal stability. Temperature-induced changes in surfactant packing...31 228. SPECTROSCOPIC CHARACTERIZATION OF CdS NANOPARTICLES WITH DIFFERENT CAPPING ENVIONMENTS . Bingsuo ZOU, Reginald Little, Jianping Wang and...Mostafa A. El- Sayed, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332 CdS nanoparticles in AOT reverse micelle

Inclusion of Paracetamol into β-cyclodextrin nanocavities in solution and in the solid state

NASA Astrophysics Data System (ADS)

El-Kemary, Maged; Sobhy, Saffaa; El-Daly, Samy; Abdel-Shafi, Ayman

2011-09-01

We report on steady-state UV-visible absorption and emission characteristics of Paracetamol, drug used as antipyretic agent, in water and within cyclodextrins (CDs): β-CD, 2-hydroxypropyl- β-CD (HP- β-CD) and 2,6-dimethyl- β-CD (Me- β-CD). The results reveal that Paracetamol forms a 1:1 inclusion complex with CD. Upon encapsulation, the emission intensity enhances, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the Me- β-CD shows the largest effect for the drug. The observed binding constant showing the following trend: Me- β-CD > HP- β-CD > β-CD. The less complexing effectiveness of HP- β-CD is due to the steric effect of the hydroxypropyl-substituents, which can hamper the inclusion of the guest molecules. The solid state inclusion complex was prepared by co-precipitation method and its characterization was investigated by Fourier transform infrared spectroscopy, 1H NMR and X-ray diffractometry. These approaches indicated that Paracetamol was able to form an inclusion complex with CDs, and the inclusion compounds exhibited different spectroscopic features and properties from Paracetamol.

Substrate driven photochemistry of CdSe quantum dot films: charge injection and irreversible transformations on oxide surfaces.

PubMed

Tvrdy, Kevin; Kamat, Prashant V

2009-04-23

The photochemical behavior of CdSe quantum dots anchored to different surfaces was probed through their deposition on glass, SiO2, and TiO2 films. Following visible light irradiation under ambient conditions, CdSe quantum dots deposited on semiconducting TiO2 surface degraded, where no such degradation was observed when deposited on inert SiO2 surface or glass. Fluorescence decay and transient absorption experiments confirmed that charge injection from excited CdSe into TiO2 occurs with an apparent rate constant of 5.62 x 10(8) s(-1) and is the primary event responsible for photodegradation. In the presence of air, injected electrons are scavenged by surface adsorbed oxygen leaving behind reactive holes which induce anodic corrosion of CdSe quantum dots. In a vacuum environment, minimal CdSe degradation was observed as electron scavenging by oxygen is replaced with charge recombination between injected electrons and holes in CdSe nanocrystals. Spectroscopic measurements presented in this study highlight the role of both substrate and medium in dictating the photochemistry of CdSe quantum dots.

Enhanced Circular Dichroism via Symmetry Breaking in a Chiral Plasmonic Nanoparticle Oligomer

NASA Astrophysics Data System (ADS)

Le, Khai Q.

2018-02-01

A chiral plasmonic nanoparticle oligomer, consisting of four symmetrically arranged nanodisks of different heights and having different optical absorption responses to left and right-handed circularly polarized light illumination, has been experimentally reported in the literature. The resulting circular dichroism (CD) signal was detectable with state of the art CD spectrometers but was much weaker than those of existing chiral nanostructures, i.e., three-dimensional (3-D) chiral metamaterials. In this letter, via symmetry breaking in such an oligomer, the author demonstrates that the CD can be enhanced up to six times compared to that of a symmetric oligomer, and is in the range of a relevant 3-D chiral metamolecule. Through investigation of geometrical parameters including particle size, asymmetric and symmetric gaps, the CD evolution was reported, which provides a useful guideline for design of two-dimensional chiral oligomers adopted as efficient probes for CD spectroscopic applications.

New sesquiterpenoids from the edible mushroom Pleurotus cystidiosus and their inhibitory activity against α-glucosidase and PTP1B.

PubMed

Tao, Qiao-Qiao; Ma, Ke; Bao, Li; Wang, Kai; Han, Jun-Jie; Zhang, Jin-Xia; Huang, Chen-Yang; Liu, Hong-Wei

2016-06-01

Nine new sesquiterpenoids, clitocybulol derivatives, clitocybulols G-O (1-9) and three known sesquiterpenoids, clitocybulols C-E (10-12), were isolated from the solid culture of the edible fungus Pleurotus cystidiosus. The structures of compounds 1-12 were determined by spectroscopic methods. The absolute configurations of compounds 1-9 were assigned via the circular dichroism (CD) data analysis. Compounds 1, 6 and 10 showed moderate inhibitory activity against protein tyrosine phosphatase-1B (PTP1B) with IC50 values of 49.5, 38.1 and 36.0μM, respectively. Copyright © 2016. Published by Elsevier B.V.

Cyclodepsipeptides and other O-containing heterocyclic metabolites from Beauveria felina EN-135, a marine-derived entomopathogenic fungus.

PubMed

Du, Feng-Yu; Li, Xiao-Ming; Zhang, Peng; Li, Chun-Shun; Wang, Bin-Gui

2014-05-13

Bioassay-guided fractionation of a culture extract of Beauveria felina EN-135, an entomopathogenic fungus isolated from a marine bryozoan, led to the isolation of a new cyclodepsipeptide, iso-isariin D (1); two new O-containing heterocyclic compounds that we have named felinones A and B (2 and 3); and four known cyclodepsipeptides (4-7). The structures were elucidated via spectroscopic analysis, and the absolute configurations of 1 and 2 were determined using single-crystal X-ray diffraction and CD, respectively. All isolated compounds were evaluated for antimicrobial activity and brine-shrimp (Artemia salina) lethality.

Structural, crystal structure, Hirshfeld surface analysis and physicochemical studies of a new chlorocadmate template by 1-(2-hydroxyethyl)piperazine

NASA Astrophysics Data System (ADS)

Soudani, S.; Jeanneau, E.; Jelsch, C.; Lefebvre, F.; Ben Nasr, C.

2016-11-01

The synthesis, crystal structure and spectroscopic characterization of a new chlorocadmate template by the 1-(2-hydroxyethyl)piperazine ligand are reported. In the atomic arrangement, the CdCl5O entities are deployed in corrugated rows along the a-axis at y = 1/4 and y = 3/4 to form layers parallel to the (a,b) plane. In these crystals, piperazinediium cations are in a chair conformation and are inserted between these layers through Nsbnd H⋯Cl, Csbnd H⋯Cl, Osbnd H⋯Cl and Nsbnd H⋯O hydrogen bonds to form infinite three-dimensional network. Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that H⋯Cl and Csbnd H⋯Hsbnd C intermolecular interactions are the most abundant contacts of the organic cation in the crystal packing. The crystal contacts enrichments reveals that, the Cd++ … Cl- salt bridges, the Cd⋯O complexation and Osbnd H⋯Cl- and Nsbnd H⋯Cl-strong H-bonds are the driving forces in the packing formation. The presence of twelve independent chloride anions and four organic cation in the asymmetric unit allowed comparing their contact propensities. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. Additional characterization of this compound has also been performed by IR spectroscopy.

Laser-induced breakdown spectroscopic detection of trace level heavy metal in solutions on a laser-pretreated metallic target.

PubMed

Niu, Sheng; Zheng, Lijuan; Khan, Abdul Qayyum; Feng, Guang; Zeng, Heping

2018-03-01

A fast and sensitive analysis for trace level heavy metals in aqueous solution was realized by using an improved laser induced breakdown spectroscopy (LIBS) methodology. Solutions containing heavy metal elements, Ni, Cr, and Cd, were concentrated in a laser-pretreated area (25 × 20mm 2 ) of a polished aluminum target surface, wherein pretreated grooves enabled homogeneous distribution of the metallic solutions in the well-defined area, and laser ablation of the aluminum target produced unique plasma excitation of various metallic ions. For 1-mL solutions deposited, we obtained an analytical precision of about 7% relative standard deviation (RSD), and limits of detection (LODs) of 22, 19, and 184μg/L for Ni, Cr, and Cd, respectively. Moreover, the laser-pretreated metallic microstructure allowed more solution deposited with the help of a hot plate, which supported improvement of LODs to sub-μg/L level for Cr and Ni and μg/L level for Cd with about 20-mL solution engaged in the enrichment processes. The applicability of the proposed methodology was validated on certified reference materials and real river water. Copyright © 2017 Elsevier B.V. All rights reserved.

Concentration effect of Er{sup 3+} ions on structural and spectroscopic properties of CdNb{sub 2}O{sub 6} phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghafouri, Sanaz Aian; Erdem, Murat, E-mail: merdem@marmara.edu.tr; Ekmekçi, M. Kaan

2014-12-15

Excitation and emission spectra of a visible room-temperature Er{sup 3+} ions luminescence from powders. - Highlights: • This is the first report on spectroscopic properties of CdNb{sub 2}O{sub 6}:Er{sup 3+}. • The crystalline sizes are affected as the concentration of Er{sup 3+} ions increased. • Quenching of the luminescence was observed to be above 1.0 mol% Er{sup 3+}. - Abstract: This study is focused on the synthesis and characterization of CdNb{sub 2}O{sub 6} compounds doped with of Er{sup 3+} ions. Powders were synthesized by using the molten salt method and annealed at 900 °C for 4 h. The synthesized particlesmore » were structurally characterized by using X-ray diffraction, scanning electron microscopy. A single phase of the CdNb{sub 2}O{sub 6} was determined and the size of the particles was found to be affected by the presence and the concentration of Er{sup 3+} ions. Luminescence properties of each sample were investigated by measuring accurately the emission and excitation spectra at room temperature in the wavelength range of 200–1700 nm by exciting the Er{sup 3+} ions at 379 nm and 805 nm. Quenching of the luminescence in both visible and near infrared spectral regions was observed to be above 1.0 mol% Er{sup 3+} concentration.« less

Exploring inclusion complexes of ionic liquids with α- and β- cyclodextrin by NMR, IR, mass, density, viscosity, surface tension and conductance study

NASA Astrophysics Data System (ADS)

Barman, Biraj Kumar; Rajbanshi, Biplab; Yasmin, Ananya; Roy, Mahendra Nath

2018-05-01

The formation of the host-guest inclusion complexes of ionic liquids namely [BMIm]Cl and [HMIm]Cl with α-CD and β-CD were studied by means of physicochemical and spectroscopic methods. Conductivity and surface tension study were in good agreement with the 1H NMR and FT-IR studies which confirm the formation of the inclusion complexes. The Density and viscosity study also supported the formation of the ICs. Further the stoichiometry was determined 1:1 for each case and the association constants and thermodynamic parameters derived supported the most feasible formation of the [BMIm]Cl- β-CD inclusion complex.

Interaction study of some macrocyclic inorganic schiff base complexes with calf thymus DNA using spectroscopic and voltammetric methods

NASA Astrophysics Data System (ADS)

Bordbar, Maryam; Tavoosi, Fariba; Yeganeh-Faal, Ali; Zebarjadian, Mohammad Hasan

2018-01-01

The interaction of Cd(II), Zn(II) and Mn(II)-L (4,8-bis(2-pyridylmethyl)-4,8-diazaundecane-1,11-diamine) transition metal complexes with calf thymus DNA (CT-DNA) has been investigated using electronic, fluorescence and circular dichroism (CD) spectroscopy, thermal denaturation and cyclic voltammetry (CV). Based on the UV-Vis study, binding constants of the complexes with CT-DNA were calculated. Changes in the band of the CD spectrum, DNA melting temperature and in the ipa and ipc of the complexes in the presenceCT-DNA, overall, showed that the studied complex exhibited good DNA interaction ability with partial intercalation mode.

Optical spectroscopy of cobalt-doped cadmium telluride

NASA Astrophysics Data System (ADS)

Turner, Eric J.; Evans, Jonathan; Harris, Thomas

2018-02-01

Spectroscopic investigation of Co2+:CdTe was performed to evaluate it's potential as a lasing medium. The sample had a targeted doping concentration of 2% and measurements were performed from 10 - 120K. Cross-sections for Co:CdTe were calculated using Füchtbauer-Ladenburg and reciprocity methods. Calculations suggest the potential for efficient lasing at 3.7μm when pumped by a 3μm laser source on the 4A2 <-> 4T2 transition. The fluorescence lifetime was measured to quantify the temperature dependence of the non-radiative relaxation rate. This work aims to characterize Co:CdTe as a novel gain medium for compact, tunable mid-infrared lasers operating within the atmospheric transmission window.

Aryl-Aryl Interactions in Designed Peptide Folds: Spectroscopic Characteristics and Placement Issues for Optimal Structure Stabilization

PubMed Central

Anderson, Jordan M.; Kier, Brandon; Jurban, Brice; Byrne, Aimee; Shu, Irene; Eidenschink, Lisa A.; Shcherbakov, Alexander A.; Hudson, Mike; Fesinmeyer, R. M.; Andersen, Niels H.

2017-01-01

We have extended our studies of Trp/Trp to other Aryl/Aryl through-space interactions that stabilize hairpins and other small polypeptide folds. Herein we detail the NMR and CD spectroscopic features of these types of interactions. NMR data remains the best diagnostic for characterizing the common T-shape orientation. Designated as an edge-to-face (EtF or FtE) interaction, large ring current shifts are produced at the edge aryl ring hydrogens and, in most cases, large exciton couplets appear in the far UV circular dichroic (CD) spectrum. The preference for the face aryl in FtE clusters is W≫Y≥F (there are some exceptions in the Y/F order); this sequence corresponds to the order of fold stability enhancement and always predicts the amplitude of the lower energy feature of the exciton couplet in the CD spectrum. The CD spectra for FtE W/W, W/Y, Y/W, and Y/Y pairs all include an intense feature at 225–232 nm. An additional couplet feature seen for W/Y, W/F, Y/Y and F/Y clusters, is a negative feature at 197–200 nm. Tyr/Tyr (as well as F/Y and F/F) interactions produce much smaller exciton couplet amplitudes. The Trp-cage fold was employed to search for the CD effects of other Trp/Trp and Trp/Tyr cluster geometries: several were identified. In this account, we provide additional examples of the application of cross-strand aryl/aryl clusters for the design of stable β-sheet models and a scale of fold stability increments associated with all possible FtE Ar/Ar clusters in several structural contexts. PMID:26850220

Spectroscopic studies on the interaction of sodium benzoate, a food preservative, with calf thymus DNA.

PubMed

Zhang, Guowen; Ma, Yadi

2013-11-01

The interaction between sodium benzoate (SB) and calf thymus DNA in simulated physiological buffer (pH 7.4) using acridine orange (AO) dye as a fluorescence probe, was investigated by UV-Vis absorption, fluorescence and circular dichroism (CD) spectroscopy along with DNA melting studies and viscosity measurements. An expanded UV-Vis spectral data matrix was resolved by multivariate curve resolution-alternating least squares (MCR-ALS) approach. The equilibrium concentration profiles and the pure spectra for SB, DNA and DNA-SB complex from the high overlapping composite response were simultaneously obtained. The results indicated that SB could bind to DNA, and hydrophobic interactions and hydrogen bonds played a vital role in the binding process. Moreover, SB was able to quench the fluorescence of DNA-AO complex through a static procedure. The quenching observed was indicative of an intercalative mode of interaction between SB and DNA, which was supported by melting studies, viscosity measurements and CD analysis. Copyright © 2013 Elsevier Ltd. All rights reserved.

Optical critical dimension metrology for directed self-assembly assisted contact hole shrink

NASA Astrophysics Data System (ADS)

Dixit, Dhairya; Green, Avery; Hosler, Erik R.; Kamineni, Vimal; Preil, Moshe E.; Keller, Nick; Race, Joseph; Chun, Jun Sung; O'Sullivan, Michael; Khare, Prasanna; Montgomery, Warren; Diebold, Alain C.

2016-01-01

Directed self-assembly (DSA) is a potential patterning solution for future generations of integrated circuits. Its main advantages are high pattern resolution (˜10 nm), high throughput, no requirement of high-resolution mask, and compatibility with standard fab-equipment and processes. The application of Mueller matrix (MM) spectroscopic ellipsometry-based scatterometry to optically characterize DSA patterned contact hole structures fabricated with phase-separated polystyrene-b-polymethylmethacrylate (PS-b-PMMA) is described. A regression-based approach is used to calculate the guide critical dimension (CD), DSA CD, height of the PS column, thicknesses of underlying layers, and contact edge roughness of the post PMMA etch DSA contact hole sample. Scanning electron microscopy and imaging analysis is conducted as a comparative metric for scatterometry. In addition, optical model-based simulations are used to investigate MM elements' sensitivity to various DSA-based contact hole structures, predict sensitivity to dimensional changes, and its limits to characterize DSA-induced defects, such as hole placement inaccuracy, missing vias, and profile inaccuracy of the PMMA cylinder.

Reducing beam hardening effects and metal artefacts in spectral CT using Medipix3RX

NASA Astrophysics Data System (ADS)

Rajendran, K.; Walsh, M. F.; de Ruiter, N. J. A.; Chernoglazov, A. I.; Panta, R. K.; Butler, A. P. H.; Butler, P. H.; Bell, S. T.; Anderson, N. G.; Woodfield, T. B. F.; Tredinnick, S. J.; Healy, J. L.; Bateman, C. J.; Aamir, R.; Doesburg, R. M. N.; Renaud, P. F.; Gieseg, S. P.; Smithies, D. J.; Mohr, J. L.; Mandalika, V. B. H.; Opie, A. M. T.; Cook, N. J.; Ronaldson, J. P.; Nik, S. J.; Atharifard, A.; Clyne, M.; Bones, P. J.; Bartneck, C.; Grasset, R.; Schleich, N.; Billinghurst, M.

2014-03-01

This paper discusses methods for reducing beam hardening effects and metal artefacts using spectral x-ray information in biomaterial samples. A small-animal spectral scanner was operated in the 15 to 80 keV x-ray energy range for this study. We use the photon-processing features of a CdTe-Medipix3RX ASIC in charge summing mode to reduce beam hardening and associated artefacts. We present spectral data collected for metal alloy samples, its analysis using algebraic 3D reconstruction software and volume visualisation using a custom volume rendering software. The cupping effect and streak artefacts are quantified in the spectral datasets. The results show reduction in beam hardening effects and metal artefacts in the narrow high energy range acquired using the spectroscopic detector. A post-reconstruction comparison between CdTe-Medipix3RX and Si-Medipix3.1 is discussed. The raw data and processed data are made available (http://hdl.handle.net/10092/8851) for testing with other software routines.

Studies on the binding behavior of prodigiosin with bovine hemoglobin by multi-spectroscopic techniques

NASA Astrophysics Data System (ADS)

Tang, Jing; Yang, Chao; Zhou, Lin; Ma, Fei; Liu, Shuchao; Wei, Shaohua; Zhou, Jiahong; Zhou, Yanhuai

2012-10-01

In this article, the interaction mechanism of prodigiosin (PG) with bovine hemoglobin (BHb) is studied in detail using various spectroscopic technologies. UV-vis absorption and fluorescence spectra demonstrate the interaction process. The Stern-Volmer plot and the time-resolved fluorescence study suggest the quenching mechanism of fluorescence of BHb by PG is a static quenching procedure, and the hydrophobic interactions play a major role in binding of PG to BHb. Furthermore, synchronous fluorescence studies, Fourier transform infrared (FTIR) and circular dichroism (CD) spectra reveal that the conformation of BHb is changed after conjugation with PG.

Optical and AFM study of electrostatically assembled films of CdS and ZnS colloid nanoparticles

NASA Astrophysics Data System (ADS)

Suryajaya; Nabok, A.; Davis, F.; Hassan, A.; Higson, S. P. J.; Evans-Freeman, J.

2008-05-01

CdS and ZnS semiconducting colloid nanoparticles coated with the organic shell, containing either SO 3- or NH 2+ groups, were prepared using the aqueous phase synthesis. The multilayer films of CdS (or ZnS) were deposited onto glass, quartz and silicon substrates using the technique of electrostatic self-assembly. The films produced were characterized with UV-vis spectroscopy, spectroscopic ellipsometry and atomic force microscopy. A substantial blue shift of the main absorption band with respect to the bulk materials was found for both CdS and ZnS films. The Efros equation in the effective mass approximation (EMA) theoretical model allowed the evaluation of the nanoparticle radius of 1.8 nm, which corresponds well to the ellipsometry results. AFM shows the formation of larger aggregates of nanoparticles on solid surfaces.

Synthetic endeavors on cadmium species bearing glycolate and aromatic chelators with structure-specific biotoxic correlations in vitro.

PubMed

Iordanidou, C; Tsave, O; Gabriel, C; Hatzidimitriou, A; Yavropoulou, M P; Mateescu, C; Salifoglou, A

2017-11-01

Cadmium is a well-known metallotoxin widespread in the environment and easily reaching cellular targets in lower and higher organisms, including humans. The form(s) of that metal ion through which it interacts with biomolecular targets in a cellular milieu are critical in cell survival. Poised to investigate the structure-specific activity of Cd(II) in a cellular environment and delve into the associated biotoxic processes, binary and ternary systems of that metal ion in the presence of the physiological α-hydroxycarboxylic acid glycolic acid and aromatic (N,N')-binders 2,2'-bipyridine (2,2'-bipy) and 4,4'-bipyridine (4,4'-bipy) were examined synthetically in aqueous media and a pH-specific fashion. The arising new materials [Cd(C 2 H 3 O 3 ) 2 ] n (1), [Cd(C 2 H 3 O 3 )(C 10 H 8 N 2 )(NO 3 )] n ·nH 2 O (2), and {[Cd(C 2 H 3 O 3 )(C 10 H 8 N 2 )(H 2 O)](NO 3 )} n ·2nH 2 O (3) project coordination polymers, which were physicochemically characterized through elemental analysis, FT-IR, NMR, luminescence and X-ray crystallography. The distinct spectroscopic features of 1-3, with luminescence exemplifying distinct behavior (2,3), further corroborated by crystallographic analysis, lend credence to a structure-specific selection of species employed in ensuing in vitro biological studies. The emerging results in two different cell lines (3T3-L1, Saos-2) reveal a concentration-dependent, structure-specific and cell line-specific toxicity profile of Cd(II), reflecting its coordination composition and formulation, rendering it soluble and bioavailable (1,2). Mechanistic information riding on caspase-dependent investigation unravels that metal ion's specific behavior compromising cell survival and integrity. Employment of ethylenediamine tetraacetic acid (EDTA) a) shows efficient sequestration of Cd(II) away from its toxic reactivity denoting the strength of interactions involved, and b) lends credence to further development of appropriately configured organic binders, selectively providing molecular protection from Cd(II) toxicity. Copyright © 2017 Elsevier Inc. All rights reserved.

Binding modes of environmental endocrine disruptors to human serum albumin: insights from STD-NMR, ITC, spectroscopic and molecular docking studies.

PubMed

Yang, Hongqin; Huang, Yanmei; Liu, Jiuyang; Tang, Peixiao; Sun, Qiaomei; Xiong, Xinnuo; Tang, Bin; He, Jiawei; Li, Hui

2017-09-11

Given that bisphenols have an endocrine-disrupting effect on human bodies, thoroughly exposing their potential effects at the molecular level is important. Saturation transfer difference (STD) NMR-based binding studies were performed to investigate the binding potential of two bisphenol representatives, namely, bisphenol B (BPB) and bisphenol E (BPE), toward human serum albumin (HSA). The relative STD (%) suggested that BPB and BPE show similar binding modes and orientations, in which the phenolic rings were spatially close to HSA binding site. ITC analysis results showed that BPB and BPE were bound to HSA with moderately strong binding affinity through electrostatic interactions and hydrogen bonds. The order of binding affinity of HSA for two test bisphenols is as follows: BPE > BPB. The results of fluorescence competitive experiments using 5-dimethylaminonaphthalene-1-sulfonamide and dansylsarcosine as competitors, combined with molecular docking indicated that both bisphenols are prone to attach to the binding site II in HSA. Spectroscopic results (FT-IR, CD, synchronous and 3D fluorescence spectra) showed that BPB/BPE induces different degrees of microenvironmental and conformational changes to HSA.

Molecular modeling and spectroscopic studies on the interaction of the chiral drug venlafaxine hydrochloride with bovine serum albumin

NASA Astrophysics Data System (ADS)

Shahabadi, Nahid; Hadidi, Saba

2014-03-01

This study was designed to examine the interaction of racemic antidepressant drug "S,R-venlafaxine hydrochloride (VEN)" with bovine serum albumin (BSA) under physiological conditions. The mechanism of interaction was studied by spectroscopic techniques combination with molecular modeling. Stern-Volmer analysis of fluorescence quenching data shows the presence of the static quenching mechanism. The thermodynamic parameters indicated that the hydrogen bonding and weak van der Waals interactions are the predominant intermolecular forces stabilizing the complex. The number of binding sites (n) was calculated. Through the site marker competitive experiment, VEN was confirmed to be located in subdomain IIIA of BSA. The binding distance (r = 4.93 nm) between the donor BSA and acceptor VEN was obtained according to Förster's non-radiative energy transfer theory. According to UV-vis spectra and CD data binding of VEN leaded to conformational changes of BSA. Molecular docking simulations of S and R-VEN revealed that both isomers have similar interaction and the same binding sites, from this point of view S and R isomers are equal.

4-Cyano-α-methyl-l-phenylalanine as a spectroscopic marker for the investigation of peptaibiotic-membrane interactions.

PubMed

De Zotti, Marta; Bobone, Sara; Bortolotti, Annalisa; Longo, Edoardo; Biondi, Barbara; Peggion, Cristina; Formaggio, Fernando; Toniolo, Claudio; Dalla Bona, Andrea; Kaptein, Bernard; Stella, Lorenzo

2015-04-01

Two analogs of the ten-amino acid residue, membrane-active lipopeptaibiotic trichogin GA IV, mono-labeled with 4-cyano-α-methyl-L-phenylalanine, a potentially useful fluorescence and IR absorption probe of the local microenvironment, were synthesized by the solid-phase methodology and conformationally characterized. The single modification was incorporated either at the N-terminus (position 1) or near the C-terminus (position 8) of the peptide main chain. In both cases, the replaced amino acid was the equally helicogenic α-aminoisobutyric acid (Aib) residue. We performed a solution conformational analysis by use of FT-IR absorption, CD, and 2D-NMR spectroscopies. The results indicate that both labeled analogs essentially maintain the overall helical propensity of the naturally occurring lipopeptaibiotic. Peptide-membrane interactions were assessed by fluorescence and ATR-IR absorption techniques. Analogies and differences between the two peptides were highlighted. Taken together, our data confirm literature results that some of the spectroscopic parameters of the 4-cyanobenzyl chromophore are sensitive markers of the local microenvironment. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

Structural, optical and dielectric investigation of CdFe2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Sagadevan, Suresh; Pal, Kaushik; Zaman Chowdhury, Zaira; Enamul Hoque, Md

2017-07-01

A simple thermal decomposition technique has been executed for the synthesis of cadmium ferrite (CdFe2O4) nanoparticles. With the help of x-ray diffraction; scanning electron microscopy, energy-dispersive x-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy the prepared nanoparticles were identified. The crystal size of the average particles aggregated and was found approximately to be 10-14 nm by means of XRD studies. However, the results of high-resolution transmission electron microscopy (HR-TEM) investigation ensured distinguished nanoparticles, and also the polycrystalline nature of those nanoparticles was confirmed by selected area diffraction (SAED) patterns. The scanning electron microscopy (SEM) images explored a random distribution of grains within the sample. Thin film surface topology of roughness and surface current measurement were studied by atomic force microscopy (TP-AFM, C-AFM). Hence, from the ultraviolet-visible (UV) spectroscopic absorption illustrated significant optical properties. Moreover, the optical energy band gap (E g) of CdFe2O4 nanoparticle was determined to be 1.74 eV. By studying the variation of dielectric constant and dielectric loss with respect to frequency, the CdFe2O4 nanoparticles electrical properties were analyzed. Analysis in the real and imaginary part of impedance explained their frequency and temperature dependence of the CdFe2O4 nanoparticles. The traditional solution-phase organometallic approach provides an effective way to synthesize high quality hydrophobic semiconductor-CdFe2O4 nanoparticles. Our simple, cost-effective approach is quite general, which is applicable to other nanomaterials, and it utilizes the currently mature in Nano-chemistry. The nanocomposite assemblies’ exhibit strong anisotropic optical and electrical properties are open up new possibilities in remarkable applications for optoelectronics in the near future.

Fluorescent reversible regulation based on the interactions of topotecan hydrochloride, neutral red and quantum dots

NASA Astrophysics Data System (ADS)

Wang, Linlin; Shen, Yizhong; Liu, Shaopu; Yang, Jidong; Liang, Wanjun; Li, Dan; He, Youqiu

2015-02-01

The interactions of topotecan hydrochloride (THC), neutral red (NR) and thioglycolic acid (TGA) capped CdTe/CdS quantum dots (QDs) built a solid base for the controlling of the fluorescent reversible regulation of the system. This study was developed by means of ultraviolet-visible (UV-vis) absorption, fluorescence (FL), resonance Rayleigh scattering (RRS) spectroscopy and transmission electron microscopy (TEM). Corresponding experimental results revealed that the fluorescence of TGA-CdTe/CdS QDs could be effectively quenched by NR, while the RRS of the QDs enhanced gradually with the each increment of NR concentration. After the addition of THC, the strong covalent conjugation between NR and THC which was in carboxylate state enabled NR to be dissociated from the surface of TGA-CdTe/CdS QDs to form more stable complex with THC, thereby enhancing the fluorescence of the TGA-CdTe/CdS QDs-NR system. What is more, through analyzing the optical properties and experimental data of the reaction between TGA-CdTe/CdS QDs and NR, the possible reaction mechanism of the whole system was discussed. This combination of multiple spectroscopic techniques could contribute to the investigation for the fluorescent reversible regulation of QDs and a method could also be established to research the interactions between camptothecin drugs and dyes.

Dye sensitized solar cell applications of CdTiO{sub 3}–TiO{sub 2} composite thin films deposited from single molecular complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy

2015-10-15

A heterobimetallic complex [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO{sub 3}–TiO{sub 2} composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity,more » phase identification and chemical composition of microspherical architectured CdTiO{sub 3}–TiO{sub 2} composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application. - Graphical abstarct: Microspherical designed CdTiO{sub 3}–TiO{sub 2} composite oxides photoanode film has been fabricated from single source precursor [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF via aerosol assisted chemical vapor deposition technique for dye sensitized solar cell application. - Highlights: • Synthesis and characterization of a heterobimetallic Cd–Ti complex. • Fabrication of CdTiO{sub 3}–TiO{sub 2} thin film photoelectrode. • Application as dye sensitized photoanode for solar application.« less

Lignans from the root of Wikstroemia indica and their cytotoxic activity against PANC-1 human pancreatic cancer cells.

PubMed

Chang, Hang; Wang, Yuwei; Gao, Xue; Song, Zehai; Awale, Suresh; Han, Na; Liu, Zhihui; Yin, Jun

2017-09-01

Six new compounds, wikstronin A (1), wikstronin B (2), wikstresinol (3), acetylwikstresinol (4), bis-5',5'-(+)-matairesinol (5), bis-5,5'-(+)-matairesinol (6), together with 20 known compounds (7-26) were isolated from the CH 2 Cl 2 extract of roots of Wikstroemia indica. Structures of compounds 1-6 were determined by extensive NMR and CD spectroscopic analysis. In vitro preferential cytotoxicity of all the isolates was evaluated against a PANC-1 human pancreatic cell line. Compounds 8 and 12 displayed mild preferential cytotoxicity in the nutrient-deprived medium (NDM) and without causing toxicity in normal nutrient-rich conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Metabolites with Gram-negative bacteria quorum sensing inhibitory activity from the marine animal endogenic fungus Penicillium sp. SCS-KFD08.

PubMed

Kong, Fan Dong; Zhou, Li Man; Ma, Qing Yun; Huang, Sheng Zhuo; Wang, Pei; Dai, Hao Fu; Zhao, You Xing

2017-01-01

Three new compounds named penicitor A, aculene E and penicitor B, as well as four known compounds, were isolated from the fermentation broth of Penicillium sp. SCS-KFD08 associated with a marine animal Sipunculus nudus from the Haikou bay of China. Their planar structures and absolute configurations were unambiguously elucidated by spectroscopic data, Mosher's method, CD spectrum analysis along with quantum ECD calculation. Among them, compounds 2-7 showed quorum sensing inhibitory activity against Chromobacterium violaceum CV026, and could significantly reduce violacein production in N-hexanoyl-l-homoserine lactone (C6-HSL) induced C. violaceum CV026 cultures at sub-inhibitory concentrations.

Activation Thermodynamics and H/D Kinetic Isotope Effect of the Hox to HredH+ Transition in [FeFe] Hydrogenase.

PubMed

Ratzloff, Michael W; Wilker, Molly B; Mulder, David W; Lubner, Carolyn E; Hamby, Hayden; Brown, Katherine A; Dukovic, Gordana; King, Paul W

2017-09-20

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox →H red H + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ∼2.5-fold kinetic isotope effect. Overall, these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox →H red H + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.

Quenching interaction of BSA with DTAB is dynamic in nature: A spectroscopic insight

NASA Astrophysics Data System (ADS)

Das, Nirmal Kumar; Pawar, Lavanya; Kumar, Naveen; Mukherjee, Saptarshi

2015-08-01

The role of electrostatic interactions between the protein, Bovine Serum Albumin (BSA) and the cationic surfactant, dodecyltrimethylammonium bromide (DTAB) has been substantiated using spectroscopic approaches. The primary mechanism of fluorescence quenching of the tryptophan of BSA is most probably dynamic in nature as the complex formation resulting in a protein-surfactant assembly is not very spontaneous. The weak interaction buries the tryptophan amino acid residue inside the protein scaffolds which have been quantitatively proved by our acrylamide quenching studies. The loss in the secondary structure of the protein as a result of interaction with DTAB has been elucidated by CD spectroscopy.

Characteristic effects of substituent and external pressure on group-inclusion complexation with p-sulfonatocalix[8]arene and γ-cyclodextrin

NASA Astrophysics Data System (ADS)

Miyazono, Keitaro; Hanaya, Tadashi; Sueishi, Yoshimi

2014-07-01

By synthesizing unique nitroxide probes (α-substituted phenyl-2,4,6-trimethoxybenzyl(t-butyl)nitroxide), we have shown that p-sulfonatocalix[8]arene (Calix-S8) and γ-cyclodextin (γ-CD) form electron spin resonance spectroscopically separable group-inclusion complexes (α-substituted phenyl-in (R-in) and t-butyl-in complexes) and determined the group-inclusion constants of Calix-S8 and γ-CD. Using nitroxide probes, we have examined the effects of substituent and external pressure on group-inclusion complexation with Calix-S8 and γ-CD. Experiments on pressure dependence enabled us to calculate the reaction volume (Δ V) for R-in and t-butyl-in complex formations. Δ V for group-in complexation with Calix-S8 had negative values. In contrast, Δ V values for γ-CD showed positive values, which is responsible for the repelled water molecules in the CD cavity. The characteristic pressure effects on group-in complexation suggest that group recognition by γ-CD is sensitive when compared with that by Calix-S8.

Investigation of trypsin-CdSe quantum dot interactions via spectroscopic methods and effects on enzymatic activity.

PubMed

Kaur, Gurvir; Tripathi, S K

2015-01-05

The paper presents the interactions between trypsin and water soluble cadmium selenide (CdSe) quantum dots investigated by spectrophotometric methods. CdSe quantum dots have strong ability to quench the intrinsic fluorescence of trypsin by a static quenching mechanism. The quenching has been studied at three different temperatures where the results revealed that electrostatic interactions exist between CdSe quantum dots and trypsin and are responsible to stabilize the complex. The Scatchard plot from quenching revealed 1 binding site for quantum dots by trypsin, the same has been confirmed by making isothermal titrations of quantum dots against trypsin. The distance between donor and acceptor for trypsin-CdSe quantum dot complexes is calculated to be 2.8 nm by energy transfer mechanisms. The intrinsic fluorescence of CdSe quantum dots has also been enhanced by the trypsin, and is linear for concentration of trypsin ranging 1-80 μl. All the observations evidence the formation of trypsin-CdSe quantum dot conjugates, where trypsin retains the enzymatic activity which in turn is temperature and pH dependent. Copyright © 2014 Elsevier B.V. All rights reserved.

Glutathione-capped CdTe nanocrystals as probe for the determination of fenbendazole

NASA Astrophysics Data System (ADS)

Li, Qin; Tan, Xuanping; Li, Jin; Pan, Li; Liu, Xiaorong

2015-04-01

Water-soluble glutathione (GSH)-capped CdTe quantum dots (QDs) were synthesized. In pH 7.1 PBS buffer solution, the interaction between GSH-capped CdTe QDs and fenbendazole (FBZ) was investigated by spectroscopic methods, including fluorescence spectroscopy, ultraviolet-visible absorption spectroscopy, and resonance Rayleigh scattering (RRS) spectroscopy. In GSH-capped CdTe QDs solution, the addition of FBZ results in the fluorescence quenching and RRS enhancement of GSH-capped CdTe QDs. And the quenching intensity (enhanced RRS intensity) was proportional to the concentration of FBZ in a certain range. Investigation of the interaction mechanism, proved that the fluorescence quenching and RRS enhancement of GSH-capped CdTe QDs by FBZ is the result of electrostatic attraction. Based on the quenching of fluorescence (enhancement of RRS) of GSH-capped CdTe QDs by FBZ, a novel, simple, rapid and specific method for FBZ determination was proposed. The detection limit for FBZ was 42 ng mL-1 (3.4 ng mL-1) and the quantitative determination range was 0-2.8 μg mL-1 with a correlation of 0.9985 (0.9979). The method has been applied to detect FBZ in real simples and with satisfactory results.

Spectroscopic micro-tomography of metallic-organic composites by means of photon-counting detectors

NASA Astrophysics Data System (ADS)

Pichotka, M.; Jakubek, J.; Vavrik, D.

2015-12-01

The presumed capabilities of photon counting detectors have aroused major expectations in several fields of research. In the field of nuclear imaging ample benefits over standard detectors are to be expected from photon counting devices. First of all a very high contrast, as has by now been verified in numerous experiments. The spectroscopic capabilities of photon counting detectors further allow material decomposition in computed tomography and therefore inherently adequate beam hardening correction. For these reasons measurement setups featuring standard X-ray tubes combined with photon counting detectors constitute a possible replacement of the much more cost intensive tomographic setups at synchrotron light-sources. The actual application of photon counting detectors in radiographic setups in recent years has been impeded by a number of practical issues, above all by restrictions in the detectors size. Currently two tomographic setups in Czech Republic feature photon counting large-area detectors (LAD) fabricated in Prague. The employed large area hybrid pixel-detector assemblies [1] consisting of 10×10/10×5 Timepix devices have a surface area of 143×143 mm2 / 143×71,5 mm2 respectively, suitable for micro-tomographic applications. In the near future LAD devices featuring the Medipix3 readout chip as well as heavy sensors (CdTe, GaAs) will become available. Data analysis is obtained by a number of in house software tools including iterative multi-energy volume reconstruction.In this paper tomographic analysis of of metallic-organic composites is employed to illustrate the capabilities of our technology. Other than successful material decomposition by spectroscopic tomography we present a method to suppress metal artefacts under certain conditions.

Metal (II) Complexes Derived from Naphthofuran-2-carbohydrazide and Diacetylmonoxime Schiff Base: Synthesis, Spectroscopic, Electrochemical, and Biological Investigation

PubMed Central

Sumathi, R. B.; Halli, M. B.

2014-01-01

A new Schiff base and a new series of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) complexes were synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime. Metal complexes of the Schiff base were prepared from their chloride salts of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) in ethanol. The ligand along with its metal complexes have been characterized on the basis of analytical data, IR, electronic, mass, 1HNMR, ESR spectral data, thermal studies, magnetic susceptibility, and molar conductance measurements. The nonelectrolytic behaviour of the complexes was assessed from the measured low conductance data. The elemental analysis of the complexes confirm the stoichiometry of the type CuL2Cl2 and MLCl2 where M = Ni(II), Co(II), Cd(II), and Hg(II) and L = Schiff base. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In the light of these results, Co(II), Ni(II), and Cu(II) complexes are assigned octahedral geometry, Cd(II), and Hg(II) complexes tetrahedral geometry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleaving capacity of all the complexes was analysed by agarose gel electrophoresis method. PMID:24592203

Uniform thin films of CdSe and CdSe(ZnS) core(shell) quantum dots by sol-gel assembly: enabling photoelectrochemical characterization and electronic applications.

PubMed

Korala, Lasantha; Wang, Zhijie; Liu, Yi; Maldonado, Stephen; Brock, Stephanie L

2013-02-26

Optoelectronic properties of quantum dot (QD) films are limited by (1) poor interfacial chemistry and (2) nonradiative recombination due to surface traps. To address these performance issues, sol-gel methods are applied to fabricate thin films of CdSe and core(shell) CdSe(ZnS) QDs. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging with chemical analysis confirms that the surface of the QDs in the sol-gel thin films are chalcogen-rich, consistent with an oxidative-induced gelation mechanism in which connectivity is achieved by formation of dichalcogenide covalent linkages between particles. The ligand removal and assembly process is probed by thermogravimetric, spectroscopic, and microscopic studies. Further enhancement of interparticle coupling via mild thermal annealing, which removes residual ligands and reinforces QD connectivity, results in QD sol-gel thin films with superior charge transport properties, as shown by a dramatic enhancement of electrochemical photocurrent under white light illumination relative to thin films composed of ligand-capped QDs. A more than 2-fold enhancement in photocurrent, and a further increase in photovoltage can be achieved by passivation of surface defects via overcoating with a thin ZnS shell. The ability to tune interfacial and surface characteristics for the optimization of photophysical properties suggests that the sol-gel approach may enable formation of QD thin films suitable for a range of optoelectronic applications.

Uniform Thin Films of CdSe and CdSe(ZnS) Core(shell) Quantum Dots by Sol-Gel Assembly: Enabling Photoelectrochemical Characterization and Electronic Applications

PubMed Central

Korala, Lasantha; Wang, Zhijie; Liu, Yi; Maldonado, Stephen; Brock, Stephanie L.

2013-01-01

Optoelectronic properties of quantum dot (QD) films are limited by (1) poor interfacial chemistry and (2) non-radiative recombination due to surface traps. To address these performance issues, sol-gel methods are applied to fabricate thin films of CdSe and core(shell) CdSe(ZnS) QDs. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging with chemical analysis confirms that the surface of the QDs in the sol-gel thin films are chalcogen-rich, consistent with an oxidative-induced gelation mechanism in which connectivity is achieved by formation of dichalcogenide covalent linkages between particles. The ligand removal and assembly process is probed by thermogravimetric, spectroscopic and microscopic studies. Further enhancement of inter-particle coupling via mild thermal annealing, which removes residual ligands and reinforces QD connectivity, results in QD sol-gel thin films with superior charge transport properties, as shown by a dramatic enhancement of electrochemical photocurrent under white light illumination relative to thin films composed of ligand-capped QDs. A more than 2-fold enhancement in photocurrent, and a further increase in photovoltage can be achieved by passivation of surface defects via overcoating with a thin ZnS shell. The ability to tune interfacial and surface characteristics for the optimization of photophysical properties suggests that the sol-gel approach may enable formation of QD thin films suitable for a range of optoelectronic applications. PMID:23350924

Binding affinities of Schiff base Fe(II) complex with BSA and calf-thymus DNA: Spectroscopic investigations and molecular docking analysis

NASA Astrophysics Data System (ADS)

Rudra, Suparna; Dasmandal, Somnath; Patra, Chiranjit; Kundu, Arjama; Mahapatra, Ambikesh

2016-09-01

The binding interaction of a synthesized Schiff base Fe(II) complex with biological macromolecules viz., bovine serum albumin (BSA) and calf thymus(ct)-DNA have been investigated using different spectroscopic techniques coupled with viscosity measurements at physiological pH and 298 K. Regular amendments in emission intensities of BSA upon the action of the complex indicate significant interaction between them, and the binding interaction have been characterized by Stern Volmer plots and thermodynamic binding parameters. On the basis of this quenching technique one binding site with binding constant (Kb = (7.6 ± 0.21) × 105) between complex and protein have been obtained at 298 K. Time-resolved fluorescence studies have also been encountered to understand the mechanism of quenching induced by the complex. Binding affinities of the complex to the fluorophores of BSA namely tryptophan (Trp) and tyrosine (Tyr) have been judged by synchronous fluorescence studies. Secondary structural changes of BSA rooted by the complex has been revealed by CD spectra. On the other hand, hypochromicity of absorption spectra of the complex with the addition of ct-DNA and the gradual reduction in emission intensities of ethidium bromide bound ct-DNA in presence of the complex indicate noticeable interaction between ct-DNA and the complex with the binding constant (4.2 ± 0.11) × 106 M- 1. Life-time measurements have been studied to determine the relative amplitude of binding of the complex to ct-DNA base pairs. Mode of binding interaction of the complex with ct-DNA has been deciphered by viscosity measurements. CD spectra have also been used to understand the changes in ct-DNA structure upon binding with the metal complex. Density functional theory (DFT) and molecular docking analysis have been employed in highlighting the interactive phenomenon and binding location of the complex with the macromolecules.

Ag-doped CdO nanocatalysts: Preparation, characterization and catechol oxidase activity

NASA Astrophysics Data System (ADS)

El-Kemary, Maged; El-Mehasseb, Ibrahim; El-Shamy, Hany

2018-06-01

Silver doped cadmium oxide (Ag/CdO) nanoparticles with an average size of 41 nm have been successfully synthesized via thermal decomposition and liquid impregnation technique. The structural characterization has been performed by using several spectroscopic techniques, e.g., X-ray diffraction (XRD), scanning electron microscopy (SEM) and fourier-transform infrared (FT-IR). The catechol oxidase has been studied by UV-visible absorption spectroscopy and fourier-transform infrared as well as the mechanism has been assured by cyclic voltammetry and fluorescence spectroscopy. The results indicate that the oxidation does not occur in the presence of unsupported cadmium oxide particles by silver and in the same time, the catechol oxidase activity of silver doped CdO nanoparticles were improved by about three orders of magnitude than silver ions.

Transcriptional and functional studies of a Cd(II)/Pb(II)-responsive transcriptional regulator(CmtR) from Acidithiobacillus ferrooxidans ATCC 23270.

PubMed

Zheng, Chunli; Li, Yanjun; Nie, Li; Qian, Lin; Cai, Lu; Liu, Jianshe

2012-08-01

The acidophilic Acidithiobacillus ferrooxidans can resist exceptionally high cadmium (Cd) concentrations. This property is important for its use in biomining processes, where Cd and other metal levels range usually between 15 and 100 mM. To learn about the mechanisms that allow A. ferrooxidans cells to survive in this environment, a bioinformatic search of its genome showed the presence of that a Cd(II)/Pb(II)-responsive transcriptional regulator (CmtR) was possibly related to Cd homeostasis. The expression of the CmtR was studied by real-time reverse transcriptase PCR using A. ferrooxidans cells adapted for growth in the presence of high concentrations of Cd. The putative A. ferrooxidans Cd resistance determinant was found to be upregulated when this bacterium was exposed to Cd in the range of 15-30 mM. The CmtR from A. ferrooxidans was cloned and expressed in Escherichia coli, the soluble protein was purified by one-step affinity chromatography to apparent homogeneity. UV-Vis spectroscopic measurements showed that the reconstruction CmtR was able to bind Cd(II) forming Cd(II)-CmtR complex in vitro. The sequence alignment and molecular modeling showed that the crucial residues for CmtR binding were likely to be Cys77, Cys112, and Cys121. The results reported here strongly suggest that the high resistance of the extremophilic A. ferrooxidans to Cd including the Cd(II)/Pb(II)-responsive transcriptional regulator.

Photocatalytic degradation of organic contaminants under solar light using carbon dot/titanium dioxide nanohybrid, obtained through a facile approach

NASA Astrophysics Data System (ADS)

Hazarika, Deepshikha; Karak, Niranjan

2016-07-01

In the present study, a novel, simple and green method was developed to synthesize highly luminescent nitrogen containing carbon dot (CD) using carbon resources like bio-based citric acid and glycerol in the presence of cost free cow urine. The as-synthesized CD showed exciting wavelength dependent down- and up-conversion flourescence properties. To utilize the advantage of up-conversion flourescence, a nanohybrid (CD@TiO2) was synthesized from the above carbon resources and titanium butoxide through a facile one pot single step hydrothermal protocol. Nanomaterials like bare TiO2 and nanohybrid of TiO2 in presence of CD (CD/TiO2) were also synthesized for comparison purpose. The optical properties and structural characteristics of the prepared CD, bare TiO2, CD@TiO2 and CD/TiO2 were examined by Fourier transform infrared (FTIR), UV-vis and fluorescence spectroscopic, scanning electron microscopic (SEM), transmission electron microscopic (TEM) and X-ray diffraction (XRD) studies. The elemental compositions of bare CD and CD@TiO2 nanohybrid were obtained from EDX analyses. The poor crystalline nature and narrow distribution of spherical CD and anatase form of TiO2 were confirmed from XRD and TEM studies. Amongst the studied nanomaterials, CD@TiO2 exhibited the most promising photocatalytic degradation of organic pollutants like benzene and phenol as well as an anthrogenic pesticide under sunlight.

Two-photon absorption properties of cationic 1,4-bis(styryl)benzene derivative and its inclusion complexes with cyclodextrins.

PubMed

Nag, Okhil Kumar; Nayak, Rati Ranjan; Lim, Chang Su; Kim, In Hong; Kyhm, Kwangseuk; Cho, Bong Rae; Woo, Han Young

2010-07-29

Two-photon absorption properties of 1,4-bis{4'-[N,N-bis(6''-trimethylammoniumhexyl)amino]styryl}benzene tetrabromide (C1) and its inclusion complexes (ICs) with cyclodextrins (CDs) have been studied. Upon complexation with CDs, the absorption spectra of C1 showed a slight red shift, whereas the emission spectra showed a blue shift with concomitant increase in the fluorescence quantum efficiency. A Stern-Volmer study using K(3)Fe(CN)(6) as a quencher revealed significant reduction in the photoinduced charge transfer quenching, in accord with the IC formation. Comparison of the spectroscopic results reveals that C1 forms increasingly more stable ICs in the order C1/beta-CD < C1/gamma-CD < C1/(3gamma:beta)-CD (gamma-CD/beta-CD 3:1, mole ratio). Moreover, the two-photon action cross section of C1 increased from 200 GM for C1 to 400 GM for C1/beta-CD, 460 GM for C1/gamma-CD, and 650 GM for C1/(3gamma:beta)-CD, respectively. Furthermore, the two-photon microscopy images of HeLa cells stained with C1 emitted strong two-photon excited fluorescence in the plasma membrane. These results provide a useful guideline for the development of efficient two-photon materials for bioimaging applications.

The application of BTEM to UV-vis and UV-vis CD spectroscopies: the reaction of Rh4(CO)12 with chiral and achiral ligands.

PubMed

Cheng, Shuying; Gao, Feng; Krummel, Karl I; Garland, Marc

2008-02-15

Two different organometallic ligand substitution reactions were investigated: (1) an achiral reactive system consisting of Rh(4)(CO)(12)+PPh(3)right harpoon over left harpoonRh(4)(CO)(11)PPh(3)+CO in n-hexane under argon; and (2) a chiral reactive system consisting of Rh(4)(CO)(12)+(S)-BINAPright harpoon over left harpoonRh(4)(CO)(10)BINAP+2CO in cyclohexane under argon. These two reactions were run at ultra high dilution. In both multi-component reactive systems the concentrations of all the solutes were less than 40ppm and many solute concentrations were just 1-10ppm. In situ spectroscopic measurements were carried out using UV-vis (Ultraviolet-visible) spectroscopy and UV-vis CD spectroscopy on the reactive organometallic systems (1) and (2), respectively. The BTEM algorithm was applied to these spectroscopic data sets. The reconstructed UV-vis pure component spectra of Rh(4)(CO)(12), Rh(4)(CO)(11)PPh(3) and Rh(4)(CO)(10)BINAP as well as the reconstructed UV-vis CD pure component spectra of Rh(4)(CO)(10)BINAP were successfully obtained from BTEM analyses. All these reconstructed pure component spectra are in good agreement with the experimental reference spectra. The concentration profiles of the present species were obtained by performing a least square fit with mass balance constraints for the reactions (1) and (2). The present results indicate that UV-vis and UV-vis-CD spectroscopies can be successfully combined with an appropriate chemometric technique in order to monitor reactive organometallic systems having UV and Vis chromophores.

In-cell overlay metrology by using optical metrology tool

NASA Astrophysics Data System (ADS)

Lee, Honggoo; Han, Sangjun; Hong, Minhyung; Kim, Seungyoung; Lee, Jieun; Lee, DongYoung; Oh, Eungryong; Choi, Ahlin; Park, Hyowon; Liang, Waley; Choi, DongSub; Kim, Nakyoon; Lee, Jeongpyo; Pandev, Stilian; Jeon, Sanghuck; Robinson, John C.

2018-03-01

Overlay is one of the most critical process control steps of semiconductor manufacturing technology. A typical advanced scheme includes an overlay feedback loop based on after litho optical imaging overlay metrology on scribeline targets. The after litho control loop typically involves high frequency sampling: every lot or nearly every lot. An after etch overlay metrology step is often included, at a lower sampling frequency, in order to characterize and compensate for bias. The after etch metrology step often involves CD-SEM metrology, in this case in-cell and ondevice. This work explores an alternative approach using spectroscopic ellipsometry (SE) metrology and a machine learning analysis technique. Advanced 1x nm DRAM wafers were prepared, including both nominal (POR) wafers with mean overlay offsets, as well as DOE wafers with intentional across wafer overlay modulation. After litho metrology was measured using optical imaging metrology, as well as after etch metrology using both SE and CD-SEM for comparison. We investigate 2 types of machine learning techniques with SE data: model-less and model-based, showing excellent performance for after etch in-cell on-device overlay metrology.

Separation and Identification of Anthocyanins Extracted from Blueberry Wine Lees and Pigment Binding Properties toward β-Glucosidase.

PubMed

Wu, Qian; Zhang, Yang; Tang, Hu; Chen, Yashu; Xie, Bijun; Wang, Chao; Sun, Zhida

2017-01-11

Anthocyanins were isolated from blueberry wine lees using Sephadex LH-20 column chromatography and semipreparative high-performance liquid chromatography (semipreparative HPLC) and then identified by HPLC-DAD-ESI-MS/MS. Our results show that malvidin-3-hexose (Mv-3-hex) and malvidin-3-(6'acetyl)-hexose (Mv-3-ace-hex) are the major components in the anthocyanin extracts of blueberry wine lees (>90%). The binding characteristics of Mv-3-hex and Mv-3-ace-hex with β-glucosidase were investigated by fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and molecular docking. Spectroscopic analysis revealed that β-glucosidase fluorescence quenched by Mv-3-hex and Mv-3-ace-hex follows a static mode. Binding of Mv-3-hex and Mv-3-ace-hex to β-glucosidase mainly depends on electrostatic force. The result from CD spectra shows that adaptive structure rearrangement and increase of β-sheet structure occur only in the presence of Mv-3-ace-hex. A molecular docking study suggests that Mv-3-ace-hex has stronger binding with β-glucosidase than Mv-3-hex.

STRONG GRAVITATIONAL LENSING BY THE SUPER-MASSIVE cD GALAXY IN ABELL 3827

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carrasco, E. R.; Gomez, P. L.; Lee, H.

2010-06-01

We have discovered strong gravitational lensing features in the core of the nearby cluster Abell 3827 by analyzing Gemini South GMOS images. The most prominent strong lensing feature is a highly magnified, ring-shaped configuration of four images around the central cD galaxy. GMOS spectroscopic analysis puts this source at z {approx} 0.2. Located {approx}20'' away from the central galaxy is a secondary tangential arc feature which has been identified as a background galaxy with z {approx} 0.4. We have modeled the gravitational potential of the cluster core, taking into account the mass from the cluster, the brightest cluster galaxy (BCG),more » and other galaxies. We derive a total mass of (2.7 {+-} 0.4) x 10{sup 13} M {sub sun} within 37 h {sup -1} kpc. This mass is an order of magnitude larger than that derived from X-ray observations. The total mass derived from lensing data suggests that the BCG in this cluster is perhaps the most massive galaxy in the nearby universe.« less

Understanding the shrinkage of optical absorption edges of nanostructured Cd-Zn sulphide films for photothermal applications

NASA Astrophysics Data System (ADS)

Hossain, Md. Sohrab; Kabir, Humayun; Rahman, M. Mahbubur; Hasan, Kamrul; Bashar, Muhammad Shahriar; Rahman, Mashudur; Gafur, Md. Abdul; Islam, Shariful; Amri, Amun; Jiang, Zhong-Tao; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.

2017-01-01

In this article Cd-Zn sulphide thin films deposited onto soda lime glass substrates via chemical bath deposition (CBD) technique were investigated for photovoltaic applications. The synthesized films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet visible (UV-vis) spectroscopic methodologies. A higher degree of crystallinity of the films was attained with the increase of film thicknesses. SEM micrographs exhibited a partial crystalline structure with a particulate appearance surrounded by the amorphous grain boundaries. The optical absorbance and absorption coefficient of the films were also enhanced significantly with the increase in film thicknesses. Optical band-gap analysis indicated a monotonic decrease in direct and indirect band-gaps with the increase of thicknesses of the films. The presence of direct and indirect transitional energies due to the exponential falling edges of the absorption curves may either be due to the lack of long-range order or to the existence of defects in the films. The declination of the optical absorption edges was also confirmed via Urbach energy and steepness parameters studies.

Probing the binding of phenolic aldehyde vanillin with bovine serum albumin: Evidence from spectroscopic and docking approach.

PubMed

Siddiqui, Gufran Ahmed; Siddiqi, Mohammad Khursheed; Khan, Rizwan Hasan; Naeem, Aabgeena

2018-05-08

The interactions of bovine serum albumin (BSA) with vanillin (VAN) were studied using UV-vis absorption, fluorescence, synchronous fluorescence, three dimensional fluorescence spectroscopy (3D), Fourier transform infrared spectroscopy (FTIR), circular dichroism (CD), and molecular docking techniques. The results revealed that VAN causes the static quenching of BSA by forming BSA-VAN complex. The thermodynamic parameters obtained using isothermal titration calorimetry (ITC) showed that the interaction between BSA and VAN is spontaneous and hydrogen bonding, van der Waals forces are mainly involved in stabilizing the complex. The distance between the donor and the acceptor was analyzed using fluorescence resonance energy transfer (FRET) which showed Forster distance of 2.58 nm. Molecular docking technique was applied to study the modes of interaction between BSA-VAN system and it was found that VAN bound to the sub-domain IIA of BSA. Structural analysis using 3D, synchronous fluorescence FTIR, and CD showed that upon binding of VAN, BSA exhibits small micro-environmental changes around tryptophan amino acid residue. Copyright © 2018. Published by Elsevier B.V.

Spectroscopic Identification of the Carbyne Hydride Structure of the Dehydrogenation Product of Methane Activation by Osmium Cations

NASA Astrophysics Data System (ADS)

Armentrout, P. B.; Kuijpers, Stach E. J.; Lushchikova, Olga V.; Hightower, Randy L.; Boles, Georgia C.; Bakker, Joost M.

2018-04-01

The present work explores the structures of species formed by dehydrogenation of methane (CH4) and perdeuterated methane (CD4) by the 5d transition metal cation osmium (Os+). Using infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT), the structures of the [Os,C,2H]+ and [Os,C,2D]+ products are explored. This study complements previous work on the related species formed by dehydrogenation of methane by four other 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Osmium cations are formed in a laser ablation source, react with methane pulsed into a reaction channel downstream, and the resulting products spectroscopically characterized through photofragmentation using the Free-Electron Laser for IntraCavity Experiments (FELICE) in the 300-1800 cm-1 range. Photofragmentation was monitored by the loss of H2/D2. Comparison of the experimental spectra and DFT calculated spectra leads to identification of the ground state carbyne hydride, HOsCH+ (2A') as the species formed, as previously postulated theoretically. Further, a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy, is achieved. A full rotational contour analysis explains the observed linewidths as well as the observation of doublet structures in several bands, consistent with previous observations for HIrCH+ (2A'). [Figure not available: see fulltext.

Probing the mechanism of interaction of metoprolol succinate with human serum albumin by spectroscopic and molecular docking analysis.

PubMed

Pawar, Suma K; Jaldappagari, Seetharamappa

2017-09-01

In the present work, the mechanism of the interaction between a β1 receptor blocker, metoprolol succinate (MS) and human serum albumin (HSA) under physiological conditions was investigated by spectroscopic techniques, namely fluorescence, Fourier transform infra-red spectroscopy (FT-IR), fluorescence lifetime decay and circular dichroism (CD) as well as molecular docking and cyclic voltammetric methods. The fluorescence and lifetime decay results indicated that MS quenched the intrinsic intensity of HSA through a static quenching mechanism. The Stern-Volmer quenching constants and binding constants for the MS-HSA system at 293, 298 and 303 K were obtained from the Stern-Volmer plot. Thermodynamic parameters for the interaction of MS with HSA were evaluated; negative values of entropy change (ΔG°) indicated the spontaneity of the MS and HSA interaction. Thermodynamic parameters such as negative ΔH° and positive ΔS° values revealed that hydrogen bonding and hydrophobic forces played a major role in MS-HSA interaction and stabilized the complex. The binding site for MS in HSA was identified by competitive site probe experiments and molecular docking studies. These results indicated that MS was bound to HSA at Sudlow's site I. The efficiency of energy transfer and the distance between the donor (HSA) and acceptor (MS) was calculated based on the theory of Fosters' resonance energy transfer (FRET). Three-dimensional fluorescence spectra and CD results revealed that the binding of MS to HSA resulted in an obvious change in the conformation of HSA. Cyclic voltammograms of the MS-HSA system also confirmed the interaction between MS and HSA. Furthermore, the effects of metal ions on the binding of MS to HSA were also studied. Copyright © 2017 John Wiley & Sons, Ltd.

Microheterogeneity in binary mixtures of water with CH3OH and CD3OH: ATR-IR spectroscopic, chemometric and DFT studies

NASA Astrophysics Data System (ADS)

Tomza, Paweł; Wrzeszcz, Władysław; Mazurek, Sylwester; Szostak, Roman; Czarnecki, Mirosław Antoni

2018-05-01

Here we report ATR-IR spectroscopic study on the separation at a molecular level (microheterogeneity) and the degree of deviation of H2O/CH3OH and H2O/CD3OH mixtures from the ideal mixture. Of particular interest is the effect of isotopic substitution in methyl group on molecular structure and interactions in both mixtures. To obtain comprehensive information from the multivariate data we applied the excess molar absorptivity spectra together with two-dimensional correlation analysis (2DCOS) and chemometric methods. In addition, the experimental results were compared and discussed with the structures of various model clusters obtained from theoretical (DFT) calculations. Our results evidence the presence of separation at a molecular level and deviation from the ideal mixture for both mixtures. The experimental and theoretical results show that the maximum of these deviations appears at equimolar mixture. Both mixtures consist of three kinds of species: homoclusters of water and methanol and mixed clusters (heteroclusters). The heteroclusters exist in the whole range of mole fractions with the maximum close to the equimolar mixture. At this mixture composition near 55-60% of molecules are involved in heteroclusters. In contrast, the homoclusters of water occur in a limited range of mole fractions (XME < 0.85-0.9). Upon mixing the molecules of methanol form weaker hydrogen bonding as compared with the pure alcohol. In contrast, the molecules of water in the mixture are involved in stronger hydrogen bonding than those in bulk water. All these results indicate that both mixtures have similar degree of deviation from the ideal mixture.

Microheterogeneity in binary mixtures of water with CH3OH and CD3OH: ATR-IR spectroscopic, chemometric and DFT studies.

PubMed

Tomza, Paweł; Wrzeszcz, Władysław; Mazurek, Sylwester; Szostak, Roman; Czarnecki, Mirosław Antoni

2018-05-15

Here we report ATR-IR spectroscopic study on the separation at a molecular level (microheterogeneity) and the degree of deviation of H 2 O/CH 3 OH and H 2 O/CD 3 OH mixtures from the ideal mixture. Of particular interest is the effect of isotopic substitution in methyl group on molecular structure and interactions in both mixtures. To obtain comprehensive information from the multivariate data we applied the excess molar absorptivity spectra together with two-dimensional correlation analysis (2DCOS) and chemometric methods. In addition, the experimental results were compared and discussed with the structures of various model clusters obtained from theoretical (DFT) calculations. Our results evidence the presence of separation at a molecular level and deviation from the ideal mixture for both mixtures. The experimental and theoretical results show that the maximum of these deviations appears at equimolar mixture. Both mixtures consist of three kinds of species: homoclusters of water and methanol and mixed clusters (heteroclusters). The heteroclusters exist in the whole range of mole fractions with the maximum close to the equimolar mixture. At this mixture composition near 55-60% of molecules are involved in heteroclusters. In contrast, the homoclusters of water occur in a limited range of mole fractions (X ME  < 0.85-0.9). Upon mixing the molecules of methanol form weaker hydrogen bonding as compared with the pure alcohol. In contrast, the molecules of water in the mixture are involved in stronger hydrogen bonding than those in bulk water. All these results indicate that both mixtures have similar degree of deviation from the ideal mixture. Copyright © 2018 Elsevier B.V. All rights reserved.

Spectroscopic properties of 130Sb, 132Te and 134I nuclei in 100-132Sn magic cores

NASA Astrophysics Data System (ADS)

Benrachi, Fatima; Khiter, Meriem; Laouet, Nadjet

2017-09-01

We have performed shell model calculations by means of Oxbash nuclear structure code using recent experimental single particle (spes) and single hole (shes) energies with valence space models above the 100sn and 132sn doubly magic cores. The two-body matrix elements (tbme) of original CD-Bonn realistic interaction are introduced after have been modified taking into account the three-body forces. We have focused our study on spectroscopic properties evaluation of 130Sb, 132Te and 134I nuclei, in particular their energy spectra, transition probabilities and moments have been determined. The getting spectra are in reasonable agreement with the experimental data.

Spectroscopic exploration of interaction between PEG-functionalized Ag2S nanoparticles with bovine serum albumin

NASA Astrophysics Data System (ADS)

Prasanth, S.; RitheshRaj, D.; Vineeshkumar, T. V.; Sudarsanakumar, C.

2018-05-01

The introduction of nanoparticles into biological fluids often leads to the formation of biocorona over the surface of nanoparticles. For the effective use of nanoparticles in biological applications it is very essential to understand their interactions with proteins. Herein, we investigated the interactions of Poly ethylene glycol capped Ag2S nanoparticles with Bovine Serum Albumin by spectroscopic techniques. By the addition of Ag2S nanoparticles, a ground state complex is formed. The CD spectroscopy reveals that the secondary structure of BSA is altered by complexation with PEG-Ag2S nanoparticles, while the overall tertiary structure remains closer to that of native BSA.

(+)- and (-)-Pestaloxazine A, a Pair of Antiviral Enantiomeric Alkaloid Dimers with a Symmetric Spiro[oxazinane-piperazinedione] Skeleton from Pestalotiopsis sp.

PubMed

Jia, Yan-Lai; Wei, Mei-Yan; Chen, Hai-Yan; Guan, Fei-Fei; Wang, Chang-Yun; Shao, Chang-Lun

2015-09-04

A pair of new enantiomeric alkaloid dimers, (+)- and (-)-pestaloxazine A (1), with an unprecedented symmetric spiro[oxazinane-piperazinedione] skeleton, consisting of 22 carbons and 12 heteroatoms, were isolated from a Pestalotiopsis sp. fungus derived from a soft coral. Separation of the enantiomeric alkaloid dimers was achieved by chiral HPLC. Their structures including absolute configurations were elucidated on the basis of a comprehensive analysis of their spectroscopic and X-ray diffraction data and CD calculations. (+)-Pestaloxazine A exhibited potent antiviral activity against EV71 with an IC50 value of 14.2 ± 1.3 μM, which was stronger than that of the positive control ribavirin (IC50 = 256.1 ± 15.1 μM).

Synthesis, spectroscopic, biological activity and thermal characterization of ceftazidime with transition metals

NASA Astrophysics Data System (ADS)

Masoud, Mamdouh S.; Ali, Alaa E.; Elasala, Gehan S.; Kolkaila, Sherif A.

2018-03-01

Synthesis, physicochemical characterization and thermal analysis of ceftazidime complexes with transition metals (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were discussed. It's obtained that ceftazidime act as bidentate ligand. From magnetic measurement and spectral data, octahedral structures were proposed for all complexes except for cobalt, nickel and mercury had tetrahedral structural. Hyper chemistry program confirmed binding sites of ceftazidime. Ceftazidime complexes show higher activity than ceftazidime for some strains. From TG and DTA curves the thermal decomposition mechanisms of ceftazidime and their metal complexes were suggested. The thermal decomposition of the complexes ended with the formation of metal oxides as a final product except in case of Hg complex.

Drimane sesquiterpenoids from the Aspergillus oryzae QXPC-4.

PubMed

Ren, Ren; Chen, Chao-Jun; Hu, Sha-Sha; Ge, Hui-Ming; Zhu, Wen-Yong; Tan, Ren-Xiang; Jiao, Rui-Hua

2015-03-01

Three new drimane sesquiterpenoids, astellolides C-E (1-3, resp.), four new drimane sesquiterpenoid p-hydroxybenzoates, astellolides F-I (4-7, resp.), together with two known compounds astellolides A and B (8 and 9, resp.), have been isolated from the liquid culture of Aspergillus oryzae (strain No. QXPC-4). Their structures were established by comprehensive analysis of spectroscopic data. The relative and absolute configurations were determined on the basis of NOESY and CD data, together with single-crystal X-ray diffraction analyses of compounds 1-3. The metabolites were evaluated for their cytotoxic activities, however, no compounds showed a significant cytotoxicity against the tested cell lines at a concentration of 20 μM. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

Analysis of calcium-induced effects on the conformation of fengycin.

PubMed

Nasir, Mehmet Nail; Laurent, Pascal; Flore, Christelle; Lins, Laurence; Ongena, Marc; Deleu, Magali

2013-06-01

Fengycin is a natural lipopeptide with antifungal and eliciting properties and able to inhibit the activity of phospholipase A2. A combination of CD, FT-IR, NMR and fluorescence spectroscopic techniques was applied to elucidate its conformation in a membrane-mimicking environment and to investigate the effect of calcium ions on it. We mainly observed that fengycin adopts a turn conformation. Our results showed that calcium ions are bound by the two charged glutamates. The calcium binding has an influence on the fengycin conformation and more particularly, on the environment of the tyrosine residues. The modulation of the fengycin conformation by the environmental conditions may influence its biological properties. Copyright © 2013 Elsevier B.V. All rights reserved.

Three new 12-carbamoylated streptothricins from Streptomyces sp. I08A 1776.

PubMed

Gan, Maoluo; Zheng, Xudong; Liu, Yufeng; Guan, Yan; Xiao, Chunling

2012-10-01

Two new streptothricins (1 and 2) and a new streptothricin acid derivative (3), all with the carbamoyl group substituted at C-12 of the gulosamine moiety, together with the known N(β)-acetylstreptothricin D acid (4), have been isolated from the culture broth of Streptomyces sp. I08A 1776. The structures of the new compounds were determined by MS, CD, and 1D and 2D NMR spectroscopic data analysis. The isolated compounds were evaluated for antibacterial and antifungal activities. Streptothricin E (6) showed potent activity against the clinically isolated extensively drug-resistant Mycobacterium tuberculosis with MIC values of 0.25-0.5μg/mL. Copyright © 2012 Elsevier Ltd. All rights reserved.

Encapsulation of serotonin in β-cyclodextrin nano-cavities: Fluorescence spectroscopic and molecular modeling studies

NASA Astrophysics Data System (ADS)

Chaudhuri, Sudip; Chakraborty, Sandipan; Sengupta, Pradeep K.

2010-06-01

Serotonin is a physiologically important biogenic amine, deficiency of which leads to mental disorders such as Alzheimer's disease, schizophrenia, infantile autism, and depression. Both β-cyclodextrin (β-CD) and its chemically substituted synthetic varieties (often possessing enhanced aqueous solubility and improved drug complexing abilities) are finding wide applications as drug delivery vehicles. Here we have studied the encapsulation of serotonin in β-CD and succinyl-2-hydroxypropyl β-cyclodextrin (SHP-β-CD) by exploiting the intrinsic serotonin fluorescence. Enhanced fluorescence emission intensity (which increases by ˜18% and 34% in β-CD and SHPβ-CD respectively) and anisotropy ( r) ( r = 0.075 and 0.1 in β-CD and SHPβ-CD respectively) are observed in presence of the cyclodextrins. From the fluorescence data host-guest interaction with 1:1 stoichiometry is evident, the association constants ( K) being 126.06 M -1 and 461.62 M -1 for β-CD and SHPβ-CD respectively. Additionally, molecular docking and semiempirical calculations have been carried out which provide, for the first time, detailed insights regarding the encapsulation process. In particular, it is evident that the indole ring is inserted within the β-CD cavity with the aliphatic amine side chain protruding towards the primary rim of the β-CD cavity. Docking calculations reveal that hydrogen bonding interactions are involved in the formation of the inclusion complex. Semiempirical calculations indicate that formation of the 1:1 inclusion complex is energetically favorable which is consistent with the fluorescence data.

Chemical fingerprints of He-sdO stars

NASA Astrophysics Data System (ADS)

Schindewolf, Markus; Németh, Peter; Heber, Ulrich; Battich, Tiara; Bertolami, Marcelo M. Miller; Latour, Marilyn

2018-02-01

The chemical composition of helium-rich hot subluminous O stars plays an important role to understand and model their formation history. We present a spectroscopic analysis of four He-sdO stars,CD-31° 4800, [CW83] 0904- 02, LSS 1274 and LS IV +10° 9. The analysis is based on archival optical and UV high-resolution spectra. We used Tlusty200/Synspec48 to compute line blanketed non-LTE model atmospheres and their corresponding synthetic spectra and derive the atmospheric parameters as well as the abundances of the most prominent elements. All stars have helium-dominated atmospheres with hardly any hydrogen and temperatures between 42000 K and 47000 K while their surface gravity spans between log g = 5.4 and 5.7. CD-31° 4800 shows an enrichment of nitrogen and the characteristic pattern of hydrogen burning via the CNO-cycle, while the rest of the elements have about the solar abundance. This points to the slow merger of two helium white dwarfs as the most likely origin for this system. The other three stars are enriched in carbon, nitrogen and neon while their intermediate mass element's abundance scatters around the solar value. They were possibly formed in the deep mixing late hot flasher scenario.

Proteolytically-induced changes of secondary structural protein conformation of bovine serum albumin monitored by Fourier transform infrared (FT-IR) and UV-circular dichroism spectroscopy

NASA Astrophysics Data System (ADS)

Güler, Günnur; Vorob'ev, Mikhail M.; Vogel, Vitali; Mäntele, Werner

2016-05-01

Enzymatically-induced degradation of bovine serum albumin (BSA) by serine proteases (trypsin and α-chymotrypsin) in various concentrations was monitored by means of Fourier transform infrared (FT-IR) and ultraviolet circular dichroism (UV-CD) spectroscopy. In this study, the applicability of both spectroscopies to monitor the proteolysis process in real time has been proven, by tracking the spectral changes together with secondary structure analysis of BSA as proteolysis proceeds. On the basis of the FTIR spectra and the changes in the amide I band region, we suggest the progression of proteolysis process via conversion of α-helices (1654 cm- 1) into unordered structures and an increase in the concentration of free carboxylates (absorption of 1593 and 1402 cm- 1). For the first time, the correlation between the degree of hydrolysis and the concentration of carboxylic groups measured by FTIR spectroscopy was revealed as well. The far UV-CD spectra together with their secondary structure analysis suggest that the α-helical content decreases concomitant with an increase in the unordered structure. Both spectroscopic techniques also demonstrate that there are similar but less spectral changes of BSA for the trypsin attack than for α-chymotrypsin although the substrate/enzyme ratio is taken the same.

Activation Thermodynamics and H/D Kinetic Isotope Effect of the H ox to H red H + Transition in [FeFe] Hydrogenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratzloff, Michael W.; Wilker, Molly B.; Mulder, David W.

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here in this paper we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox→H redH + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ~2.5-foldmore » kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox→H redH + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.« less

Activation Thermodynamics and H/D Kinetic Isotope Effect of the H ox to H red H + Transition in [FeFe] Hydrogenase

DOE PAGES

Ratzloff, Michael W.; Wilker, Molly B.; Mulder, David W.; ...

2017-08-29

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here in this paper we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox→H redH + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ~2.5-foldmore » kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox→H redH + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.« less

Laser mass spectrometry with circularly polarized light: circular dichroism of cold molecules in a supersonic gas beam.

PubMed

Titze, Katharina; Zollitsch, Tilo; Heiz, Ulrich; Boesl, Ulrich

2014-09-15

An experiment on chiral molecules that combines circular dichroism (CD) spectroscopy, mass-selective detection by laser mass spectrometry (MS), and cooling of molecules by using a supersonic beam is presented. The combination of the former two techniques (CD-laser-MS) is a new method to investigate chiral molecules and is now used by several research groups. Cooling in a supersonic beam supplies a substantial increase in spectroscopic resolution, a feature that has not yet been used in CD spectroscopy. In the experiments reported herein, a large variation in the electronic CD of carbonyl 3-methylcyclopentanone was observed depending on the excited vibrational modes in the n → π* transition. This finding should be of interest for the detection of chiral molecules and for the theoretical understanding of the CD of vibronic bands. It is expected that this effect will show up in other chiral carbonyls because the n → π* transition is typical for the carbonyl group. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intraoperative metastases detection by laser-induced fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Vari, Sandor G.; Papazoglou, Theodore G.; van der Veen, Maurits J.; Fishbein, Michael C.; Young, J. D.; Chandra, Mudjianto; Papaioannou, Thanassis; Beeder, Clain; Shi, Wei-Qiang; Grundfest, Warren S.

1991-06-01

The authors studied the ability of Laser Induced Fluorescence Spectroscopy (LIFS) for the intraoperative identification of metastases using a photosensitizing agent Photofrin IIr to enhance spectroscopic detection. A He-Cd laser source (442 nm) was used to produce low-power illumination of tissue via a hand-held 400 micrometers fiberoptic probe. Through the same fiber, reflected and emitted light was returned to an optical multi-channel analyzer (OMA III) for analysis. Spectroscopic signals were displayed on a screen for immediate examination. Lobund Wistar rats, inoculated with Pollard rat adenocarcinoma cells, were used as an animal model. Photofrin IIr was administered intraperitoneal 24 or 48 hours prior to surgical exploration in doses varying from 0.75-7.5 mg/kg. Metastases detection was performed during abdominal exploration directed to ipsilateral and contralateral inguinal, iliac, para-aortic and renal lymph nodes. Nineteen tissue samples, identified as abnormal by LIFS, were removed for histologic analysis; 11 of these samples were larger than 5mm and histologic examination revealed malignancy in all cases. While LIFS signals showed malignancy in 8 tissue samples with dimensions less than 5mm, histology confirmed this in only 3. However, serial histologic sections were not performed. From the initial results, it was concluded that LIFS detection of malignant tissue is feasible and enhanced by the addition of Photofrin IIr. LIFS may be a promising technique for the intraoperative detection of primary malignant and metastatic tissue.

Fluconazole and its interaction with metal (II) complexes: SEM, Spectroscopic and antifungal studies.

PubMed

Ali, Mohsin; Ahmed, Mansoor; Ahmed, Shakil; Ali, Syed Imran; Perveen, Samina; Mumtaz, Majid; Haider, Syed Moazzam; Nazim, Urooj

2017-01-01

The human digestive tract contains some 100 trillion cells and thousands of species of micro-organisms may be present as normal flora of this tract as well as other mucocutaneous junctions of the body. Candida specie is the most common organism residing in these areas and can easily invade the internal tissues in cases of loss of host defenses. Modifications of previously existing antifungal agents may provide new options to fight against these species. Inorganic compounds of different antifungals are under investigations. Present study report six complexes of fluconazole with Cu (II)), Fe(II), Cd(II), Co(II), Ni(II) and Mn(II) have been synthesized and characterized by elemental analysis, IR, UV and H-NMR. The elemental analysis and spectroscopic data were found in agreement with the expected values as the metal to ligand value was 1:2 ratios with two chlorides in coordination sphere. The morphology of each complex was studied using scanning electron microscope and compared with fluconazole molecule the flaky-slab rock like particles of pure fluconazole was also observed as reported earlier. However, the complexes of fluconazole were showed different morphology in their micrograph. Fluconazole and its complex derivatives have also been screened in vitro for their antifungal activity against Candida albican and Aspergillus niger by MIC method. The complexes showed varied activity ranging from 2-20%.

Synthesis of CdS/ZnO/graphene composite with high-efficiency photoelectrochemical activities under solar radiation

NASA Astrophysics Data System (ADS)

Han, Weijia; Ren, Long; Qi, Xiang; Liu, Yundan; Wei, Xiaolin; Huang, Zongyu; Zhong, Jianxin

2014-04-01

A novel ternary CdS/ZnO/graphene composite has been successfully prepared by loading ZnO and CdS nanoparticles in graphene nanosheets via a facile one-step hydrothermal method. The microstructures and properties have been examined by X-ray diffraction (XRD), scanning electron microscopy with an energy dispersive spectroscope (EDS), transmission electron microscopy, Raman and UV-vis diffuse reflectance spectra (DRS). The characterization results reveal that the crystalline of the composite is very well, the graphene sheets were tightly coated with ZnO and CdS nanoparticles, and the light-harvesting was effectively strengthened. Taking photoelectrochemical test, the ternary CdS/ZnO/graphene composite exhibits enhanced photocatalytic activity compared with its foundation matrix binary composites and pure ZnO and CdS. The improved photocatalytic performance can be attributed to the enhanced light absorption, the extremely efficient charge separation, as well as superior durability of the ternary composite. It is proposed that graphene-based composites by coupling graphene to suitable, multiple semiconductors can not only greatly improve the capacity for photocatalytic, but also expand the exploration and utilization of graphene-based nanocomposites for energy conversion.

Spectroscopic investigation of sulfonate phthalocyanine to probe enzyme reactions for heavy metals detection.

PubMed

Chaure, Shweta; Paul, Deepen; Vadagma, Pankaj; Ray, Asim K

2010-01-15

Optical absorption and Raman spectra of the sulfonated copper phthalocyanine (CuTsPc) layer were exploited for detection of cadmium (Cd) contaminants in water. Acetylcholine esterase was immobilized by freely suspending them in calcium alginate microbeads and this gel was then spincoated on the drop cast sulfonated copper phthalocyanine film on a glass substrate to form a bilayer. The inhibition of catalytic reaction between acetylcholine chloride and enzyme due to Cd contaminants was monitored by recording changes in spectra of drop cast CuTsPc as an indicator. The detection limit of cadmium content in water was found to be 1 ppm.

Glutathione-capped CdTe nanocrystals as probe for the determination of fenbendazole.

PubMed

Li, Qin; Tan, Xuanping; Li, Jin; Pan, Li; Liu, Xiaorong

2015-04-15

Water-soluble glutathione (GSH)-capped CdTe quantum dots (QDs) were synthesized. In pH 7.1 PBS buffer solution, the interaction between GSH-capped CdTe QDs and fenbendazole (FBZ) was investigated by spectroscopic methods, including fluorescence spectroscopy, ultraviolet-visible absorption spectroscopy, and resonance Rayleigh scattering (RRS) spectroscopy. In GSH-capped CdTe QDs solution, the addition of FBZ results in the fluorescence quenching and RRS enhancement of GSH-capped CdTe QDs. And the quenching intensity (enhanced RRS intensity) was proportional to the concentration of FBZ in a certain range. Investigation of the interaction mechanism, proved that the fluorescence quenching and RRS enhancement of GSH-capped CdTe QDs by FBZ is the result of electrostatic attraction. Based on the quenching of fluorescence (enhancement of RRS) of GSH-capped CdTe QDs by FBZ, a novel, simple, rapid and specific method for FBZ determination was proposed. The detection limit for FBZ was 42 ng mL(-1) (3.4 ng mL(-1)) and the quantitative determination range was 0-2.8 μg mL(-1) with a correlation of 0.9985 (0.9979). The method has been applied to detect FBZ in real simples and with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

Infrared and Raman spectroscopic studies on alkali borate glasses: evidence of mixed alkali effect.

PubMed

Padmaja, G; Kistaiah, P

2009-03-19

A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition.

Photometric and Spectroscopic Study of the Delta Scuti Stars FH Cam, CU CVn and CC Lyn

NASA Astrophysics Data System (ADS)

Conidis, G. J.; Gazeas, K. D.; Capobianco, C. C.; Ogloza, W.

2010-06-01

Three short period (P ˜ 1 day) variable stars from the Hipparcos catalogue targets were observed after suspected misclassification as Beta Lyr eclipsing systems (Perryman et al. 1997), as no secondary component had been noticed in the inspection of their Broadening Functions (BFs) (Rucinski 2002). FH Cam is found to be a multiple star system with a member exhibiting Delta Scuti behaviour. The dominant pulsation frequency is found to be 7.3411 ± 0.0002 c/d, which corresponds to a pulsation mode of l ≤ 1. We confirmed the pulsations of CU CVn using photometric observations and found a pulsation frequency of 14.7626 ± 0.0250 c/d, which is in agreement with the period given in literature. CC Lyn is a non-eclipsing visual binary (CCDM J07359+4302AB), the brighter component (A) is found to be a multi-mode Delta Scuti pulsator, with pulsation frequencies of 5.6402 ± 0.0004 c/d and 7.3368 ± 0.0005 c/d.

Molecularly Imprinted Core-Shell CdSe@SiO2/CDs as a Ratiometric Fluorescent Probe for 4-Nitrophenol Sensing

NASA Astrophysics Data System (ADS)

Liu, Mingyue; Gao, Zhao; Yu, Yanjun; Su, Rongxin; Huang, Renliang; Qi, Wei; He, Zhimin

2018-01-01

4-Nitrophenol (4-NP) is a priority pollutant in water and is both carcinogenic and genotoxic to humans and wildlife even at very low concentrations. Thus, we herein fabricated a novel molecularly imprinted core-shell nanohybrid as a ratiometric fluorescent sensor for the highly sensitive and selective detection of 4-NP. This sensor was functioned by the transfer of fluorescence resonance energy between photoluminescent carbon dots (CDs) and 4-NP. This sensor was synthesized by linking organosilane-functionalized CDs to silica-coated CdSe quantum dots (CdSe@SiO2) via Si-O bonds. The nanohybrids were further modified by anchoring a molecularly imprinted polymer (MIP) layer on the ratiometric fluorescent sensor through a facile sol-gel polymerization method. The morphology, chemical structure, and optical properties of the resulting molecularly imprinted dual-emission fluorescent probe were characterized by transmission electron microscopy and spectroscopic analysis. The probe was then applied in the detection of 4-NP and exhibited good linearity between 0.051 and 13.7 μg/mL, in addition to a low detection limit of 0.026 μg/mL. Furthermore, the simplicity, reliability, high selectivity, and high sensitivity of the developed sensor demonstrate that the combination of MIPs and ratiometric fluorescence allows the preparation of excellent fluorescent sensors for the detection of trace or ultra-trace analytes.

New Eudesmane-Type Sesquiterpenoids from the Mangrove-Derived Endophytic Fungus Penicillium sp. J-54.

PubMed

Qiu, Liuming; Wang, Pei; Liao, Ge; Zeng, Yanbo; Cai, Caihong; Kong, Fandong; Guo, Zhikai; Proksch, Peter; Dai, Haofu; Mei, Wenli

2018-03-28

Four new eudesmane-type sesquiterpenoids, penicieudesmol A-D ( 1 - 4 ), were isolated from the fermentation broth of the mangrove-derived endophytic fungus Penicillium sp. J-54. Their structures were determined by spectroscopic methods, the in situ dimolybdenum CD method, and modified Mosher's method. The bioassays results showed that 2 exhibited weak cytotoxicity against K-562 cells.

VizieR Online Data Catalog: Cyanomethyl anion and its deuterated derivatives (Liton+, 2014)

NASA Astrophysics Data System (ADS)

Liton, M.; Das., A.; Chakrabarti, S. K.

2013-11-01

We performed detailed quantum chemical simulations to present the spectral properties (infrared, electronic, and rotational) of various forms of the cyanomethyl radical. Moller-Plesset perturbation theory along with the triple-zeta, correlation-consistent basis set is used to obtain different spectroscopic constants of CH2CN-, CHDCN-, and CD2CN- in the gas phase. (4 data files).

VizieR Online Data Catalog: Cyanomethyl anion and its deuterated derivatives (Majumdar+, 2014)

NASA Astrophysics Data System (ADS)

Majumdar, L.; Das., A.; Chakrabarti, S. K.

2013-11-01

We performed detailed quantum chemical simulations to present the spectral properties (infrared, electronic, and rotational) of various forms of the cyanomethyl radical. Moller-Plesset perturbation theory along with the triple-zeta, correlation-consistent basis set is used to obtain different spectroscopic constants of CH2CN-, CHDCN-, and CD2CN- in the gas phase. (4 data files).

Effect of preparation methods and doping on the structural and tunable emissions of CdS

NASA Astrophysics Data System (ADS)

Mohamed, Mohamed Bakr; Abdel-Kader, M. H.; Alhazime, Ali A.; Almarashi, Jamal Q. M.

2018-03-01

Fe, Mn and Mg doped CdS samples were prepared by thermolysis method in air and under flow of nitrogen. Structural, compositional and optical properties of the prepared samples were investigated using x-ray powder diffraction (XRD), scanning electron microscope (SEM/EDS mapping), Fourier transform infrared red (FTIR), UV-vis absorption and photoluminescence (PL) spectroscopes. Rietveld refinement of x-ray data showed that all the undoped and doped CdS samples prepared in air and under flow of nitrogen have both cubic and hexagonal structures. The percentages of hexagonal and cubic phases for all prepared samples were determined. The crystallite size increased for CdS prepared under flow of N2 compared with the sample prepared in air. The energy gap of all the samples was calculated using UV data. The intensity of PL emission changed according to the method of preparation and the kind of doping elements. PL emission revealed a blue shift for CdS prepared in air compared with CdS prepared under flow of nitrogen; also all doped samples showed a red shift of PL spectra compared with undoped samples. Undoped and doped CdS with Fe and Mg samples emitted violet and blue sub-spectra. Mn doped CdS prepared in air revealed violet, blue and yellow sub-spectra, while the sample prepared under flow of N2 emitted violet, blue and green sub-spectra.

Interaction of sodium benzoate with trypsin by spectroscopic techniques

NASA Astrophysics Data System (ADS)

Mu, Yue; Lin, Jing; Liu, Rutao

2011-12-01

The toxicity of sodium benzoate to trypsin was investigated by fluorescence spectroscopy, synchronous fluorescence spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy under mimic physiological conditions. Sodium benzoate could unfold trypsin by decreasing the β-sheet structure, which leads to more exposure of internal amino acid groups and the obvious intrinsic fluorescence quenching with the rising concentration of sodium benzoate. The results of spectroscopic measurements indicated that sodium benzoate changed the internal microenvironment of trypsin and induced the alteration of the whole molecule, which were performed toxic effects on the organism. Trypsin and sodium benzoate interacted with each other to produce a substance by van der Waals forces and hydrogen bond, the model of which was shown by AutoDock software.

Epitaxial Growth of Cadmium Telluride Films on Silicon and Indium Antimonide Substrates Using a Closed Hot Wall Epitaxy System

NASA Astrophysics Data System (ADS)

Kuo, Tien-Chuan

For many applications, such as infrared detector and high speed devices, we need high quality cadmium telluride (CdTe) films. To fabricate CdTe films we are using a home -built Closed Hot Wall Epitaxy system (CHWE). This system consists of two growth chambers, preheat chamber, substrate exchange load lock and ultra-high vacuum system. It can exchange the substrates without disturbing the vacuum environment and prevents the source materials from contamination. Two different substrate materials, Si and InSb, are used in this work. Deposition parameters were varied in order to determine the growth condition for obtaining good quality CdTe films. The characteristics of the films were investigated by Scanning Electron Microscope, X-ray diffractormeter and Auger Electron Spectroscope. The electrical properties of Al/CdTe/InSb MIS diodes are also examined. Experimental results show that the quality of the CdTe films on these two substrates are functions of the source and substrate temperatures. The surface of CdTe films grown on Si substrate are rougher than CdTe films grown on InSb substrate. X -ray patterns show that the crystal orientations of the CdTe films are, (100) and (111), similar to those of the substrates under optimum growth conditions. The CdTe film are stoichiometric based on the results of Auger survey. Electrical measurement also indicates that CdTe films grown on InSb substrates have very high purity and are insulator. The induced stresses due to the differences of lattice constant and thermal expansion coefficient between CdTe films and substrates were observed in CdTe films. The critical thickness of CdTe films on InSb substrates are measured by X-ray diffraction to be 2.63 um.

Four new steroids from the endophytic fungus Chaetomium sp. M453 derived of Chinese herbal medicine Huperzia serrata.

PubMed

Yu, Fei-Xue; Li, Zhe; Chen, Yao; Yang, Yin-He; Li, Guo-Hong; Zhao, Pei-Ji

2017-03-01

An endophytic fungus, Chaetomium sp. M453, was isolated from Huperzia serrata (Thunb. ex Murray) Trev. and subjected to phytochemical investigation. Three unusual C25 steroids, neocyclocitrinols E-G (1-3), and 3β-hydroxy-5,9-epoxy-(22E,24R)-ergosta-7,22-dien-6-one (4) together with three known steroids were isolated from solid fermentation products of the fungus, which were elucidated by extensive spectroscopic analyses, including 1D-, 2D-NMR, and HR-ESI-MS experiments. The absolute configuration of 1 was determined by X-ray crystallographic analysis and CD analyses. The acetylcholinesterase inhibitory activities of compounds 1-4 were tested in vitro. Compound 4 showed weak acetylcholinesterase inhibitory activity. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of band structure parameters and the quasi-particle gap of CdSe quantum dots by cyclic voltammetry.

PubMed

Inamdar, Shaukatali N; Ingole, Pravin P; Haram, Santosh K

2008-12-01

Band structure parameters such as the conduction band edge, the valence band edge and the quasi-particle gap of diffusing CdSe quantum dots (Q-dots) of various sizes were determined using cyclic voltammetry. These parameters are strongly dependent on the size of the Q-dots. The results obtained from voltammetric measurements are compared to spectroscopic and theoretical data. The fit obtained to the reported calculations based on the semi-empirical pseudopotential method (SEPM)-especially in the strong size-confinement region, is the best reported so far, according to our knowledge. For the smallest CdSe Q-dots, the difference between the quasi-particle gap and the optical band gap gives the electron-hole Coulombic interaction energy (J(e1,h1)). Interband states seen in the photoluminescence spectra were verified with cyclic voltammetry measurements.

New Eudesmane-Type Sesquiterpenoids from the Mangrove-Derived Endophytic Fungus Penicillium sp. J-54

PubMed Central

Qiu, Liuming; Wang, Pei; Liao, Ge; Zeng, Yanbo; Cai, Caihong; Kong, Fandong; Guo, Zhikai; Proksch, Peter; Dai, Haofu; Mei, Wenli

2018-01-01

Four new eudesmane-type sesquiterpenoids, penicieudesmol A–D (1–4), were isolated from the fermentation broth of the mangrove-derived endophytic fungus Penicillium sp. J-54. Their structures were determined by spectroscopic methods, the in situ dimolybdenum CD method, and modified Mosher’s method. The bioassays results showed that 2 exhibited weak cytotoxicity against K-562 cells. PMID:29597304

The synthesis and the spectroscopic, thermal, and structural properties of the M2[(fumarate)Ni(CN)4]·2(1,4-Dioxane) clathrate (M = Co, Ni, Cd and Hg)

NASA Astrophysics Data System (ADS)

Kartal, Zeki; Yavuz, Abdülkerim

2018-03-01

In this study, the clathrates of fumarate-tetracyanonickel-dioxane, given by the formula M2[(fumarate)Ni(CN)4]·2(1,4-Dioxane) (M = Co, Ni, Cd and Hg), have been obtained for the first time through chemical methods. These clathrates have been characterized by elemental, thermal, FT-IR, and FT-Raman spectroscopies. The parameters of structures of clathrates have been determined by X-ray powder diffraction. The thermal behaviors of these clathrates have been also investigated by thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), and derivative thermal gravimetric analysis (DTG) in the range of 20-900 °C. X-ray powder diffraction data have been recorded at ambient temperature in the 2θ range 5-50°. The FT-IR and FT-Raman spectra of clathrates have been recorded in the region of 4000-400 cm-1 and 4000-100 cm-1, respectively. The results of the spectral and thermal analyses of the newly synthesized clathrates of fumarate-tetracyanonickel-dioxane suggest that these clathrates are new examples of the Hofmann-type dioxane clathrates. In our study, the Hofmann-type dioxane clathrates, which are formed by bounding electrons of oxygen-donor atoms of fumarate ion ligand molecule to transition metal atoms, consist of the corrugated |M-Ni(CN)4|∞ polymeric layers, which are held in parallel through the chain of (-M-fumarate-M-).

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Carroll, Gerard Michael

This thesis presents investigations for two related fields of semiconductor electrochemistry: redox potential determination of colloidal semiconductor nanocrystals, and mechanistic analysis of photoelectrochemical water oxidation with electrocatalyst modified mesostructured hematite photoanodes. Adapting electrochemical techniques to colloidal semiconductor nanocrystals (SC NC) is a long-standing challenge for this class of materials. Subject to a variety of complications, standard voltammetric techniques are not as straight forward for SC NCs as they are for small molecules. As a result, researchers have developed creative ways to side step these complications by coupling electrochemistry with NC spectroscopy. Chapter 1 discusses the fundamental electronic and spectroscopic properties of SC NCs at different redox states. We present a brief review of some of the notable studies employing SC NC spectroelectrochemistry that provide the theoretical and experimental context for the following chapters. Chapter 2 presents an investigation on NC redox potentials of photochemically reduced colloidal ZnO NCs using a solvated redox-indicator method. In the one electron limit, conduction band electrons show evidence of quantum confinement, but at higher electron concentrations, the NC Fermi-level becomes dependent on the electron density across all NC sizes. Chapter 3 outlines a poteniometric method for monitoring the NC redox potentials in situ. NC redox potentials for ZnO and CdSe are measured, and as predicted from these measurements, spontaneous electron transfer from CdSe to ZnO is demonstrated. Chapter 4 details the impact of the surface of CdSe NCs on the NC redox potentials. We find that the ratio of Cd2+:Se2- on the surface of CdSe NCs changes both the NC band edge potentials, as well as the maximum electron density achievable by photochemical reduction. These changes are proposed to arise from interfacial dipoles when CdSe has a Se2-rich surface. Chapters 5 and 6 examine the mechanistic pathways of solar water oxidation on Co-Pi modified alpha-Fe2O3 photoanodes. A rate constant analysis of water oxidation and electron-hole recombination paired with the identification of surface-morphology-dependent current-voltage characteristics reveal new insights into the role of the semiconductor/electrocatalyst interface on the overall solar water oxidation efficiency. These findings reconcile disparate observations from previous studies.

Interaction Mode between Inclusion Complex of Vitamin K3 with γ- Cyclodextrin and Herring-Sperm DNA.

PubMed

Tang, Yan; Cai, Li; Xue, Kang; Wang, Chunling; Xiong, Xiaoli

2016-05-03

Methods including spectroscopy, electronic chemistry and thermodynamics were used to study the inclusion effect between γ-cyclodextrin (CD) and vitamin K3(K3), as well as the interaction mode between herring-sperm DNA (hsDNA) and γ-CD-K3 inclusion complex. The results from ultraviolet spectroscopic method indicated that VK3 and γ-CD formed 1:1 inclusion complex, with the inclusion constant Kf = 1.02 × 10(4) L/mol, which is based on Benesi-Hildebrand's viewpoint. The outcomes from the probe method and Scatchard methods suggested that the interaction mode between γ-CD-K3 and DNA was a mixture mode, which included intercalation and electrostatic binding effects. The binding constants were K (θ)25°C = 2.16 × 10(4) L/mol, and K(θ)37°C = 1.06 × 10(4) L/mol. The thermodynamic functions of the interaction between γ-CD-K3 and DNA were ΔrHm(θ) = -2.74 × 10(4) J/mol, ΔrSm(θ) = 174.74 J·mol(-1)K(-1), therefore, both ΔrHm(θ) (enthalpy) and ΔrSm(θ) (entropy) worked as driven forces in this action.

Progress in the Development of CdZnTe Unipolar Detectors for Different Anode Geometries and Data Corrections

PubMed Central

Zhang, Qiushi; Zhang, Congzhe; Lu, Yanye; Yang, Kun; Ren, Qiushi

2013-01-01

CdZnTe detectors have been under development for the past two decades, providing good stopping power for gamma rays, lightweight camera heads and improved energy resolution. However, the performance of this type of detector is limited primarily by incomplete charge collection problems resulting from charge carriers trapping. This paper is a review of the progress in the development of CdZnTe unipolar detectors with some data correction techniques for improving performance of the detectors. We will first briefly review the relevant theories. Thereafter, two aspects of the techniques for overcoming the hole trapping issue are summarized, including irradiation direction configuration and pulse shape correction methods. CdZnTe detectors of different geometries are discussed in detail, covering the principal of the electrode geometry design, the design and performance characteristics, some detector prototypes development and special correction techniques to improve the energy resolution. Finally, the state of art development of 3-D position sensing and Compton imaging technique are also discussed. Spectroscopic performance of CdZnTe semiconductor detector will be greatly improved even to approach the statistical limit on energy resolution with the combination of some of these techniques. PMID:23429509

Investigations on the interactions of aurintricarboxylic acid with bovine serum albumin: Steady state/time resolved spectroscopic and docking studies.

PubMed

Bardhan, Munmun; Chowdhury, Joydeep; Ganguly, Tapan

2011-01-10

In this paper, the nature of the interactions between bovine serum albumin (BSA) and aurintricarboxylic acid (ATA) has been investigated by measuring steady state and time-resolved fluorescence, circular dichroism (CD), FT-IR and fluorescence anisotropy in protein environment under physiological conditions. From the analysis of the steady state and time-resolved fluorescence quenching of BSA in aqueous solution in presence of ATA it has been inferred that the nature of the quenching originates from the combined effect of static and dynamic modes. From the determination of the thermodynamic parameters obtained from temperature-dependent changes in K(b) (binding constant) it was apparent that the combined effect of hydrophobic association and electrostatic attraction is responsible for the interaction of ATA with BSA. The effect of ATA on the conformation of BSA has been examined by analyzing CD spectrum. Though the observed results demonstrate some conformational changes in BSA in presence of ATA but the secondary structure of BSA, predominantly of α-helix, is found to retain its identity. Molecular docking of ATA with BSA also indicates that ATA docks through hydrophobic interaction. Copyright © 2010 Elsevier B.V. All rights reserved.

Separation and identification of anthocyanin extracted from mulberry fruit and the pigment binding properties toward human serum albumin.

PubMed

Sheng, Feng; Wang, Yuning; Zhao, Xingchen; Tian, Na; Hu, Huali; Li, Pengxia

2014-07-16

Purple pigments were isolated from mulberry extracts using preparative high-speed countercurrent chromatography (HSCCC) and identified by ESI-MS/MS and high performance liquid chromatography (HPLC) techniques. The solvent system containing methyl tert-butyl ether, 1-butanol, acetonitrile, water, and trifluoroacetic acid (10:30:10:50:0.05; %, v/v) was developed in order to separate anthocyanins with different polarities. Cyanidin 3-O-(6″-O-α-rhamnopyranosyl-β-galactopyranoside) (also known as keracyanin) is the major component present in mulberry (41.3%). Other isolated pigments are cyanidin 3-O-(6″-O-α-rhamnopyranosyl-β-glucopyranoside) and petunidin 3-O-β-glucopyranoside. The binding characteristics of keracyanin with human serum albumin (HSA) were investigated by fluorescence and circular dichroism (CD) spectroscopy. Spectroscopic analysis reveals that HSA fluorescence quenched by keracyanin follows a static mode. Binding of keracyanin to HSA mainly depends on van der Waals force or H-bonds with average binding distance of 2.82 nm. The results from synchronous fluorescence, three-dimensional fluorescence, and CD spectra show that adaptive structure rearrangement and decrease of α-helical structure occur in the presence of keracyanin.

Co(II) and Cd(II) Complexes Derived from Heterocyclic Schiff-Bases: Synthesis, Structural Characterisation, and Biological Activity

PubMed Central

Ahmed, Riyadh M.; Yousif, Enaam I.; Al-Jeboori, Mohamad J.

2013-01-01

New monomeric cobalt and cadmium complexes with Schiff-bases, namely, N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]furan-2-carbohydrazide (L1) and N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]thiophene-2-carbohydrazide (L2) are reported. Schiff-base ligands L1 and L2 were derived from condensation of 3-hydroxy-4-methoxybenzaldehyde (iso-vanillin) with furan-2-carboxylic acid hydrazide and thiophene-2-carboxylic acid hydrazide, respectively. Complexes of the general formula [M(L)2]Cl2 (where M = Co(II) or Cd(II), L = L1 or L2) have been obtained from the reaction of the corresponding metal chloride with the ligands. The ligands and their metal complexes were characterised by spectroscopic methods (FTIR, UV-Vis, 1H, and 13C NMR spectra), elemental analysis, metal content, magnetic measurement, and conductance. These studies revealed the formation of four-coordinate complexes in which the geometry about metal ion is tetrahedral. Biological activity of the ligands and their metal complexes against gram positive bacterial strain Bacillus (G+) and gram negative bacteria Pseudomonas (G−) revealed that the metal complexes become less resistive to the microbial activities as compared to the free ligands. PMID:24027449

Crystal structure, complexation, spectroscopic characterization and antimicrobial evaluation of 3,4-dihydroxybenzylidene isonicotinyl-hydrazone

NASA Astrophysics Data System (ADS)

Jeragh, Bakir; Ali, Mayada S.; El-Asmy, Ahmed A.

2015-06-01

A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO2+, Zr4+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Pd2+ complexes of HBINH have been prepared and spectroscopically characterized. The data confirmed the formulae [Co(HBINH)(H2O)Cl]Cl·H2O, [Pd(HBINH)Cl2], [Zn(HBINH)2Cl2], [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)], [Ni2(HBINH)(H2O)6Cl2]Cl2, [Cu2(HBINH-3H)(H2O)2(OAc)]·3H2O, [Zr2(HBINH-3H)Cl4]Cl, [Hg2(HBINH)Cl4] and the dimer {[Cu(HBINH)Cl]Cl}2. Most of the complexes have intense colors and high melting points and some are electrolytes in DMSO solution. The ligand behaves as a neutral bidentate in the Co(II), Cu(II), Pd(II), Zn(II) and Cd(II) complexes; dibasic tetradentate in [Ni2(HBINH)(H2O)6Cl2]Cl2 and tribasic tetradentate in [Cu2(HBINH-3H)(OAc)]·5H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Zr2(HBINH-3H)Cl4]Cl by the loss of 3H+ due to the deprotonation of the two hydroxyl groups and the enolization of the amide (Odbnd CNH) group. A tetrahedral geometry was proposed for the Co(II), Cu(II), Zn(II) and Hg(II) complexes; square-planar for the Pd(II) complex; square-pyramid for the VO2+ complex and octahedral for the Ni(II) and Cd(II) complexes. The complexes [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Cu2(HBINH-3H)-(H2O)2(OAc)]·3H2O have activities against Bacillus sp. M3010, Candida albicans, Escherichia coli, Staphylococcus aureus and Slamonella sp. PA393.

Spectroscopic analysis and control

DOEpatents

Tate; , James D.; Reed, Christopher J.; Domke, Christopher H.; Le, Linh; Seasholtz, Mary Beth; Weber, Andy; Lipp, Charles

2017-04-18

Apparatus for spectroscopic analysis which includes a tunable diode laser spectrometer having a digital output signal and a digital computer for receiving the digital output signal from the spectrometer, the digital computer programmed to process the digital output signal using a multivariate regression algorithm. In addition, a spectroscopic method of analysis using such apparatus. Finally, a method for controlling an ethylene cracker hydrogenator.

A multi-analytical investigation of semi-conductor pigments with time-resolved spectroscopy and imaging

NASA Astrophysics Data System (ADS)

Nevin, A.; Cesaratto, A.; D'Andrea, C.; Valentini, Gianluca; Comelli, D.

2013-05-01

We present the non-invasive study of historical and modern Zn- and Cd-based pigments with time-resolved fluorescence spectroscopy, fluorescence multispectral imaging and fluorescence lifetime imaging (FLIM). Zinc oxide and Zinc sulphide are semiconductors which have been used as white pigments in paintings, and the luminescence of these pigments from trapped states is strongly dependent on the presence of impurities and crystal defects. Cadmium sulphoselenide pigments vary in hue from yellow to deep red based on their composition, and are another class of semiconductor pigments which emit both in the visible and the near infrared. The Fluorescence lifetime of historical and modern pigments has been measured using both an Optical Multichannel Analyser (OMA) coupled with a Nd:YAG nslaser, and a streak camera coupled with a ps-laser for spectrally-resolved fluorescence lifetime measurements. For Znbased pigments we have also employed Fluorescence Lifetime Imaging (FLIM) for the measurement of luminescence. A case study of FLIM applied to the analysis of the painting by Vincent Van Gogh on paper - "Les Bretonnes et le pardon de Pont-Aven" (1888) is presented. Through the integration of complementary, portable and non-invasive spectroscopic techniques, new insights into the optical properties of Zn- and Cd-based pigments have been gained which will inform future analysis of late 19th] and early 20th C. paintings.

Cyclodextrin-based metal-organic frameworks particles as efficient carriers for lansoprazole: Study of morphology and chemical composition of individual particles.

PubMed

Li, Xue; Guo, Tao; Lachmanski, Laurent; Manoli, Francesco; Menendez-Miranda, Mario; Manet, Ilse; Guo, Zhen; Wu, Li; Zhang, Jiwen; Gref, Ruxandra

2017-10-15

Cyclodextrin-based metal-organic frameworks (CD-MOFs) represent an environment-friendly and biocompatible class of MOFs drawing increasing attention in drug delivery. Lansoprazole (LPZ) is a proton-pump inhibitor used to reduce the production of acid in the stomach and recently identified as an antitubercular prodrug. Herein, LPZ loaded CD-MOFs were successfully synthesized upon the assembly with γ-CD in the presence of K + ions using an optimized co-crystallization method. They were characterized in terms of morphology, size and crystallinity, showing almost perfect cubic morphologies with monodispersed size distributions. The crystalline particles, loaded or not with LPZ, have mean diameters of around 6μm. The payloads reached 23.2±2.1% (wt) which corresponds to a molar ratio of 1:1 between LPZ and γ-CD. It was demonstrated that even after two years storage, the incorporated drug inside the CD-MOFs maintained its spectroscopic characteristics. Molecular modelling provided a deeper insight into the interaction between the LPZ and CD-MOFs. Raman spectra of individual particles were recorded, confirming the formation of inclusion complexes within the tridimensional CD-MOF structures. Of note, it was found that each individual particle had the same chemical composition. The LPZ-loaded particles had remarkable homogeneity in terms of both drug loading and size. These results pave the way towards the use of CD-MOFs for drug delivery purposes. Copyright © 2017 Elsevier B.V. All rights reserved.

Unique Features of the Photocatalytic Reduction of H2O and CO2 by New Catalysts Based on the Analogues of CdS, Cd4P2X3 (X = Cl, Br, I).

PubMed

Roy, Anand; Chhetri, Manjeet; Prasad, Suchitra; Waghmare, Umesh V; Rao, C N R

2018-01-24

Photochemical reduction of H 2 O and CO 2 has been investigated with a new family of catalysts of the formula Cd 4 P 2 X 3 (X= Cl, Br, I), obtained by the complete aliovalent substitution of the sulfide ions in CdS by P and X (Cl, Br, I). Unlike CdS, the Cd 4 P 2 X 3 compounds exhibit hydrogen evolution and CO 2 reduction from water even in the absence of a sacrificial agent or a cocatalyst. Use of Ni x P y as the cocatalyst, enhances hydrogen evolution, reaching 3870 (apparent quantum yield (AQY) = 4.11) and 9258 (AQY = 9.83) μmol h -1 g -1 , respectively, under artificial and natural (sunlight) irradiation, in the case of Cd 4 P 2 Br 3 /Ni x P y . Electrochemical and spectroscopic studies have been employed to understand the photocatalytic activity of this family of compounds. Unlike most of the semiconductor-based photocatalysts, Cd 4 P 2 X 3 catalysts reduce CO 2 to CO and CH 4 in the absence of sacrificial-agent or cocatalyst using water as the electron source. CO, CH 4 , and H 2 have been obtained with these catalysts under artificial as well as sun-light irradiation. First-principles, calculations have been carried out to understand the electronic structure and catalytic features of these new catalysts.

Structural and functional characterization of recombinant napin-like protein of Momordica charantia expressed in methylotrophic yeast Pichia pastoris.

PubMed

Yadav, Shailesh Kumar R; Sahu, Tejram; Dixit, Aparna

2016-08-01

Napin and napin-like proteins belong to the 2S albumin seed storage family of proteins and have been shown to display a variety of biological activities. However, due to a high degree of polymorphism, purification of a single napin or napin-like protein exhibiting biological activity is extremely difficult. In the present study, we have produced the napin-like protein of Momordica charantia using the methylotrophic Pichia pastoris expression system. The recombinant napin-like protein (rMcnapin) secreted in the extracellular culture supernatant was enriched by ammonium sulfate precipitation, and purified using size exclusion chromatography at a yield of ∼290 mg/L of culture. Secondary structure analysis of the purified rMcnapin revealed it to be predominantly α-helical with minimal β strand content. CD spectroscopic and fluorescence spectroscopic analyses revealed the rMcnapin to be stable at a wide range of temperatures and pH. The rMcnapin exhibited antifungal activity against Trichoderma viride with an IC50 of ∼3.7 μg/ml and trypsin inhibitor activity with an IC50 of 4.2 μM. Thus, large amounts of homogenous preparations of the biologically active rMcnapin could be obtained at shake flask level, which is otherwise difficult from its natural source.

Multi-spectroscopic and molecular docking studies on the interaction of darunavir, a HIV protease inhibitor with calf thymus DNA

NASA Astrophysics Data System (ADS)

Shi, Jie-Hua; Zhou, Kai-Li; Lou, Yan-Yue; Pan, Dong-Qi

2018-03-01

Molecular interaction of darunavir (DRV), a HIV protease inhibitor with calf thymus deoxyribonucleic acid (ct-DNA) was studied in physiological buffer (pH 7.4) by multi-spectroscopic approaches hand in hand with viscosity measurements and molecular docking technique. The UV absorption and fluorescence results together revealed the formation of a DRV-ct-DNA complex having binding affinities of the order of 103 M- 1, which was more in keeping with the groove binding. The results that DRV bound to ct-DNA via groove binding mode was further evidenced by KI quenching studies, viscosity measurements, competitive binding investigations with EB and Rhodamine B and CD spectral analysis. The effect of ionic strength indicated the negligible involvement of electrostatic interaction between DRV and ct-DNA. The thermodynamic parameters regarding the binding interaction of DRV with ct-DNA in terms of enthalpy change (ΔH0) and entropy change (ΔS0) were - 63.19 kJ mol- 1 and - 141.92 J mol- 1 K- 1, indicating that hydrogen bonds and van der Waals forces played a predominant role in the binding process. Furthermore, molecular simulation studies suggested that DRV molecule was prone to bind in the A-T rich region of the minor groove of DNA.

Interaction of sodium benzoate with trypsin by spectroscopic techniques.

PubMed

Mu, Yue; Lin, Jing; Liu, Rutao

2011-12-01

The toxicity of sodium benzoate to trypsin was investigated by fluorescence spectroscopy, synchronous fluorescence spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy under mimic physiological conditions. Sodium benzoate could unfold trypsin by decreasing the β-sheet structure, which leads to more exposure of internal amino acid groups and the obvious intrinsic fluorescence quenching with the rising concentration of sodium benzoate. The results of spectroscopic measurements indicated that sodium benzoate changed the internal microenvironment of trypsin and induced the alteration of the whole molecule, which were performed toxic effects on the organism. Trypsin and sodium benzoate interacted with each other to produce a substance by van der Waals forces and hydrogen bond, the model of which was shown by AutoDock software. Copyright © 2011 Elsevier B.V. All rights reserved.

The effects of biological buffers TRIS, TAPS, TES on the stability of lysozyme.

PubMed

Pannuru, Pavani; Rani, Anjeeta; Venkatesu, Pannuru; Lee, Ming-Jer

2018-06-01

To explore the mechanism of lysozyme stabilization in buffer system, we have investigated the interactions between lysozyme and the biological buffers (TRIS, TAPS, and TES) using spectroscopic techniques, including ultraviolet-visible (UV-Vis), fluorescence, thermal fluorescence, dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and circular dichroism (CD) spectroscopy. From the series of spectroscopic studies, it is found that the native structure of the protein remains intact in the different concentrations (0.05, 0.1, 0.25, 0.5, and 1.0M) of the biological buffer aqueous solutions at pH7.0. Moreover, all these three investigated buffers are able to protect lysozyme against thermal denaturation, particularly in high concentration (1.0M) of the buffer aqueous solutions. Copyright © 2018 Elsevier B.V. All rights reserved.

Investigation of 112Cd via the (d,p) Reaction and a Reassessment of the Quadrupole-Octupole Coupled Excitation

NASA Astrophysics Data System (ADS)

Jamieson, D. S.; Garrett, P. E.; Ball, G. C.; Demand, G. A.; Faestermann, T.; Finlay, P.; Green, K. L.; Hertenberger, R.; Leach, K. G.; Phillips, A. A.; Sumithrarachchi, C. S.; Svensson, C. E.; Triambak, S.; Wirth, H.-F.; Wong, J.

The single-particle neutron states in 112Cd have been probed with the 111Cd(d,p) reaction. Beams of up to 1.2 µA of polarized 22 MeV deuterons bombarded 111Cd targets. The reaction protons were momentum analyzed with a Q3D magnetic spectrograph, with spectra were recorded at 10 angles between 10 and 60° with a resolution of 6-7 keV FWHM. In addition to the (d,p) transfer data, (d,d) elastic-scattering data were also obtained and used to ascertain the proper optical model parameters. Cross sections and analyzing powers for all levels observed to be populated were fit to results of DWBA and ADWA calculations, and spectroscopic factors were determined. The 5- level at 2373 keV, previously assigned as a member on the quadrupole-octupole quintuplet set of states because of its enhanced B(E2;5 - to 31 - ) value, was observed to be one of the strongest peaks in the spectrum, and is reassigned as the s1/2 otimes h11/2 two-quasineutron configuration.

Rational design of tetraphenylethylene-based luminescent down-shifting molecules: photophysical studies and photovoltaic applications in a CdTe solar cell from small to large units.

PubMed

Li, Yilin; Li, Zhipeng; Ablekim, Tursunjan; Ren, Tianhui; Dong, Wen-Ji

2014-12-21

A rational design strategy of novel fluorophores for luminescent down-shifting (LDS) application was proposed and tested in this paper. Three new fluorophores (1a-c) with specific intramolecular charge transfer (ICT) and aggregation-induced emission (AIE) characteristics were synthesized as LDS molecules for increasing the output short circuit current density (Jsc) of a CdTe solar cell. Photophysical studies of their solution and solid states, and photovoltaic measurements of their PMMA solid films applied on a CdTe solar cell suggested that the specific spectroscopic properties and Jsc enhancement effects of these molecules were highly related to their chemical structures. The Jsc enhancement effects of these fluorophores were measured on both a CdTe small cell and a large panel. An increase in the output Jsc by as high as 5.69% for a small cell and 8.88% for a large panel was observed. Compared to a traditional LDS molecule, Y083, these fluorophores exhibited more superior capabilities of LDS.

Phytosterols isolated from Clinacanthus nutans induce immunosuppressive activity in murine cells.

PubMed

Le, Cheng-Foh; Kailaivasan, Thina Hareesh; Chow, Sek-Chuen; Abdullah, Zunoliza; Ling, Sui-Kiong; Fang, Chee-Mun

2017-03-01

Clinacanthus nutans (Burm. f.) Lindau is a traditional medicinal plant belonging to the Acanthaceae family. Its therapeutic potentials have been increasingly documented particularly the antiviral activity against Herpes Simplex Virus (HSV), anti-cancer, anti-oxidant, anti-inflammatory and immunomodulatory activities. However, majority of these studies used crude or fractionated extracts and not much is known about individual compounds from these extracts and their biological activities. In the present study, we have isolated four compounds (CN1, CN2, CN3 and CN4) from the hexane fractions of C. nutans leaves. Using NMR spectroscopic analysis, these compounds were identified to be shaftoside (CN1), stigmasterol (CN2), β-sitosterol (CN3) and a triterpenoid lupeol (CN4). To determine the immunosuppressive potential of these compounds, their effects on mitogens induced T and B lymphocyte proliferation and the secretion of helper T cell cytokines were examined. Among the four compounds, stigmasterol (CN2) and β-sitosterol (CN3) were shown to readily inhibit T cell proliferation mediated by Concanavalin A (ConA). However, only β-sitosterol (CN3) and not stigmasterol (CN2) blocks the secretion of T helper 2 (Th2) cytokines (IL-4 and IL-10). Both compounds have no effect on the secretion of Th1 cytokines (IL-2 and IFN-γ), suggesting that β-sitosterol treatment selectively suppresses Th2 activity and promotes a Th1 bias. CN3 was also found to significantly reduce the proliferation of both T helper cells (CD4 + CD25 + ) and cytotoxic T cells (CD8 + CD25 + ) following T cell activation induced by ConA. These results suggested that phytosterols isolated from C. nutans possess immunomodulatory effects with potential development as immunotherapeutics. Copyright © 2017 Elsevier B.V. All rights reserved.

Estrogen-Induced Depurination of DNA: A Novel Target for Breast Cancer Prevention

DTIC Science & Technology

2006-05-01

of Dietary N- Acetylcysteine on Neonatal Initiation of Uterine Adenocarcinomas in Female CD-1 mice by Catechol Estrogens To begin to study the...ability of selected natural compounds to prevent estrogen-initiated cancers, we planned to study the effect of N- acetylcysteine (NAcCys) on the initiation...Jankowiak, R. Development of monoclonal antibodies to 4-hydroxyestrogen-2-N- acetylcysteine conjugates: Immunoaffinity and spectroscopic studies

Characterization of domain-specific interaction of synthesized dye with serum proteins by spectroscopic and docking approaches along with determination of in vitro cytotoxicity and antiviral activity.

PubMed

Rudra, Suparna; Dasmandal, Somnath; Patra, Chiranjit; Patel, Biman Kumar; Paul, Suvendu; Mahapatra, Ambikesh

2017-11-20

The interaction between a synthesized dye with proteins, bovine, and human serum albumin (BSA, HSA, respectively) under physiological conditions has been characterized in detail, by means of steady-state and time-resolved fluorescence, UV-vis absorption, and circular dichroism (CD) techniques. An extensive time-resolved fluorescence spectroscopic characterization of the quenching process has been undertaken in conjugation with temperature-dependent fluorescence quenching studies to divulge the actual quenching mechanism. From the thermodynamic observations, it is clear that the binding process is a spontaneous molecular interaction, in which van der Waals and hydrogen bonding interactions play the major roles. The UV-vis absorption and CD results confirm that the dye can induce conformational and micro-environmental changes of both the proteins. In addition, the dye binding provokes the functionality of the native proteins in terms of esterase-like activity. The average binding distance (r) between proteins and dye has been calculated using FRET. Cytotoxicity and antiviral effects of the dye have been found using Vero cell and HSV-1F virus by performing MTT assay. The AutoDock-based docking simulation reveals the probable binding location of dye within the sub-domain IIA of HSA and IB of BSA.

Quasi-aromatic Möbius Metal Chelates.

PubMed

Mahmoudi, Ghodrat; Afkhami, Farhad A; Castiñeiras, Alfonso; García-Santos, Isabel; Gurbanov, Atash; Zubkov, Fedor I; Mitoraj, Mariusz P; Kukułka, Mercedes; Sagan, Filip; Szczepanik, Dariusz W; Konyaeva, Irina A; Safin, Damir A

2018-04-16

We report the design as well as structural and spectroscopic characterizations of two new coordination compounds obtained from Cd(NO 3 ) 2 ·4H 2 O and polydentate ligands, benzilbis(pyridin-2-yl)methylidenehydrazone (L I ) and benzilbis(acetylpyridin-2-yl)methylidenehydrazone (L II ), in a mixture with two equivalents of NH 4 NCS in MeOH, namely [Cd(SCN)(NCS)(L I )(MeOH)] (1) and [Cd(NCS) 2 (L II )(MeOH)] (2). Both L I and L II are bound via two pyridyl-imine units yielding a tetradentate coordination mode giving rise to the 12 π electron chelate ring. It has been determined for the first time (qualitatively and quantitatively), using the EDDB electron population-based method, the HOMA index, and the ETS-NOCV charge and energy decomposition scheme, that the chelate ring containing Cd II can be classified as a quasi-aromatic Möbius motif. Notably, using the methyl-containing ligand L II controls the exclusive presence of the NCS - connected with the Cd II atom (structure 2), while applying L I allows us to simultaneously coordinate NCS - and SCN - ligands (structure 1). Both systems are stabilized mostly by hydrogen bonding, C-H···π interactions, aromatic π···π stacking, and dihydrogen C-H···H-C bonds. The optical properties have been investigated by diffused reflectance spectroscopy as well as molecular and periodic DFT/TD-DFT calculations. The DFT-based ETS-NOCV analysis as well as periodic calculations led us to conclude that the monomers which constitute the obtained chelates are extremely strongly bonded to each other, and the calculated interaction energies are found to be in the regime of strong covalent connections. Intramolecular van der Waals dispersion forces, due to the large size of L I and L II , appeared to significantly stabilize these systems as well as amplify the aromaticity phenomenon.

Ground calibration of the spatial response and quantum efficiency of the CdZnTe hard x-ray detectors for NuSTAR

NASA Astrophysics Data System (ADS)

Grefenstette, Brian W.; Bhalerao, Varun; Cook, W. Rick; Harrison, Fiona A.; Kitaguchi, Takao; Madsen, Kristin K.; Mao, Peter H.; Miyasaka, Hiromasa; Rana, Vikram

2017-08-01

Pixelated Cadmium Zinc Telluride (CdZnTe) detectors are currently flying on the Nuclear Spectroscopic Telescope ARray (NuSTAR) NASA Astrophysics Small Explorer. While the pixel pitch of the detectors is ≍ 605 μm, we can leverage the detector readout architecture to determine the interaction location of an individual photon to much higher spatial accuracy. The sub-pixel spatial location allows us to finely oversample the point spread function of the optics and reduces imaging artifacts due to pixelation. In this paper we demonstrate how the sub-pixel information is obtained, how the detectors were calibrated, and provide ground verification of the quantum efficiency of our Monte Carlo model of the detector response.

Calibration method for spectroscopic systems

DOEpatents

Sandison, David R.

1998-01-01

Calibration spots of optically-characterized material placed in the field of view of a spectroscopic system allow calibration of the spectroscopic system. Response from the calibration spots is measured and used to calibrate for varying spectroscopic system operating parameters. The accurate calibration achieved allows quantitative spectroscopic analysis of responses taken at different times, different excitation conditions, and of different targets.

Calibration method for spectroscopic systems

DOEpatents

Sandison, D.R.

1998-11-17

Calibration spots of optically-characterized material placed in the field of view of a spectroscopic system allow calibration of the spectroscopic system. Response from the calibration spots is measured and used to calibrate for varying spectroscopic system operating parameters. The accurate calibration achieved allows quantitative spectroscopic analysis of responses taken at different times, different excitation conditions, and of different targets. 3 figs.

Vaccinols J-S, ten new salicyloid derivatives from the marine mangrove-derived endophytic fungus Pestalotiopsis vaccinii.

PubMed

Wang, Jun-Feng; Liang, Rui; Liao, Sheng-Rong; Yang, Bin; Tu, Zheng-Chao; Lin, Xiu-Ping; Wang, Bin-Gui; Liu, Yonghong

2017-07-01

Ten new salicyloid derivatives, namely vaccinols J-S (1-10), along with five known compounds (11-15) were isolated from Pestalotiopsis vaccinii (cgmcc3.9199) endogenous with the mangrove plant Kandelia candel (L.) Druce (Rhizophoraceae). Their structures including absolute configurations were established on the basis of spectroscopic analysis, optical rotation, CD spectra, quantum ECD calculations. To the best of our knowledge, vaccinol J (1) is the first example of salicyloid derivatives containing 2-methylfuran moiety. All of the new compounds were tested for their anti-enterovirus 7l (EV71) and cytotoxic activities. Among them, vaccinol J (1) exhibited in vitro anti-EV71 with IC 50 value of 30.7μM (IC 50 177.0μM for the positive control ribavirin). Copyright © 2017. Published by Elsevier B.V.

Kinetic and CD/MCD spectroscopic studies of the atypical, three-His-ligated, non-heme Fe2+ center in diketone dioxygenase: the role of hydrophilic outer shell residues in catalysis.

PubMed

Straganz, Grit D; Diebold, Adrienne R; Egger, Sigrid; Nidetzky, Bernd; Solomon, Edward I

2010-02-09

Diketone cleaving enzyme (Dke1) is a dioxygenase with an atypical, three-histidine-ligated, mononuclear non-heme Fe(2+) center. To assess the role in enzyme catalysis of the hydrophilic residues in the active site pocket, residues Glu98, Arg80, Tyr70, and Thr107 were subjected to mutational analysis. Steady state and pre-steady state kinetics indicated a role for Glu98 in promoting both substrate binding and O(2) reduction. Additionally, the Glu98 substitution eliminated the pH dependence of substrate binding (k(cat)(app)/K(M)(app)-pH profile) present in wild-type Dke1 (pK(a) = 6.3 +/- 0.4 and 8.4 +/- 0.4). MCD spectroscopy revealed that the Glu98 --> Gln mutation leads to the conversion of the six-coordinate (6C) resting Fe(2+) center present in the wild-type enzyme at pH 7.0 to a mixture of five-coordinate (5C) and 6C sites. The 6C geometry was restored with a pH shift to 9.5 which also resulted in ligand field (LF) energy splittings identical to that found for wild-type (WT) Dke1 at pH 9.5. In WT Dke1, these LF transitions are shifted up in energy by approximately 300 cm(-1) at pH 9.5 relative to pH 7.0. These data, combined with CD pH titrations which reveal a pK(a) of approximately 8.2 for resting WT Dke1 and the Glu98 --> Gln variant, indicate the deprotonation of a metal-ligated water. Together, the kinetic and spectroscopic data reveal a stabilizing effect of Glu98 on the 6C geometry of the metal center, priming it for substrate ligation. Arg80 and Tyr70 are shown to promote O(2) reduction, while Thr107 stabilizes the Fe(II) cofactor.

Interaction between phillygenin and human serum albumin based on spectroscopic and molecular docking

NASA Astrophysics Data System (ADS)

Song, W.; Ao, M. Z.; Shi, Y.; Yuan, L. F.; Yuan, X. X.; Yu, L. J.

2012-01-01

In this paper, the interaction of human serum albumin (HSA) with phillygenin was investigated by fluorescence, circular dichroism (CD), UV-vis spectroscopic and molecular docking methods under physiological conditions. The Stern-Volmer analysis indicated that the fluorescence quenching of HSA by phillygenin resulted from static mechanism, and the binding constants were 1.71 × 10 5, 1.61 × 10 5 and 1.47 × 10 4 at 300, 305 and 310 K, respectively. The results of UV-vis spectra show that the secondary structure of the protein has been changed in the presence of phillygenin. The CD spectra showed that HSA conformation was altered by phillygenin with a major reduction of α-helix and an increase in β-sheet and random coil structures, indicating a partial protein unfolding. The distance between donor (HSA) and acceptor (phillygenin) was calculated to be 3.52 nm and the results of synchronous fluorescence spectra showed that binding of phillygenin to HSA can induce conformational changes in HSA. Molecular docking experiments found that phillygenin binds with HSA at IIIA domain of hydrophobic pocket with hydrogen bond interactions. The ionic bonds were formed with the O (4), O (5) and O (6) of phillygenin with nitrogen of ASN109, ARG186 and LEU115, respectively. The hydrogen bonds are formed between O (2) of phillygenin and SER419. In the presence of copper (II), iron (III) and alcohol, the apparent association constant KA and the number of binding sites of phillygenin on HSA were both decreased in the range of 88.84-91.97% and 16.09-18.85%, respectively. In view of the evidence presented, it is expected to enrich our knowledge of the interaction dynamics of phillygenin to the important plasma protein HSA, and it is also expected to provide important information of designs of new inspired drugs.

Wave Function Engineering in CdSe/PbS Core/Shell Quantum Dots.

PubMed

Wieliczka, Brian M; Kaledin, Alexey L; Buhro, William E; Loomis, Richard A

2018-05-25

The synthesis of epitaxial CdSe/PbS core/shell quantum dots (QDs) is reported. The PbS shell grows in a rock salt structure on the zinc blende CdSe core, thereby creating a crystal structure mismatch through additive growth. Absorption and photoluminescence (PL) band edge features shift to lower energies with increasing shell thickness, but remain above the CdSe bulk band gap. Nevertheless, the profiles of the absorption spectra vary with shell growth, indicating that the overlap of the electron and hole wave functions is changing significantly. This leads to over an order of magnitude reduction of absorption near the band gap and a large, tunable energy shift, of up to 550 meV, between the onset of strong absorption and the band edge PL. While the bulk valence and conduction bands adopt an inverse type-I alignment, the observed spectroscopic behavior is consistent with a transition between quasi-type-I and quasi-type-II behavior depending on shell thickness. Three effective mass approximation models support this hypothesis and suggest that the large difference in effective masses between the core and shell results in hole localization in the CdSe core and a delocalization of the electron across the entire QD. These results show the tuning of wave functions and transition energies in CdSe/PbS nanoheterostructures with prospects for use in optoelectronic devices for luminescent solar concentration or multiexciton generation.

Complex formation and vectorization of a phosphorothioate oligonucleotide with an amphipathic leucine- and lysine-rich peptide: study at molecular and cellular levels.

PubMed

Boukhalfa-Heniche, Fatima-Zohra; Hernández, Belén; Gaillard, Stéphane; Coïc, Yves-Marie; Huynh-Dinh, Tam; Lecouvey, Marc; Seksek, Olivier; Ghomi, Mahmoud

2004-04-15

Optical spectroscopic techniques such as CD, Raman scattering, and fluorescence imaging allowed us to analyze the complex formation and vectorization of a single-stranded 20-mer phosphorothioate oligodeoxynucleotide with a 15-mer amphipathic peptide at molecular and cellular levels. Different solvent mixtures (methanol and water) and molecular ratios of peptide/oligodeoxynucleotide complexes were tested in order to overcome the problems related to solubility. Optimal conditions for both spectroscopic and cellular experiments were obtained with the molecular ratio peptide/oligodeoxynucleotide equal to 21:4, corresponding to a 7:5 ratio for their respective +/- charge ratio. At the molecular level, CD and Raman spectra were consistent with a alpha-helix conformation of the peptide in water or in a methanol-water mixture. The presence of methanol increased considerably the solubility of the peptide without altering its alpha-helix conformation, as evidenced by CD and Raman spectroscopies. UV absorption melting profile of the oligodeoxynucleotide gave rise to a flat melting profile, corresponding to its random structure in solution. Raman spectra of oligodeoxynucleotide/peptide complexes could only be studied in methanol/water mixture solutions. Drastic changes observed in Raman spectra have undoubtedly shown: (a) the perturbation occurred in the peptide secondary structure, and (b) possible interaction between the lysine residues of the peptide and the oligodeoxynucleotide. At the cellular level, the complex was prepared in a mixture of 10% methanol and 90% cell medium. Cellular uptake in optimal conditions for the oligodeoxynucleotide delivery with low cytotoxicity was controlled by fluorescence imaging allowing to specifically locate the compacted oligonucleotide labeled with fluorescein at its 5'-terminus with the peptide into human glioma cells after 1 h of incubation at 37 degrees C. Copyright 2004 Wiley Periodicals, Inc.

Synthesis and spectroscopic studies on the new Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transition metal complexes. Influence on biologically active peptides-regulating aminopeptidases.

PubMed

Hueso-Ureña, Francisco; Illán-Cabeza, Nuria A; Moreno-Carretero, Miguel N; Martínez-Martos, José M; Ramírez-Expósito, María J

2003-04-01

The synthesis, spectroscopic (IR, 1H and 13C NMR, UV-Vis-NIR, EPR), magnetic measurements and biological studies of a number of complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Au(III) and Hg(II) of the Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol and 5-aminouracil, ((5-[[(3-[[(2,4-dioxopyrimidin-5(1H,3H)-yl)imino]methyl]-2-hydroxy-5-methylphenyl)methylene]amino]pyrimidine-2,4(1H,3H)-dione, hereafter denoted as BDF5AU) are reported. In all cases, the complexes appear to be monomeric. The deprotonated ligand in the phenolic oxygen atom shows a tridentate coordination mode through the two azomethine nitrogen atoms and the phenolic oxygen atom. The coordination of the neutral ligand takes place through the phenolic oxygen atom and one azomethine nitrogen atom and the carbonylic oxygen atom in fourth position of one uracil ring. The biological properties of some perchlorate complexes on the activity of some neutral, acid, basic and omega aminopeptidases (AP) are assayed, demonstrating a general inhibitory effect. Neutral and basic AP are mainly inhibited by Cu(II), Ni(II) and Cd(II) complexes, although tyrosyl-AP is activated by Zn(II) complex. Glutamyl-AP but not aspartyl-AP is inhibited by all the complexes assayed excepting Zn(II) complex. Finally, omega AP is inhibited by Ni(II) and Cd(II) complexes. Copyright 2003 Elsevier Science Inc.

Some contributions to the application of LC-NMR, LC-MS, and LC-CD to the biosynthesis of isoquinoline alkaloids using callus cultures.

PubMed

Iwasa, K; Moriyasu, M; Wiegrebe, W

2012-07-01

Hyphenated spectroscopic techniques in combination with a special extraction and work-up of plant calli cultures of Berberidaceae, Fumariaceae, and Papaveraceae families, e.g., enabled us to get deeper insight into the sequential biochemical conversions of precursors into simple isoquinoline- and protoberberine-alkaloids and their follow-up-products with different skeletons. Some new alkaloids of these types have been found.

Radiation hardness studies of CdTe thin films for clinical high-energy photon beam detectors

NASA Astrophysics Data System (ADS)

Shvydka, Diana; Parsai, E. I.; Kang, J.

2008-02-01

In radiation oncology applications, the need for higher-quality images has been driven by recent advances in radiation delivery systems that require online imaging. The existing electronic imaging devices commonly used to acquire portal images implement amorphous silicon (a-Si) detector, which exhibits poor image quality. Efforts for improvement have mostly been in the areas of noise and scatter reduction through software. This has not been successful due to inherent shortcomings of a-Si material. Cadmium telluride (CdTe) semiconductor has long been recognized as highly suitable for use in X-ray detectors in both spectroscopic and imaging applications. Development of such systems has mostly concentrated on single crystal CdTe. Recent advances in thin-film deposition technology suggest replacement of crystalline material with its polycrystalline counterpart, offering ease of large-area device fabrication and achievement of higher resolution as well as a favorable cost difference. While bulk CdTe material was found to have superior radiation hardness, thin films have not been evaluated from that prospective, in particular under high-energy photon beam typical of radiation treatment applications. We assess the performance of thin-film CdTe devices utilizing 6 MeV photon beam and find no consistent trend for material degradation under doses far exceeding the typical radiation therapy detector lifetime dose.

The emission spectroscopy of the B2Σ- -X2 Π system of CD

NASA Astrophysics Data System (ADS)

Szajna, W.; Zachwieja, M.; Hakalla, R.

2016-06-01

The visible spectrum of CD has been investigated at high resolution between 24,500 and 27,500 cm-1 using a high accuracy dispersive optical spectroscopy technique. The CD molecules were produced and excited in a stainless steel hollow-cathode lamp with two anodes and filled with a mixture of He buffer gas and CD4. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. The 0-0, 1-0 and 1-1 bands of the B2Σ- -X2 Π transition have been registered and measured, while 2-0 and 2-1 absorption bands (Herzberg and Johns, 1969) have been reanalyzed. The current data were elaborated with help of recent X2 Π ground state parameters reported by Zachwieja et al. (2012) from investigation of the A2 Δ -X2 Π transition. This way, the improved spectroscopic constants for the B2Σ- state of CD have been provided as follows: νe = 26,050.787 (11) cm-1, ωe = 1653.019 (25) cm-1, ωexe = 123.899 (12) cm-1, Be = 7.08296 (32) cm-1, αe = 0.30741 (84) cm-1, and γe = - 0.10727 (42) cm-1.

Mm-Wave Spectroscopic Sensors, Catalogs, and Uncatalogued Lines

NASA Astrophysics Data System (ADS)

Medvedev, Ivan; Neese, Christopher F.; De Lucia, Frank C.

2014-06-01

Analytical chemical sensing based on high resolution rotational molecular spectra has been recognized as a viable technique for decades. We recently demonstrated a compact implementation of such a sensor. Future generations of these sensors will rely on automated algorithms for quantification of chemical dilutions based on their spectral libraries, as well as identification of spectral features not present in spectral catalogs. Here we present an algorithm aimed at detection of unidentified lines in complex molecular species based on spectroscopic libraries developed in our previous projects. We will discuss the approaches suitable for data mining in feature-rich rotational molecular spectra. Neese, C.F., I.R. Medvedev, G.M. Plummer, A.J. Frank, C.D. Ball, and F.C. De Lucia, "A Compact Submillimeter/Terahertz Gas Sensor with Efficient Gas Collection, Preconcentration, and ppt Sensitivity." Sensors Journal, IEEE, 2012. 12(8): p. 2565-2574

Antibacterial potential of rutin conjugated with thioglycolic acid capped cadmium telluride quantum dots (TGA-CdTe QDs)

NASA Astrophysics Data System (ADS)

Ananth, Devanesan Arul; Rameshkumar, Angappan; Jeyadevi, Ramachandran; Jagadeeswari, Sivanadanam; Nagarajan, Natarajan; Renganathan, Rajalingam; Sivasudha, Thilagar

2015-03-01

Quantum dots not only act as nanocarrier but also act as stable and resistant natural fluorescent bio markers used in various in vitro and in vivo photolabelling and biological applications. In this study, the antimicrobial potential of TGA-CdTe QDs and commercial phenolics (rutin and caffeine) were investigated against Escherichiacoli. UV absorbance and fluorescence quenching study of TGA-CdTe QDs with rutin and caffeine complex was measured by spectroscopic technique. QDs-rutin conjugate exhibited excellent quenching property due to the -OH groups present in the rutin structure. But the same time caffeine has not conjugated with QDs because of lacking of -OH group in its structure. Photolabelling of E. coli with QDs-rutin and QDs-caffeine complex was analyzed by fluorescent microscopic method. Microbe E. coli cell membrane damage was assessed by atomic force (AFM) and confocal microscopy. Based on the results obtained, it is suggested that QDs-rutin conjugate enhance the antimicrobial activity more than the treatment with QDs, rutin and caffeine alone.

Nuclear structure study for the neutron-rich nuclei beyond 132Sn: In-beam gamma-ray spectroscopy of 136Sn and 132Cd

NASA Astrophysics Data System (ADS)

Wang, He; Aoi, Nori; Takeuchi, Satoshi; Matsushita, Masafumi; Doornenbal, Pieter; Motobayashi, Tohru; Steppenbeck, David; Yoneda, Kenichiro; Baba, Hidetada; Dombrádi, Zsolt; Kobayashi, Kota; Kondo, Yosuke; Lee, Jenny; Liu, Hong-Na; Minakata, Ryogo; Nishimura, Daiki; Otsu, Hideaki; Sakurai, Hiroyoshi; Sohler, Dora; Sun, Ye-Lei; Tian, Zheng-Yang; Tanaka, Ryuki; Vajta, Zsolt; Yang, Zai-Hong; Yamamoto, Tetsuya; Ye, Yan-Lin; Yokoyama, Rin

2018-05-01

The neutron-rich nuclei 136Sn and 132Cd have been studied in the purpose of nuclear structure for the nuclei beyond the doubly-magic nucleus 132Sn. The 2+1 → 0+ gs transitions were identified for these two nuclei using in-beam γ-ray spectroscopy in coincidence with one- and two-proton removal reactions, respectively, at the RIKEN Radioactive Isotope Beam Factory. The 2+ 1 state in 136Sn is found to be similar to that for 134Sn indicating the seniority scheme may also hold for the heavy tin isotopes beyond N = 82. For 132Cd, the 2+ 1 state provides the first spectroscopic information in the even-even nuclei locating in the region "southeast" of 132Sn and the result is discussed in terms of proton-neutron configuration mixing. In both these two nuclei, it was found that the valence neutrons play an essential role in their low-lying excitations.

Two-photon absorption and efficient encapsulation of near-infrared-emitting CdSexTe1-x quantum dots

NASA Astrophysics Data System (ADS)

Szeremeta, Janusz; Lamch, Lukasz; Wawrzynczyk, Dominika; Wilk, Kazimiera A.; Samoc, Marek; Nyk, Marcin

2015-07-01

Hydrophobic CdSexTe1-x quantum dots with near infrared emission in the 700-750 nm range were synthesized by a wet chemistry technique. Their nonlinear optical properties were studied using Z-scan technique with a tunable femtosecond laser system. The peak value of the two-photon absorption cross section was found to be ∼2400 GM at 1400 nm. To demonstrate a possible way of utilizing the CdSexTe1-x quantum dots in aqueous environment we describe here a convenient method of preparation of Brij 58® micellar systems loaded with the quantum dots. The obtained nanoconstructs were characterized using optical spectroscopy, TEM and DLS. The micelles colloidal stability, and the influence of the encapsulation process on the spectroscopic properties of the quantum dots are discussed. In particular, we have observed a 60 nm blue-shift of the emission maxima upon loading quantum dots inside the micelles.

The Effect of Twin Boundaries on the Spectroscopic Performance of CdZnTe Detectors

NASA Technical Reports Server (NTRS)

Parker, Bradford H.; Stahle, C. M.; Roth, D.; Babu, S.; Tueller, Jack; Powers, Edward I. (Technical Monitor)

2001-01-01

Most single grains in cadmium zinc telluride (CdZnTe) grown by the high-pressure Bridgman (HPB) technique contain multiple twin boundaries. As a consequence, twin boundaries are one of the most common macroscopic material defects found in large area (400 to 700 sq mm) CdZnTe specimens obtained from HPB ingots. Due to the prevalence of twin boundaries, understanding their effect on detector performance is key to the material selection process. Twin boundaries in several 2 mm thick large area specimens were first, documented using infrared transmission imaging. These specimens were then fabricated into either 2 mm pixel or planar detectors in order to examine the effect of the twin boundaries on detector performance. Preliminary results show that twin boundaries, which are decorated with tellurium inclusions, produce a reduction in detector efficiency and a degradation in resolution. The extent of the degradation appears to be a function of the density of tellurium inclusions.

Cd (II) and holodirected lead (II) 3D-supramolecular coordination polymers based on nicotinic acid: Structure, fluorescence property and photocatalytic activity

NASA Astrophysics Data System (ADS)

Etaiw, Safaa El-din H.; Abd El-Aziz, Dina M.; Marie, Hassan; Ali, Elham

2018-05-01

Two new supramolecular coordination polymers namely {[Cd(NA)2(H2O)]}, SCP 1 and {[Pb(NA)2]}, SCP 2, (NA = nicotinate ligand) were synthesized by self-assembly method and structurally characterized by different analytical and spectroscopic methods. Single-crystal X-ray diffraction showed that SCP 1 extend in three dimensions containing bore structure where the 3D- network is constructed via interweaving zigzag chains. The Cd atom coordinates to (O4N2) atoms forming distorted-octahedral configuration. The structure of SCP 2 extend down the projection of the b-axis creating parallel zigzag 1D-chains connected by μ2-O2 atoms and H-bonds forming a holodirected lead (II) hexagonal bi-pyramid configuration. SCP 2 extend to 3D-network via coordinate and hydrogen bonds. The thermal stability, photoluminescence properties, photocatalytic activity for the degradation of methylene blue dye (MB) under UV-irradiation and sunlight irradiation were also studied.

Reversed oxygen sensing using colloidal quantum wells towards highly emissive photoresponsive varnishes

PubMed Central

Lorenzon, Monica; Christodoulou, Sotirios; Vaccaro, Gianfranco; Pedrini, Jacopo; Meinardi, Francesco; Moreels, Iwan; Brovelli, Sergio

2015-01-01

Colloidal quantum wells combine the advantages of size-tunable electronic properties with vast reactive surfaces that could allow one to realize highly emissive luminescent-sensing varnishes capable of detecting chemical agents through their reversible emission response, with great potential impact on life sciences, environmental monitoring, defence and aerospace engineering. Here we combine spectroelectrochemical measurements and spectroscopic studies in a controlled atmosphere to demonstrate the ‘reversed oxygen-sensing’ capability of CdSe colloidal quantum wells, that is, the exposure to oxygen reversibly increases their luminescence efficiency. Spectroelectrochemical experiments allow us to directly relate the sensing response to the occupancy of surface states. Magneto-optical measurements demonstrate that, under vacuum, heterostructured CdSe/CdS colloidal quantum wells stabilize in their negative trion state. The high starting emission efficiency provides a possible means to enhance the oxygen sensitivity by partially de-passivating the particle surfaces, thereby enhancing the density of unsaturated sites with a minimal cost in term of luminescence losses. PMID:25910499

Insight into the binding mechanism of imipenem to human serum albumin by spectroscopic and computational approaches.

PubMed

Rehman, Md Tabish; Shamsi, Hira; Khan, Asad U

2014-06-02

The mechanism of interaction between imipenem and HSA was investigated by various techniques like fluorescence, UV.vis absorbance, FRET, circular dichroism, urea denaturation, enzyme kinetics, ITC, and molecular docking. We found that imipenem binds to HSA at a high affinity site located in subdomain IIIA (Sudlow's site I) and a low affinity site located in subdomain IIA.IIB. Electrostatic interactions played a vital role along with hydrogen bonding and hydrophobic interactions in stabilizing the imipenem.HSA complex at subdomain IIIA, while only electrostatic and hydrophobic interactions were present at subdomain IIA.IIB. The binding and thermodynamic parameters obtained by ITC showed that the binding of imipenem to HSA was a spontaneous process (ΔGD⁰(D)= -32.31 kJ mol(-1) for high affinity site and ΔGD⁰(D) = -23.02 kJ mol(-1) for low affinity site) with binding constants in the range of 10(4)-10(5) M(-1). Spectroscopic investigation revealed only one binding site of imipenem on HSA (Ka∼10(4) M(-1)). FRET analysis showed that the binding distance between imipenem and HSA (Trp-214) was optimal (r = 4.32 nm) for quenching to occur. Decrease in esterase-like activity of HSA in the presence of imipenem showed that Arg-410 and Tyr-411 of subdomain IIIA (Sudlow's site II) were directly involved in the binding process. CD spectral analysis showed altered conformation of HSA upon imipenem binding. Moreover, the binding of imipenem to subdomain IIIA (Sudlow's site II) of HSA also affected its folding pathway as clear from urea-induced denaturation studies.

Evaluation of bone marrow specimens with acute myelogenous leukemia for CD34, CD15, CD117, and myeloperoxidase.

PubMed

Dunphy, C H; Polski, J M; Evans, H L; Gardner, L J

2001-08-01

Immunophenotyping of bone marrow (BM) specimens with acute myelogenous leukemia (AML) may be performed by flow cytometric (FC) or immunohistochemical (IH) techniques. Some markers (CD34, CD15, and CD117) are available for both techniques. Myeloperoxidase (MPO) analysis may be performed by enzyme cytochemical (EC) or IH techniques. To determine the reliability of these markers and MPO by these techniques, we designed a study to compare the results of analyses of these markers and MPO by FC (CD34, CD15, and CD117), EC (MPO), and IH (CD34, CD15, CD117, and MPO) techniques. Twenty-nine AMLs formed the basis of the study. These AMLs all had been immunophenotyped previously by FC analysis; 27 also had had EC analysis performed. Of the AMLs, 29 had BM core biopsies and 26 had BM clots that could be evaluated. The paraffin blocks of the 29 BM core biopsies and 26 BM clots were stained for CD34, CD117, MPO, and CD15. These results were compared with results by FC analysis (CD34, CD15, and CD117) and EC analysis (MPO). Immunodetection of CD34 expression in AML had a similar sensitivity by FC and IH techniques. Immunodetection of CD15 and CD117 had a higher sensitivity by FC analysis than by IH analysis. Detection of MPO by IH analysis was more sensitive than by EC analysis. There was no correlation of French-American-British (FAB) subtype of AML with CD34 or CD117 expression. Expression of CD15 was associated with AMLs with a monocytic component. Myeloperoxidase reactivity by IH analysis was observed in AMLs originally FAB subtyped as M0. CD34 can be equally detected by FC and IH techniques. CD15 and CD117 are better detected by FC analysis and MPO is better detected by IH analysis.

Formation of β-cyclodextrin inclusion enhances the stability and aqueous solubility of natural borneol.

PubMed

Su, Jianyu; Chen, Jianping; Li, Lin; Li, Bing; Shi, Lei; Chen, Ling; Xu, Zhenbo

2012-06-01

The aims of this study were to optimize the preparation conditions of natural borneol/β-cyclodextrin (NB/β-CD) inclusion complex by ultrasound method, and to investigate its improvement of stability and solubility. The complex was characterized by different various spectroscopic techniques including Fourier transform infrared spectroscopy, X-ray diffractometry, and differential scanning calorimetry. The results demonstrate that NB could be efficiently loaded into β-CD to form an inclusion complex by ultrasound method at a molar ratio of 1: 1and mass ratio of 1: 6. The complex exhibited different physicochemical characteristics from that of free NB. Typically, formation of β-CD inclusion significantly enhanced the stability and aqueous solubility of NB. Natural borneol (NB) has the potential to be widely used in the fields of medical and functional food, due to its specificity. However, the disadvantages of unstability in the preparation and storage process due to its easy sublimation and the low water solubility limit its application. This research provides an effective way to improve the solubility and stability of NB by preparing NB/β-CD inclusion complex. Furthermore, theoretical basis is also provided for the application development of NB. © 2012 Institute of Food Technologists®

Layer-by-layer assembled composite films of side-functionalized poly(3-hexylthiophene) and CdSe nanocrystals: electrochemical, spectroelectrochemical and photovoltaic properties.

PubMed

De Girolamo, Julia; Reiss, Peter; Zagorska, Malgorzata; De Bettignies, Remi; Bailly, Severine; Mevellec, Jean-Yves; Lefrant, Serge; Travers, Jean-Pierre; Pron, Adam

2008-07-21

Regioregular poly(3-hexylthiophene) containing one diaminopyrimidine side group per ten repeat units (P3HT-co-P3(ODAP)HT) can form molecular composites with 1-(6-mercaptohexyl)thymine capped CdSe nanocrystals (CdSe(MHT)) via hydrogen bonds directed molecular recognition. Here we report complementary spectroscopic, electrochemical and spectroelectrochemical investigations of both the functionalized poly(thiophene) and its composite with the nanocrystals, the latter being fabricated using the layer-by-layer (LbL) deposition technique. UV-Vis-NIR and Raman spectroelectrochemical investigations unequivocally show that the onset of the first anodic peak in the cyclic voltammogram of the copolymer can be attributed to the oxidation of the pi-conjugated backbone in the polymer chains. For this reason, it is possible to determine the width and the position of its band gap (corresponding to the pi-pi* transition) by UV-Vis spectroscopy combined with cyclic voltammetry. These studies show that the polymer exhibits a slightly larger band gap with the HOMO level insignificantly lower in energy (by 0.03 eV) as compared to the case of regioregular poly(3-hexylthiophene) of comparable degree of polymerization. Hydrogen bond interactions of the polymer with CdSe(MHT) in the molecular composite result in a hypsochromic shift of the band corresponding to the pi-pi* transition from 504 nm to 488 nm. This can be taken as a spectroscopic manifestation of the conformational changes induced by shortening of the conjugation length. The observed spectral modifications are consistent with electrochemically determined lowering of the polymer HOMO level (from -4.91 eV in the pure polymer to -4.99 eV in the composite). Cyclic voltammetry studies supported by spectroelectrochemistry also show that the redox stability of CdSe(MHT) in the molecular composite with P3HT-co-P3(ODAP)HT is lower than that determined for stearate-capped nanocrystals. Their irreversible oxidation starts at E = +0.7 V vs. Ag/0.1 M Ag(+)i.e. at potentials by ca. 0.3 V lower than the oxidation of stearate stabilized CdSe nanocrystals of the same size. We show that-despite these modifications-the alignment of the HOMO and LUMO levels of the composite components remains appropriate for its use in hybrid solar cells, which is demonstrated by the photovoltaic effect observed for the LbL-processed composite sandwiched between two electrodes.

Raman spectroscopic study of plasma-treated salmon DNA

NASA Astrophysics Data System (ADS)

Joon Lee, Geon; Kwon, Young-Wan; Hee Kim, Yong; Ha Choi, Eun

2013-01-01

In this research, we studied the effect of plasma treatment on the optical/structural properties of the deoxyribonucleic acid (DNA) extracted from salmon sperm. DNA-cetyltrimethylammonium (CTMA) films were obtained by complexation of DNA with CTMA. Circular dichroism (CD) and Raman spectra indicated that DNA retained its double helical structure in the solid film. The Raman spectra exhibited several vibration modes corresponding to the nuclear bases and the deoxyribose-phosphate backbones of the DNA, as well as the alkylchains of CTMA. Dielectric-barrier-discharge (DBD) plasma treatment induced structural modification and damage to the DNA, as observed by changes in the ultraviolet-visible absorption, CD, and Raman spectra. The optical emission spectra of the DBD plasma confirmed that DNA modification was induced by plasma ions such as reactive oxygen species and reactive nitrogen species.

Charge-sensitive front-end electronics with operational amplifiers for CdZnTe detectors

NASA Astrophysics Data System (ADS)

Födisch, P.; Berthel, M.; Lange, B.; Kirschke, T.; Enghardt, W.; Kaever, P.

2016-09-01

Cadmium zinc telluride (CdZnTe, CZT) radiation detectors are suitable for a variety of applications, due to their high spatial resolution and spectroscopic energy performance at room temperature. However, state-of-the-art detector systems require high-performance readout electronics. Though an application-specific integrated circuit (ASIC) is an adequate solution for the readout, requirements of high dynamic range and high throughput are not available in any commercial circuit. Consequently, the present study develops the analog front-end electronics with operational amplifiers for an 8×8 pixelated CZT detector. For this purpose, we modeled an electrical equivalent circuit of the CZT detector with the associated charge-sensitive amplifier (CSA). Based on a detailed network analysis, the circuit design is completed by numerical values for various features such as ballistic deficit, charge-to-voltage gain, rise time, and noise level. A verification of the performance is carried out by synthetic detector signals and a pixel detector. The experimental results with the pixel detector assembly and a 22Na radioactive source emphasize the depth dependence of the measured energy. After pulse processing with depth correction based on the fit of the weighting potential, the energy resolution is 2.2% (FWHM) for the 511 keV photopeak.

Interaction of lafutidine in binding to human serum albumin in gastric ulcer therapy: STD-NMR, WaterLOGSY-NMR, NMR relaxation times, Tr-NOESY, molecule docking, and spectroscopic studies.

PubMed

Yang, Hongqin; Huang, Yanmei; He, Jiawei; Li, Shanshan; Tang, Bin; Li, Hui

2016-09-15

In this study, lafutidine (LAF) was used as a model compound to investigate the binding mechanism between antiulcer drugs and human serum albumin (HSA) through various techniques, including STD-NMR, WaterLOGSY-NMR, (1)H NMR relaxation times, tr-NOESY, molecule docking calculation, FT-IR spectroscopy, and CD spectroscopy. The analyses of STD-NMR, which derived relative STD (%) intensities, and WaterLOGSY-NMR, determined that LAF bound to HSA. In particular, the pyridyl group of LAF was in close contact with HSA binding pocket, whereas furyl group had a secondary binding. Competitive STD-NMR and WaterLOGSY-NMR experiments, with warifarin and ibuprofen as site-selective probes, indicated that LAF preferentially bound to site II in the hydrophobic subdomains IIIA of HSA. The bound conformation of LAF at the HSA binding site was further elucidated by transferred NOE effect (tr-NOESY) experiment. Relaxation experiments provided quantitative information about the relationship between the affinity and structure of LAF. The molecule docking simulations conducted with AutoDock and the restraints derived from STD results led to three-dimensional models that were consistent with the NMR spectroscopic data. The presence of hydrophobic forces and hydrogen interactions was also determined. Additionally, FT-IR and CD spectroscopies showed that LAF induced secondary structure changes of HSA. Copyright © 2016 Elsevier Inc. All rights reserved.

Interaction of imatinib mesylate with human serum transferrin: The comparative spectroscopic studies

NASA Astrophysics Data System (ADS)

Śliwińska-Hill, Urszula

2017-02-01

Imatinib mesylate (Imt) is a tyrosine kinase inhibitor mainly used in the treatment of Philadelphia chromosome-positive chronic myelogenous leukemia (Ph + CML). Human serum transferrin is the most abundant serum protein responsible for the transport of iron ions and many endogenous and exogenous ligands. In this study the mechanism of interactions between the imatinib mesylate and all states of transferrin (apo-Tf, Htf and holo-Tf) has been investigated by fluorescence, ultraviolet-visible (UV-vis), circular dichroism (CD) and zeta potential spectroscopic methods. Based on the experimental results it was proved that under physiological conditions the imatinib mesylate binds to the each form of transferrin with a binding constant c.a. 105 M- 1. The thermodynamic parameters indicate that hydrogen bonds and van der Waals were involved in the interaction of apo-Tf with the drug and hydrophobic and ionic strength participate in the reaction of Htf and holo-Tf with imatinib mesylate. Moreover, it was shown that common metal ions, Zn2 + and Ca2 + strongly influenced apo-Tf-Imt binding constant. The CD studies showed that there are no conformational changes in the secondary structure of the proteins. No significant changes in secondary structure of the proteins upon binding with the drug and instability of apo-Tf-Imt system are the desirable effects from pharmacological point of view.

The effect of Berberine on the secondary structure of human serum albumin

NASA Astrophysics Data System (ADS)

Li, Ying; He, WenYing; Tian, Jianniao; Tang, Jianghong; Hu, Zhide; Chen, Xingguo

2005-05-01

The presence of several high affinity binding sites on human serum albumin (HSA) makes it a possible target for many drugs. This study is designed to examine the effect of Berberine (an ancient Chinese drug used for antimicrobial, antiplasmodial, antidiarrheal and cardiovascular) on the solution structure of HSA using fluorescence, Fourier transform infrared (FT-IR), circular dichroism (CD) spectroscopic methods. The fluorescence spectroscopic results show that the fluorescence intensity of HSA was significantly decreased in the presence of Berberine. The Scatchard's plots indicated that the binding of Berberine to HSA at 296, 303, 318 K is characterized by one binding site with the binding constant is 4.071(±0.128)×10 4, 3.741(±0.089)×10 4, 3.454(±0.110)×10 4 M -1, respectively. The protein conformation is altered (FT-IR and CD data) with reductions of α-helices from 54 to 47% for free HSA to 45-32% and with increases of turn structure5% for free HSA to 18% in the presence of Berberine. The binding process was exothermic, enthalpy driven and spontaneous, as indicated by the thermodynamic analyses, Berberine bound to HSA was mainly based on hydrophobic interaction and electrostatic interaction cannot be excluded from the binding. Furthermore, the displace experiments indicate that Berberine can bind to the subdomain IIA, that is, high affinity site (site II).

Effects of oxygen partial pressure, deposition temperature, and annealing on the optical response of CdS:O thin films as studied by spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Junda, Maxwell M.; Grice, Corey R.; Subedi, Indra; Yan, Yanfa; Podraza, Nikolas J.

2016-07-01

Ex-situ spectroscopic ellipsometry measurements are made on radio frequency magnetron sputtered oxygenated cadmium sulfide (CdS:O) thin films. Films are deposited onto glass substrates at room temperature and at 270 °C with varying oxygen to total gas flow ratios in the sputtering ambient. Ellipsometric spectra from 0.74 to 5.89 eV are collected before and after annealing at 607 °C to simulate the thermal processes during close-space sublimation of overlying cadmium telluride in that solar cell configuration. Complex dielectric function (ɛ = ɛ1 + iɛ2) spectra are extracted for films as a function of oxygen gas flow ratio, deposition temperature, and post-deposition annealing using a parametric model accounting for critical point transitions and an Urbach tail for sub-band gap absorption. The results suggest an inverse relationship between degree of crystallinity and oxygen gas flow ratio, whereas annealing is shown to increase crystallinity in all samples. Direct band gap energies are determined from the parametric modeling of ɛ and linear extrapolations of the square of the absorption coefficient. As-deposited samples feature a range of band gap energies whereas annealing is shown to result in gap energies ranging only from 2.40 to 2.45 eV, which is close to typical band gaps for pure cadmium sulfide.

Multi-spectroscopic and molecular docking studies on the interaction of darunavir, a HIV protease inhibitor with calf thymus DNA.

PubMed

Shi, Jie-Hua; Zhou, Kai-Li; Lou, Yan-Yue; Pan, Dong-Qi

2018-03-15

Molecular interaction of darunavir (DRV), a HIV protease inhibitor with calf thymus deoxyribonucleic acid (ct-DNA) was studied in physiological buffer (pH7.4) by multi-spectroscopic approaches hand in hand with viscosity measurements and molecular docking technique. The UV absorption and fluorescence results together revealed the formation of a DRV-ct-DNA complex having binding affinities of the order of 10 3 M -1 , which was more in keeping with the groove binding. The results that DRV bound to ct-DNA via groove binding mode was further evidenced by KI quenching studies, viscosity measurements, competitive binding investigations with EB and Rhodamine B and CD spectral analysis. The effect of ionic strength indicated the negligible involvement of electrostatic interaction between DRV and ct-DNA. The thermodynamic parameters regarding the binding interaction of DRV with ct-DNA in terms of enthalpy change (ΔH 0 ) and entropy change (ΔS 0 ) were -63.19kJ mol -1 and -141.92J mol -1 K -1 , indicating that hydrogen bonds and van der Waals forces played a predominant role in the binding process. Furthermore, molecular simulation studies suggested that DRV molecule was prone to bind in the A-T rich region of the minor groove of DNA. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular investigation on the interaction of spermine with proteinase K by multispectroscopic techniques and molecular simulation studies.

PubMed

Hosseini-Koupaei, Mansoore; Shareghi, Behzad; Saboury, Ali Akbar; Davar, Fateme

2017-01-01

The alteration in structure, function and stability of proteinase K in the presence of spermine was investigated using spectroscopic methods and simulation techniques. The stability and enzyme activity of proteinase K-spermine complex were significantly enhanced as compared to that of the pure enzyme. The increase in the value of V max and the catalytic efficiency of Proteinase K in presence of spermine confirmed that the polyamine could bring the enzyme hyperactivation. UV-vis spectroscopy, intrinsic fluorescence and circular dichroism methods demonstrated that the binding of spermine changed the microenvironment and structure of proteinase K. The fluorescence studies, showing that spermine quenched the intensity of proteinase K with static mechanism. Thermodynamic parameters analysis suggested that hydrogen bond and van der Waals forces play a key role in complex stability which is in agreement with modeling studies. The CD spectra represented the secondary structure alteration of proteinase K with an increase in α-helicity and a decrease in β-sheet of proteinase K upon spermine conjugation. The molecular simulation results proposed that spermine could interact with proteinase K spontaneously at single binding site, which is in agreement with spectroscopic results. This agreement between experimental and theoretical results may be a worth method for protein-ligand complex studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Photomask CD and LER characterization using Mueller matrix spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Heinrich, A.; Dirnstorfer, I.; Bischoff, J.; Meiner, K.; Ketelsen, H.; Richter, U.; Mikolajick, T.

2014-10-01

Critical dimension and line edge roughness on photomask arrays are determined with Mueller matrix spectroscopic ellipsometry. Arrays with large sinusoidal perturbations are measured for different azimuth angels and compared with simulations based on rigorous coupled wave analysis. Experiment and simulation show that line edge roughness leads to characteristic changes in the different Mueller matrix elements. The influence of line edge roughness is interpreted as an increase of isotropic character of the sample. The changes in the Mueller matrix elements are very similar when the arrays are statistically perturbed with rms roughness values in the nanometer range suggesting that the results on the sinusoidal test structures are also relevant for "real" mask errors. Critical dimension errors and line edge roughness have similar impact on the SE MM measurement. To distinguish between both deviations, a strategy based on the calculation of sensitivities and correlation coefficients for all Mueller matrix elements is shown. The Mueller matrix elements M13/M31 and M34/M43 are the most suitable elements due to their high sensitivities to critical dimension errors and line edge roughness and, at the same time, to a low correlation coefficient between both influences. From the simulated sensitivities, it is estimated that the measurement accuracy has to be in the order of 0.01 and 0.001 for the detection of 1 nm critical dimension error and 1 nm line edge roughness, respectively.

Polyketide derivatives from a marine-sponge-associated fungus Pestalotiopsis heterocornis.

PubMed

Lei, Hui; Lin, Xiuping; Han, Li; Ma, Jian; Dong, Kailin; Wang, Xingbo; Zhong, Jialiang; Mu, Yu; Liu, Yonghong; Huang, Xueshi

2017-10-01

Twelve previously undescribed polyketide derivatives, heterocornols A-L, and seven known analogues were isolated from a culture of the fungus Pestalotiopsis heterocornis associated with sponge. Their structures were elucidated by a comprehensive spectroscopic data analysis and CD Cotton effects. These compounds were evaluated for cytotoxic and antibacterial activities in vitro. Among them, heterocornols A-C, F-H, methyl-(2-formyl-3-hydroxyphenyl)propanoate, agropyrenol, and vaccinol G exhibited cytotoxicities against four human cancer cell lines with IC 50 values 15-100 μM, and they also showed antibacterial activities against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis with MIC values ranging from 25 to 100 μg/mL. Moreover, compounds heterocornol C, heterocornol G, agropyrenol, and vaccinol G showed weak antifungal activities against Candida parapsilosis and Cryptococcus neoformans with MIC values 100 μg/mL. Copyright © 2017 Elsevier Ltd. All rights reserved.

Xanthurenic acid 8-O-beta-D-glucoside, a novel tryptophan metabolite in eye-color mutants of Drosophila melanogaster.

PubMed

Ferré, J; Real, M D; Ménsua, J L; Jacobson, K B

1985-06-25

An unknown fluorescent metabolite has been isolated from heads of eye-color mutants of Drosophila melanogaster. Only a few mutations cause it to accumulate, viz. cardinal (cd), dark red brown (drb), Henna-recessive (Hnr), purple (pr), Punch2 (Pu2), Punch-Grape (PuGr), and scarlet (st). After purification by ion-exchange chromatography, the spectroscopic, chemical, and enzymatic analyses revealed that it is a novel quinoline derivative: xanthurenic acid 8-O-beta-D-glucoside. Feeding experiments suggest that this glucoside is synthesized from 3-hydroxykynurenine and that free xanthurenic acid is not a precursor. The results from the analysis for its occurrence in double mutants, together with the fact that xanthurenic acid 8-glucoside share the same precursor as xanthurenic acid and xanthommatin, suggest that xanthurenic acid 8-glucoside formation is closely related to the regulation of the last step in the biosynthesis of xanthommatin.

A New N-methoxypyridone from the Co-Cultivation of Hawaiian Endophytic Fungi Camporesia sambuci FT1061 and Epicoccum sorghinum FT1062.

PubMed

Li, Chunshun; Sarotti, Ariel M; Yang, Baojun; Turkson, James; Cao, Shugeng

2017-07-12

A new N -methoxypyridone analog ( 1 ), together with four known compounds, was isolated from the co-culture of Hawaiian endophytic fungi Camporesia sambuci FT1061 and Epicoccum sorghinum FT1062. The structure of the new compound was elucidated as 11 S -hydroxy-1-methoxyfusaricide ( 1 ) by extensive spectroscopic analysis and comparison with the literature. The absolute configuration of 1 was determined by comparison with the experimental and calculated ECD spectra. The absolute configuration of compound 3 was investigated and renamed as (+)-epipyridone by comparison of the optical rotation and CD spectrum with those of 1 . The other known compounds were identified as epicoccarine B ( 2 ), D8646-2-6 ( 4 ), and iso-D8646-2-6 ( 5 ). Compounds 4 and 5 showed modest inhibitory activity towards pathogenic fungi. Epicoccarine B ( 2 ) inhibited A2780 and TK-10 with an IC 50 value of 22 μM.

Radiative lifetimes of zincblende CdSe/CdS quantum dots

DOE PAGES

Gong, Ke; Martin, James E.; Shea-Rohwer, Lauren E.; ...

2015-01-02

Recent synthetic advances have made available very monodisperse zincblende CdSe/CdS quantum dots having near-unity photoluminescence quantum yields. Because of the absence of nonradiative decay pathways, accurate values of the radiative lifetimes can be obtained from time-resolved PL measurements. Radiative lifetimes can also be obtained from the Einstein relations, using the static absorption spectra and the relative thermal populations in the angular momentum sublevels. We found that one of the inputs into these calculations is the shell thickness, and it is useful to be able to determine shell thickness from spectroscopic measurements. We use an empirically corrected effective mass model tomore » produce a “map” of exciton wavelength as a function of core size and shell thickness. These calculations use an elastic continuum model and the known lattice and elastic constants to include the effect of lattice strain on the band gap energy. The map is in agreement with the known CdSe sizing curve and with the shell thicknesses of zincblende core/shell particles obtained from TEM images. Furthermore, if selenium–sulfur diffusion is included and lattice strain is omitted from the calculation then the resulting map is appropriate for wurtzite CdSe/CdS quantum dots synthesized at high temperatures, and this map is very similar to one previously reported (J. Am. Chem. Soc. 2009, 131, 14299). Radiative lifetimes determined from time-resolved measurements are compared to values obtained from the Einstein relations, and found to be in excellent agreement. For a specific core size (2.64 nm diameter, in the present case), radiative lifetimes are found to decrease with increasing shell thickness. Thus, this is similar to the size dependence of one-component CdSe quantum dots and in contrast to the size dependence in type-II quantum dots.« less

Synthesis and structural characterization of magnetic cadmium sulfide-cobalt ferrite nanocomposite, and study of its activity for dyes degradation under ultrasound

NASA Astrophysics Data System (ADS)

Farhadi, Saeed; Siadatnasab, Firouzeh

2016-11-01

Cadmium sulfide-cobalt ferrite (CdS/CFO) nanocomposite was easily synthesized by one-step hydrothermal decomposition of cadmium diethyldithiocarbamate complex on the CoFe2O4 nanoparticles at 200 °C. Spectroscopic techniques of powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), UV-visible spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and magnetic measurements were applied for characterizing the structure and morphology of the product. The results of FT-IR, XRD and EDX indicated that the CdS/CFO was highly pure. SEM and TEM results revealed that the CdS/CFO nanocomposite was formed from nearly uniform and sphere-like nanoparticles with the size of approximately 20 nm. The UV-vis absorption spectrum of the CdS/CFO nanocomposite showed the band gap of 2.21 eV, which made it suitable for sono-/photo catalytic purposes. By using the obtained CdS/CFO nanocomposite, an ultrasound-assisted advanced oxidation process (AOP) has been developed for catalytic degradation of methylene blue (MB), Rhodamine B (RhB), and methyl orange (MO)) in the presence of H2O2 as a green oxidant. CdS/CFO nanocomposite exhibited excellent sonocatalytic activity, so that, dyes were completely degraded in less than 10 min. The influences of crucial factors such as the H2O2 amount and catalyst dosage on the degradation efficiency were evaluated. The as-prepared CdS/CFO nanocomposite exhibited higher catalytic activity than pure CdS nanoparticles. Moreover, the magnetic property of CoFe2O4 made the nanocomposite recyclable.

Optical biosensing of nitrite ions using cytochrome cd1 nitrite reductase encapsulated in a sol-gel matrix.

PubMed

Ferretti, S; Lee, S K; MacCraith, B D; Oliva, A G; Richardson, D J; Russell, D A; Sapsford, K E; Vidal, M

2000-11-01

Nitrite is an important human health and environmental analyte. As such, the European Union (EU) has imposed a limit for nitrite in potable water of 0.1 mg l-1 (2.18 microM). In order to develop an optical biosensing system for the determination of nitrite ions in environmental waters, cytochrome cd1 nitrite reductase has been extracted and purified from the bacterium Paracoccus pantotrophus. The protein has been spectroscopically characterised in solution and important kinetic parameters of nitrite reduction of the cytochrome cd1 enzyme, i.e., Km, Vmax and kcat have been determined. The influence of pH on the activity of the cytochrome cd1 has been investigated and the results suggest that this enzyme can be used for the determination of nitrite in the pH range 6-9. Biosensing experiments with the cytochrome cd1 in solution suggested that the decrease in intensity of the absorption band associated with the d1 haem (which is the nitrite binding site), at 460 nm, with increasing nitrite concentrations would enable the measurement of this analyte with the optimum limit of detection. The cytochrome cd1 has been encapsulated in a bulk sol-gel monolith with no structural changes observed and retention of enzymatic activity. The detection of nitrite ions in the range 0.075-1.250 microM was achieved, with a limit of detection of 0.075 microM. In order to increase the speed of response, a sol-gel sandwich thin film structure was formulated with the cytochrome cd1. This structure enabled the determination of nitrite concentrations within ca. 5 min. The sol-gel sandwich entrapped cytochrome cd1 enzyme was found to be stable for several months when the films were stored at 4 degrees C.

Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

NASA Astrophysics Data System (ADS)

Osuntokun, Jejenija; Ajibade, Peter A.

2016-09-01

Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato-κS,S'-bis(N,N-dimethylthiourea-κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33-7.21 nm for ZnS and 4.95-7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine

NASA Astrophysics Data System (ADS)

Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.

2007-10-01

A macrocyclic ligand, bdta (where bdta = 3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl 2 type complexes [where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine.

PubMed

Khan, Sadaf; Nami, Shahab A A; Siddiqi, K S

2007-10-01

A macrocyclic ligand, bdta (where bdta=3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl2 type complexes [where M=Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.

Study of gamma detection capabilities of the REWARD mobile spectroscopic system

NASA Astrophysics Data System (ADS)

Balbuena, J. P.; Baptista, M.; Barros, S.; Dambacher, M.; Disch, C.; Fiederle, M.; Kuehn, S.; Parzefall, U.

2017-07-01

REWARD is a novel mobile spectroscopic radiation detector system for Homeland Security applications. The system integrates gamma and neutron detection equipped with wireless communication. A comprehensive simulation study on its gamma detection capabilities in different radioactive scenarios is presented in this work. The gamma detection unit consists of a precise energy resolution system based on two stacked (Cd,Zn)Te sensors working in coincidence sum mode. The volume of each of these CZT sensors is 1 cm3. The investigated energy windows used to determine the detection capabilities of the detector correspond to the gamma emissions from 137Cs and 60Co radioactive sources (662 keV and 1173/1333 keV respectively). Monte Carlo and Technology Computer-Aided Design (TCAD) simulations are combined to determine its sensing capabilities for different radiation sources and estimate the limits of detection of the sensing unit as a function of source activity for several shielding materials.

Comparative study of the interactions between bisphenol-A and its endocrine disrupting analogues with bovine serum albumin using multi-spectroscopic and molecular docking studies.

PubMed

Ikhlas, Shoeb; Usman, Afia; Ahmad, Masood

2018-04-24

Interaction studies of bisphenol analogues; biphenol-A (BPA), bisphenol-B (BPB), and bisphenol-F (BPF) with bovine serum albumin (BSA) were performed using multi-spectroscopic and molecular docking studies at the protein level. The mechanism of binding of bisphenols with BSA was dynamic in nature. SDS refolding experiments demonstrated no stabilization of BSA structure denatured by BPB, however, BSA denatured by BPA and BPF was found to get stabilized. Also, CD spectra and molecular docking studies revealed that BPB bound more strongly and induced more conformational changes in BSA in comparison to BPA. Hence, this study throws light on the replacement of BPA by its analogues and whether the replacement is associated with a possible risk, raising a doubt that perhaps BPB is not a good substitute of BPA.

A calix[4]arene strapped calix[4]pyrrole: an ion-pair receptor displaying three different cesium cation recognition modes.

PubMed

Kim, Sung Kuk; Sessler, Jonathan L; Gross, Dustin E; Lee, Chang-Hee; Kim, Jong Seung; Lynch, Vincent M; Delmau, Laetitia H; Hay, Benjamin P

2010-04-28

An ion-pair receptor, the calix[4]pyrrole-calix[4]arene pseudodimer 2, bearing a strong anion-recognition site but not a weak cation-recognition site, has been synthesized and characterized by standard spectroscopic means and via single-crystal X-ray diffraction analysis. In 10% CD(3)OD in CDCl(3) (v/v), this new receptor binds neither the Cs(+) cation nor the F(-) anion when exposed to these species in the presence of other counterions; however, it forms a stable 1:1 solvent-separated CsF complex when exposed to these two ions in concert with one another in this same solvent mixture. In contrast to what is seen in the case of a previously reported crown ether "strapped" calixarene-calixpyrrole ion-pair receptor 1 (J. Am. Chem. Soc. 2008, 130, 13162-13166), where Cs(+) cation recognition takes place within the crown, in 2.CsF cation recognition takes place within the receptor cavity itself, as inferred from both single-crystal X-ray diffraction analyses and (1)H NMR spectroscopic studies. This binding mode is supported by calculations carried out using the MMFF94 force field model. In 10% CD(3)OD in CDCl(3) (v/v), receptor 2 shows selectivity for CsF over the Cs(+) salts of Cl(-), Br(-), and NO(3)(-) but will bind these other cesium salts in the absence of fluoride, both in solution and in the solid state. In the case of CsCl, an unprecedented 2:2 complex is observed in the solid state that is characterized by two different ion-pair binding modes. One of these consists of a contact ion pair with the cesium cation and chloride anion both being bound within the central binding pocket and in direct contact with one another. The other mode involves a chloride anion bound to the pyrrole NH protons of a calixpyrrole subunit and a cesium cation sandwiched between two cone shaped calix[4]pyrroles originating from separate receptor units. In contrast to what is seen for CsF and CsCl, single-crystal X-ray structural analyses and (1)H NMR spectroscopic studies reveal that receptor 2 forms a 1:1 complex with CsNO(3), with the ions bound in the form of a contact ion pair. Thus, depending on the counteranion, receptor 2 is able to stabilize three different ion-pair binding modes with Cs(+), namely solvent-bridged, contact, and host-separated.

Biometal binding-site mimicry with modular, hetero-bifunctionally modified architecture encompassing a Trp/His motif: insights into spatiotemporal noncovalent interactions from a comparative spectroscopic study.

PubMed

Yang, Chi Ming

2011-03-28

Metal-site Trp/His interactions are crucial to diverse metalloprotein functions. This paper presents a study using metal-motif mimicry to capture and dissect the static and transient components of physicochemical properties underlying the Trp/His aromatic side-chain noncovalent interactions across the first- and second-coordination spheres of biometal ions. Modular biomimetic constructs, EDTA-(L-Trp, L-His) or EWH and DTPA-(L-Trp, L-His) or DWH, featuring a function-significant Trp/His pair, enabled extracting the putative hydrophobic/hydrophilic aromatic interactions surrounding metal centers. Fluorescence, circular dichroism (CD) spectroscopic titrations and ESI mass spectrometry demonstrated that both the constructs stoichiometrically bind to Ca(2+), Co(2+), Cu(2+), Ni(2+), Mn(2+), Zn(2+), Cd(2+), and Fe(2+), and such binding was strongly coupled to stereospecific side-chain structure reorientations of the Trp indole and His imidazole rings. A mechanistic dichotomy corresponding to the participation of the indole unit in the binding event was revealed by a scaffold-platform correlation of steady-state fluorescence-response landscape, illuminating that secondary-coordination-sphere ligand cation-π interactions were immediately followed by subsequent transient physicochemical processes including through-space energy transfer, charge transfer and/or electron transfer, depending on the type of metals. The fluorescence quenching of Trp side chain by 3d metal ions can be ascribed to through-space d-π interactions. While the fluorescence titration was capable of illuminating a two-component energetic model, clean isosbestic/isodichroic points in the CD titration spectra indicated that the metallo-constructs, such as Cu(2+)-EWH complex, fold thermodynamically by means of a two-state equilibrium. Further, the metal-ion dependence of Trp conformational variation in the modular architecture of metal-bound scaffolds was evidenced unambiguously by the CD spectra and supported by MMFF calculations; both were capable of distinguishing between the coordination geometry and the preference for metal binding mode. The study thus helps understand how aromatic rings around metal-sites have unique capabilities through the control of the spatiotemporal distribution of noncovalent interaction elements to achieve diverse chemical functionality.

Spectroscopic geochemical study of vanadiferous marine sediments of the Gibellini claims, southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Böhlke, J.K.; Radtke, A.S.; Heropoulos, Chris; Lamothe, P.J.

1981-01-01

Samples of cuttings from three drill holes in the Gibellini claims were analyzed by emission spectroscopic techniques for a large suite of major and trace elements. Unoxidized siliceous "black shale" from drill hole NGA 7 is strongly enriched in Cd, Mo, Sb, Se, V, and Zn, and also contains relatively high concentrations of As, Ba, Cu, Ni, and Tl compared with nonmetalliferous shales. Analyses of 103 samples plotted against depth in drill holes NGA, NG31, and NGA7, and selected XRD data, show the following: 1. Groups of elements with distinct distribution patterns define most of major mineralogic components of the rocks. The "normal shale" component, which includes several detrital and authigenic phases, is indicated by covariations among Ti, Al, Fe, Na, Mg, K, B, Be, Co, Cr, Ga, La, Sc, Sr, and Zr. The shale component is diluted by varying amounts of the following minerals (and associated elements): silica (Si); dolomite (Mg, Ca, Mn, Sr); apatite (Ca, Be, Cr, La, Sr, Y); barite (Ba, Sr); sphalerite (Zn, Cd, Fe?); smithsonite (Cd, Co, Mn, Ni, Zn); bianchite (Cd, Ni, Zn) ; and bokite (V). Pyrite, gypsum, and jarosite were also identified.2. The highly siliceous kerogenous metalliferous Gibellini facies is underlain by argillaceous and (or) dolomitic rocks. The transition zone deduced from the chemical data is not well defined in all instances, but probably represents the bottom of the black shale deposit. 3. Oxidation has reached to variable depths up to at least 150 ft, and has caused profound changes in the distributions of the enriched metals. Molybdenum, Se, and V have been partially removed from the upper parts of the sections and are concentrated near or slightly above the base of the Gibellini facies. Cadmium, Ni, and Zn have been strongly leached and now occur at or below the base of the Gibellini facies. The variable depth of oxidation, the redistribution and separation of the metals, and the complex mineralogy of the deposit may make development of the claim complicated.

Time-frequency analysis in optical coherence tomography for technical objects examination

NASA Astrophysics Data System (ADS)

StrÄ kowski, Marcin R.; Kraszewski, Maciej; Trojanowski, Michał; Pluciński, Jerzy

2014-05-01

Optical coherence tomography (OCT) is one of the most advanced optical measurement techniques for complex structure visualization. The advantages of OCT have been used for surface and subsurface defect detection in composite materials, polymers, ceramics, non-metallic protective coatings, and many more. Our research activity has been focused on timefrequency spectroscopic analysis in OCT. It is based on time resolved spectral analysis of the backscattered optical signal delivered by the OCT. The time-frequency method gives spectral characteristic of optical radiation backscattered or backreflected from the particular points inside the tested device. This provides more information about the sample, which are useful for further analysis. Nowadays, the applications of spectroscopic analysis for composite layers characterization or tissue recognition have been reported. During our studies we have found new applications of spectroscopic analysis. We have used this method for thickness estimation of thin films, which are under the resolution of OCT. Also, we have combined the spectroscopic analysis with polarization sensitive OCT (PS-OCT). This approach enables to obtain a multiorder retardation value directly and may become a breakthrough in PS-OCT measurements of highly birefringent media. In this work, we present the time-frequency spectroscopic algorithms and their applications for OCT. Also, the theoretical simulations and measurement validation of this method are shown.

Modulation in prototropism of the photosensitizer Harmane by host:guest interactions between β-cyclodextrin and surfactants.

PubMed

Paul, Bijan K; Ray, Debarati; Ganguly, Aniruddha; Guchhait, Nikhil

2013-12-01

The present contribution demonstrates the photophysics of a prospective cancer cell photosensitizer Harmane (HM) belonging to the family of β-carboline in mixed microheterogeneous environments of β-cyclodextrin (β-CD) and surfactants having varying surface charges using steady-state and time-resolved fluorescence spectroscopic techniques. The remarkable modulations in prototropic activities of the micelle-bound drug in the presence of β-CD evinces for disruption of the micellar structural integrity by β-CD. The results are meticulously discussed in relevance to the effect of a potential drug delivery vehicle (CD) on the membrane-mimetic micellar system. Further, application of an extrinsic fluorescence probe for monitoring such interactions is fraught by the possibilities of no less than three equilibria that can operate simultaneously viz., (i) surfactant-cyclodextrin, (ii) surfactant-fluorophore and (iii) cyclodextrin-fluorophore. This aspect highlights the enormous importance of the issue of suitability of the fluorescence probe to study such complicated systems and interaction phenomena. Also the varying interaction scenario of β-CD with the nature of the surfactant highlights the importance of precise knowledge of the strength and locus of drug binding in delineating such complex interactions. The results of the present investigation advocate for the potential applicability of the drug (HM) itself as a fluorescence reporter in study of such complex microheterogeneous interactions. Copyright © 2013 Elsevier Inc. All rights reserved.

Study of complex formation of 5,5'-(2 E, 2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) (HYT) macrocyclic ligand with Cd2+ cation in non-aqueous solution by spectroscopic and conductometric methods

NASA Astrophysics Data System (ADS)

Mallaekeh, Hassan; Shams, Alireza; Shaker, Mohammad; Bahramzadeh, Ehsan; Arefi, Donya

2014-12-01

In this paper the complexation reaction of the 5,5'-(2 E,2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) ligand (HYT) with Cd2+ education was studied in some binary mixtures of methanol (MeOH), n-propanol (PrOH) and dimethyl-formamide (DMF) at different temperatures using the conductometry and spectrophotometry. The stability constants of the complex was determined using a GENPLOT computer program. The conductance data and absorbance-mole ratio plots show that in all solvent systems, the stoichiometry of the complex formed between (HYT) and Cd2+ cation is 1: 1. The obtained results show that the stability of (HYT)-Cd complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (Δ G ∘, Δ H ∘, and Δ S ∘) for formation of (HYT)-Cd complex were obtained from temperature dependence of the stability constant using the van't Hoff plots. The results show that in most cases, the complex are enthalpy destabilized but entropy stabilized and the complex formation is affected by pH, time, temperature and the nature of the solvent.

VTVH-MCD and DFT studies of thiolate bonding to [FeNO]7/[FeO2]8 complexes of isopenicillin N synthase: substrate determination of oxidase versus oxygenase activity in nonheme Fe enzymes.

PubMed

Brown, Christina D; Neidig, Michael L; Neibergall, Matthew B; Lipscomb, John D; Solomon, Edward I

2007-06-13

Isopenicillin N synthase (IPNS) is a unique mononuclear nonheme Fe enzyme that catalyzes the four-electron oxidative double ring closure of its substrate ACV. A combination of spectroscopic techniques including EPR, absorbance, circular dichroism (CD), magnetic CD, and variable-temperature, variable-field MCD (VTVH-MCD) were used to evaluate the geometric and electronic structure of the [FeNO]7 complex of IPNS coordinated with the ACV thiolate ligand. Density Function Theory (DFT) calculations correlated to the spectroscopic data were used to generate an experimentally calibrated bonding description of the Fe-IPNS-ACV-NO complex. New spectroscopic features introduced by the binding of the ACV thiolate at 13 100 and 19 800 cm-1 are assigned as the NO pi*(ip) --> Fe dx2-y2 and S pi--> Fe dx2-y2 charge transfer (CT) transitions, respectively. Configuration interaction mixes S CT character into the NO pi*(ip) --> Fe dx2-y2 CT transition, which is observed experimentally from the VTVH-MCD data from this transition. Calculations on the hypothetical {FeO2}8 complex of Fe-IPNS-ACV reveal that the configuration interaction present in the [FeNO]7 complex results in an unoccupied frontier molecular orbital (FMO) with correct orientation and distal O character for H-atom abstraction from the ACV substrate. The energetics of NO/O2 binding to Fe-IPNS-ACV were evaluated and demonstrate that charge donation from the ACV thiolate ligand renders the formation of the FeIII-superoxide complex energetically favorable, driving the reaction at the Fe center. This single center reaction allows IPNS to avoid the O2 bridged binding generally invoked in other nonheme Fe enzymes that leads to oxygen insertion (i.e., oxygenase function) and determines the oxidase activity of IPNS.

(+)- and (-)-Cajanusine, a pair of new enantiomeric stilbene dimers with a new skeleton from the leaves of Cajanus cajan.

PubMed

Li, Xiao-Long; Zhao, Bing-Xin; Huang, Xiao-Jun; Zhang, Dong-Mei; Jiang, Ren-Wang; Li, Ying-Jie; Jian, Yu-Qing; Wang, Ying; Li, Yao-Lan; Ye, Wen-Cai

2014-01-03

A pair of new enantiomeric stilbene dimers, (+)- and (-)-cajanusine [(+)-1 and (-)-1], with a unique coupling pattern were isolated from the leaves of Cajanus cajan . Their structures including absolute configurations were elucidated on the basis of comprehensive spectroscopic and single-crystal X-ray diffraction analyses, as well as CD calculations. The plausible biogenetic pathway of 1 was also proposed. Additionally, (±)-1, (+)-1, and (-)-1 exhibited inhibitory activities on the growth of human hepatocellular carcinoma cells.

Synthesis and spectroscopic properties of silica-dye-semiconductor nanocrystal hybrid particles.

PubMed

Ren, Ting; Erker, Wolfgang; Basché, Thomas; Schärtl, Wolfgang

2010-12-07

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with numerically calculated FRET efficiencies and by control experiments confirming attractive interaction between the nanocrystals and Texas Red freely dissolved in solution.

Characterizing the Interaction between tartrazine and two serum albumins by a hybrid spectroscopic approach.

PubMed

Pan, Xingren; Qin, Pengfei; Liu, Rutao; Wang, Jing

2011-06-22

Tartrazine is an artificial azo dye commonly used in food products. The present study evaluated the interaction of tartrazine with two serum albumins (SAs), human serum albumin (HSA) and bovine serum albumin (BSA), under physiological conditions by means of fluorescence, three-dimensional fluorescence, UV-vis absorption, and circular dichroism (CD) techniques. The fluorescence data showed that tartrazine could bind to the two SAs to form a complex. The binding process was a spontaneous molecular interaction procedure, in which van der Waals and hydrogen bond interactions played a major role. Additionally, as shown by the UV-vis absorption, three-dimensional fluorescence, and CD results, tartrazine could lead to conformational and some microenvironmental changes of both SAs, which may affect the physiological functions of SAs. The work provides important insight into the mechanism of toxicity of tartrazine in vivo.

Zn(II), Cd(II) and Hg(I) complexes of cinnamic acid: FT-IR, FT-Raman, 1H and 13C NMR studies

NASA Astrophysics Data System (ADS)

Kalinowska, M.; Świsłocka, R.; Lewandowski, W.

2011-05-01

The effect of zinc, cadmium(II) and mercury(I) ions on the electronic structure of cinnamic acid (phenylacrylic acid) was studied. In this research many miscellaneous analytical methods, which complement one another, were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance ( 1H, 13C NMR) and quantum mechanical calculations. The spectroscopic studies provide some knowledge on the distribution of the electronic charge in molecule, the delocalization energy of π-electrons and the reactivity of metal complexes. In the series of Zn(II) → Cd(II) → Hg(I) cinnamates: (1) systematic shifts of several bands in the experimental and theoretical IR and Raman spectra and (2) regular chemical shifts for protons 1H and 13C nuclei were observed.

Cadmium-sulfide crystallites in Cd-(. gamma. EC) sub n G peptide complexes from tomato. [Lycopersicon esculentum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reese, R.N.; White, C.A.; Winge, D.R.

Hydroponically grown tomato plants (Lycopersicon esculentum P. Mill cv Golden Boy) exposed to 100 micromolar cadmium sulfate produced metal-({gamma}EC){sub n}G peptide complexes containing acid-labile sulfur. The properties of the complexes resemble those of the cadmium-({gamma}EC){sub n}G peptide complexes from Schizo-saccharomyces pombe and Candida glabrata known to contain a cadmium sulfide crystallite core. The crystallite is stabilized by a sheath of peptides of general structure ({gamma}Glu-Cys){sub n}-Gly. The cadmium-peptide complexes of tomato contained predominantly peptides of n{sub 3}, n{sub 4}, and n{sub 5}. Spectroscopic analyses indicated that the tomato cadmium-sulfide-peptide complex contained CdS crystallite core particles smaller than 2.0 nanometers inmore » diameter.« less

Cd(II) and Pb(II) complexes of the polyether ionophorous antibiotic salinomycin

PubMed Central

2011-01-01

Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II) ions in in vivo experiments, despite so far no Pb(II)-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II) and lead(II). Results New metal(II) complexes of the polyether ionophorous antibiotic salinomycin with Cd(II) and Pb(II) ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa) undergoes a reaction with heavy metal(II) ions to form [Cd(Sal)2(H2O)2] (1) and [Pb(Sal)(NO3)] (2), respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II) ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II) center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II) cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II) complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock farming. PMID:21906282

Sugarcane juice derived carbon dot–graphitic carbon nitride composites for bisphenol A degradation under sunlight irradiation

PubMed Central

Wong, Jing Lin; Hak, Chen Hong; Tai, Jun Yan; Leong, Kah Hon; Saravanan, Pichiah

2018-01-01

Carbon dots (CDs) and graphitic carbon nitride (g-C3N4) composites (CD/g-C3N4) were successfully synthesized by a hydrothermal method using urea and sugarcane juice as starting materials. The chemical composition, morphological structure and optical properties of the composites and CDs were characterized using various spectroscopic techniques as well as transmission electron microscopy. X-ray photoelectron spectroscopy (XPS) results revealed new signals for carbonyl and carboxyl groups originating from the CDs in CD/g-C3N4 composites while X-ray diffraction (XRD) results showed distortion of the host matrix after incorporating CDs into g-C3N4. Both analyses signified the interaction between g-C3N4 and CDs. The photoluminescence (PL) analysis indicated that the presence of too many CDs will create trap states at the CD/g-C3N4 interface, decelerating the electron (e−) transport. However, the CD/g-C3N4(0.5) composite with the highest coverage of CDs still achieved the best bisphenol A (BPA) degradation rate at 3.87 times higher than that of g-C3N4. Hence, the charge separation efficiency should not be one of the main factors responsible for the enhancement of the photocatalytic activity of CD/g-C3N4. Instead, the light absorption capability was the dominant factor since the photoreactivity correlated well with the ultraviolet–visible diffuse reflectance spectra (UV–vis DRS) results. Although the CDs did not display upconversion photoluminescence (UCPL) properties, the π-conjugated CDs served as a photosensitizer (like organic dyes) to sensitize g-C3N4 and injected electrons to the conduction band (CB) of g-C3N4, resulting in the extended absorption spectrum from the visible to the near-infrared (NIR) region. This extended spectral absorption allows for the generation of more electrons for the enhancement of BPA degradation. It was determined that the reactive radical species responsible for the photocatalytic activity were the superoxide anion radical (O2 •−) and holes (h+) after performing multiple scavenging tests. PMID:29515949

Large single crystal growth, transport property, and spectroscopic characterizations of three-dimensional Dirac semimetal Cd3As2.

PubMed

Sankar, R; Neupane, M; Xu, S-Y; Butler, C J; Zeljkovic, I; Panneer Muthuselvam, I; Huang, F-T; Guo, S-T; Karna, Sunil K; Chu, M-W; Lee, W L; Lin, M-T; Jayavel, R; Madhavan, V; Hasan, M Z; Chou, F C

2015-08-14

The three dimensional (3D) Dirac semimetal is a new quantum state of matter that has attracted much attention recently in physics and material science. Here, we report on the growth of large plate-like single crystals of Cd3As2 in two major orientations by a self-selecting vapor growth (SSVG) method, and the optimum growth conditions have been experimentally determined. The crystalline imperfections and electrical properties of the crystals were examined with transmission electron microscopy (TEM), scanning tunneling microscopy (STM), and transport property measurements. This SSVG method makes it possible to control the as-grown crystal compositions with excess Cd or As leading to mobilities near 5-10(5) cm(2)V(-1)s(-1). Zn-doping can effectively reduce the carrier density to reach the maximum residual resistivity ratio (RRRρ300K/ρ5K) of 7.6. A vacuum-cleaved single crystal has been investigated using angle-resolved photoemission spectroscopy (ARPES) to reveal a single Dirac cone near the center of the surface Brillouin zone with a binding energy of approximately 200 meV.

Site-specific vibrational dynamics of the CD3ζ membrane peptide using heterodyned two-dimensional infrared photon echo spectroscopy

NASA Astrophysics Data System (ADS)

Mukherjee, Prabuddha; Krummel, Amber T.; Fulmer, Eric C.; Kass, Itamar; Arkin, Isaiah T.; Zanni, Martin T.

2004-06-01

Heterodyned two-dimensional infrared (2D IR) spectroscopy has been used to study the amide I vibrational dynamics of a 27-residue peptide in lipid vesicles that encompasses the transmembrane domain of the T-cell receptor CD3ζ. Using 1-13C=18O isotope labeling, the amide I mode of the 49-Leucine residue was spectroscopically isolated and the homogeneous and inhomogeneous linewidths of this mode were measured by fitting the 2D IR spectrum collected with a photon echo pulse sequence. The pure dephasing and inhomogeneous linewidths are 2 and 32 cm-1, respectively. The population relaxation time of the amide I band was measured with a transient grating, and it contributes 9 cm-1 to the linewidth. Comparison of the 49-Leucine amide I mode and the amide I band of the entire CD3ζ peptide reveals that the vibrational dynamics are not uniform along the length of the peptide. Possible origins for the large amount of inhomogeneity present at the 49-Leucine site are discussed.

A Pimarane Diterpene and Cytotoxic Angucyclines from a Marine-Derived Micromonospora sp. in Vietnam's East Sea.

PubMed

Mullowney, Michael W; Ó hAinmhire, Eoghainín; Tanouye, Urszula; Burdette, Joanna E; Pham, Van Cuong; Murphy, Brian T

2015-09-15

A screening of our actinomycete fraction library against the NCI-60 SKOV3 human tumor cell line led to the isolation of isopimara-2-one-3-ol-8,15-diene (1), lagumycin B (2), dehydrorabelomycin (3), phenanthroviridone (4), and WS-5995 A (5). These secondary metabolites were produced by a Micromonospora sp. isolated from sediment collected off the Cát Bà peninsula in the East Sea of Vietnam. Compound 1 is a novel Δ(8,9)-pimarane diterpene, representing one of approximately 20 actinomycete-produced diterpenes reported to date, while compound 2 is an angucycline antibiotic that has yet to receive formal characterization. The structures of 1 and 2 were elucidated by combined NMR and MS analysis and the absolute configuration of 1 was assigned by analysis of NOESY NMR and CD spectroscopic data. Compounds 2-5 exhibited varying degrees of cytotoxicity against a panel of cancerous and non-cancerous cell lines. Overall, this study highlights our collaborative efforts to discover novel biologically active molecules from the large, underexplored, and biodiversity-rich waters of Vietnam's East Sea.

Mid-Gap States and Normal vs Inverted Bonding in Luminescent Cu+- and Ag+-Doped CdSe Nanocrystals.

PubMed

Nelson, Heidi D; Hinterding, Stijn O M; Fainblat, Rachel; Creutz, Sidney E; Li, Xiaosong; Gamelin, Daniel R

2017-05-10

Mid-gap luminescence in copper (Cu + )-doped semiconductor nanocrystals (NCs) involves recombination of delocalized conduction-band electrons with copper-localized holes. Silver (Ag + )-doped semiconductor NCs show similar mid-gap luminescence at slightly (∼0.3 eV) higher energy, suggesting a similar luminescence mechanism, but this suggestion appears inconsistent with the large difference between Ag + and Cu + ionization energies (∼1.5 eV), which should make hole trapping by Ag + highly unfavorable. Here, Ag + -doped CdSe NCs (Ag + :CdSe) are studied using time-resolved variable-temperature photoluminescence (PL) spectroscopy, magnetic circularly polarized luminescence (MCPL) spectroscopy, and time-dependent density functional theory (TD-DFT) to address this apparent paradox. In addition to confirming that Ag + :CdSe and Cu + :CdSe NCs display similar broad PL with large Stokes shifts, we demonstrate that both also show very similar temperature-dependent PL lifetimes and magneto-luminescence. Electronic-structure calculations further predict that both dopants generate similar localized mid-gap states. Despite these strong similarities, we conclude that these materials possess significantly different electronic structures. Specifically, whereas photogenerated holes in Cu + :CdSe NCs localize primarily in Cu(3d) orbitals, formally oxidizing Cu + to Cu 2+ , in Ag + :CdSe NCs they localize primarily in 4p orbitals of the four neighboring Se 2- ligands, and Ag + is not oxidized. This difference reflects a shift from "normal" to "inverted" bonding going from Cu + to Ag + . The spectroscopic similarities are explained by the fact that, in both materials, photogenerated holes are localized primarily within covalent [MSe 4 ] dopant clusters (M = Ag + , Cu + ). These findings reconcile the similar spectroscopies of Ag + - and Cu + -doped semiconductor NCs with the vastly different ionization potentials of their Ag + and Cu + dopants.

The influence of surface coating on the properties of water-soluble CdSe and CdSe/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Coto-García, Ana María; Fernández-Argüelles, María T.; Costa-Fernández, José M.; Sanz-Medel, Alfredo; Valledor, Marta; Campo, Juan C.; Ferrero, Francisco J.

2013-01-01

It is well-known that ligands coating the surface of luminescent semiconductor nanocrystals (quantum dots [QDs]) play an important role in the preparation, stability and physical properties of the colloidal QDs in both organic and aqueous media. Here we report on the synthesis and characterization of core (CdSe QDs) and core-shell structured QDs (CdSe/ZnS QDs), both of them stabilized in aqueous medium through different mechanisms of modification of their surface chemistry. The approaches evaluated for QDs transfer to aqueous media were ligand exchange and polymer coating. Experiments were performed using two typical thioalkyl acids as ligands, namely mercaptoacetic acid (QDs-MAA) and 2-mercaptoethanesulphonic acid (QDs-MES), and an amphiphilic polymer (PQDs) based on poly(maleic anhydride) functional groups. The effects of pH (buffer solution), illumination and the presence of ions in the QD environment on the spectroscopic properties of the different synthesized QDs are reported. The stability of the prepared QDs has been comparatively evaluated aimed to elucidate which surface chemistry provides the suitable properties to be employed as fluorescence labels in distinct types of applications. The experimental results and conclusions will be useful for the development of sensitive sensors or assays adopting QDs as fluorescence labels.

Role of RGO support and irradiation source on the photocatalytic activity of CdS–ZnO semiconductor nanostructures

PubMed Central

Kumar, Suneel; Sharma, Rahul; Sharma, Vipul; Harith, Gurunarayanan; Sivakumar, Vaidyanathan

2016-01-01

Photocatalytic activity of semiconductor nanostructures is gaining much importance in recent years in both energy and environmental applications. However, several parameters play a crucial role in enhancing or suppressing the photocatalytic activity through, for example, modifying the band gap energy positions, influencing the generation and transport of charge carriers and altering the recombination rate. In this regard, physical parameters such as the support material and the irradiation source can also have significant effect on the activity of the photocatalysts. In this work, we have investigated the role of reduced graphene oxide (RGO) support and the irradiation source on mixed metal chalcogenide semiconductor (CdS–ZnO) nanostructures. The photocatalyst material was synthesized using a facile hydrothermal method and thoroughly characterized using different spectroscopic and microscopic techniques. The photocatalytic activity was evaluated by studying the degradation of a model dye (methyl orange, MO) under visible light (only) irradiation and under natural sunlight. The results reveal that the RGO-supported CdS–ZnO photocatalyst performs considerably better than the unsupported CdS–ZnO nanostructures. In addition, both the catalysts perform significantly better under natural sunlight than under visible light (only) irradiation. In essence, this work paves way for tailoring the photocatalytic activity of semiconductor nanostructures. PMID:28144518

Spectroscopic interaction study of human serum albumin and human hemoglobin with Mersilea quadrifolia leaves extract mediated silver nanoparticles having antibacterial and anticancer activity

NASA Astrophysics Data System (ADS)

Maji, Anukul; Beg, Maidul; Mandal, Amit Kumar; Das, Somnath; Jha, Pradeep K.; Kumar, Anoop; Sarwar, Shamila; Hossain, Maidul; Chakrabarti, Pinak

2017-08-01

This study looks into a safe, proficient and low-cost way for the preparation of novel silver nanoparticles by using 5% aqueous leaves extract of a medicinal plant, Marsilea quadrifolia (family: Marsileaceae) without using any external reducing and stabilizing agents. The synthesized AgNPs showed maximum UV-Vis absorbance at 435 nm due to surface plasmon resonance (SPR). The average diameter (∼22.5 nm) of AgNPs was measured from TEM analysis and was also supported by FE-SEM. The existence of a silver signal in EDX spectra supported the AgNPs formation and negative zeta potential value (-18.7 mV) which suggested its stability. FT-IR spectroscopic analysis showed that the functional groups like sbnd Osbnd H, sbnd Nsbnd H and sbnd Cdbnd O were responsible for the synthesis of AgNPs. The antibacterial activity of the AgNPs was tested against E. coli ATCC 25922. The anticancer potential of AgNPs was also assessed using two different cell lines, such as MCF-7 and HeLa. The interaction study of AgNPs with human serum albumin (HSA) and human hemoglobin (Hb) was performed by means of UV-Vis, fluorescence spectroscopy, Circular dichroism (CD) and zeta potential measurement. More negative zeta potential values of AgNPs-HSA/Hb (-21.1/-19.5 mV) complexes than AgNPs (-18.7 mV) indicated corresponding stability of bio-conjugates. The basic structure of HSA/Hb remained unchanged and its secondary structure was slightly changed upon interaction with the AgNPs concluded from Circular dichroism. So, it can be predicted that this AgNPs may be applied in the medical field.

Linear and nonlinear optical discussions of nanostructured Zn-doped CdO thin films

NASA Astrophysics Data System (ADS)

Yahia, I. S.; Salem, G. F.; Iqbal, Javed; Yakuphanoglu, F.

2017-04-01

Here, we report the doping effect of zinc (Zn) on the physical properties of cadmium oxide (CdO) at various concentrations (1, 2, 3 and 4 wt% of Zn). The studied samples were prepared using sol-gel in addition with sol gel spin coating technique. The structural, optical and dispersive properties were compared with the already reported work in the literature. The structural properties were observed by using atomic force microscopy (AFM). The AFM images show that the grain size decreases with increasing the concentration of Zn. The highest value of average cluster size (78. 71 nm) was found at 1% and the lowest (60.23 nm) when the doping concentration of Zn was 4%. Similar trend was observed in the roughness of the doped thin film when the Zn concentration was increased. The optical properties were examined using Shimadzu UV-Vis-NIR spectrophotometer and we found that the optical band gap of the un-doped CdO and the Zn-doped CdO thin films increases from 2.54 to 2.62 eV as the Zn concentration is increased from 1% to 4%. Also, the optical dispersion parameters (Eo, Ed, n2∞, λ0 and So) were calculated and discussed. We observed that the refractive index dispersion of undoped CdO and the Zn-doped CdO thin films follow the single oscillator model. Finally, spectroscopic method has been exploited to analyze the 3rd order non-linear optical susceptibility χ (3) and nonlinear refractive index n (2).

Growth, spectroscopic and physicochemical properties of bis mercury ferric chloride tetra thiocyanate: A nonlinear optical crystal

NASA Astrophysics Data System (ADS)

Ramesh, V.; Shihabuddeen Syed, A.; Jagannathan, K.; Rajarajan, K.

2013-05-01

Single crystal of bis mercury ferric chloride tetra thiocyanate [Hg2FeCl3(SCN)4; (MFCTC)] was grown from ethanol-water (3:1) mixed solvent using slow evaporation solvent technique (SEST) for the first time. The cell parameters of the grown crystal were confirmed by single crystal XRD. The coordination of transition metal ions with the SCN ligand is well-identified using FT-IR spectral analysis. The chemical composition of MFCTC was confirmed using CHNS elemental test. The ESR spectral profile of MFCTC was recorded from 298 K to 110 K, which strongly suggests the incorporation of Fe3+ ion and its environment with respect to SCN ligand. The HPLC chromatogram of MFCTC highlights the purity of the compound. The UV-Vis-NIR studies revealed the ultra violet cut-off wavelength of MFCTC in ethanol as 338 nm. The dielectric constant and dielectric loss of the sample were studied as a function of frequency and temperature. The TGA-DTA and DSC thermal analysis show that the sample is thermally stable up to 234.31 °C, which is comparatively far better than the thermal stability of Hg3CdCl2(SCN)6; (171.3 °C) and other metal-organic coordination complex crystals such as CdHg(SCN)4 (198.5 °C), Hg(N2H4CS)4Mn(SCN)4 (199.06 °C) and Hg(N2H4CS)4Zn(SCN)4 (185 °C). The SHG conversion efficiency of MFCTC is found to be higher than KDP.

Biophysical influence of isocarbophos on bovine serum albumin: Spectroscopic probing

NASA Astrophysics Data System (ADS)

Zhang, Hua-xin; Zhou, Ying; Liu, E.

Isocarbophos (ICP) is a phosphorous pesticide with high toxicity. It has been detected in several kinds of food and therefore can enter human body. In this paper, spectroscopic approaches including three-dimensional fluorescence (3D-FL) spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy were employed to explore the binding of ICP to bovine serum albumin (BSA) at simulated physiological conditions. It was found that the fluorescence quenching of BSA was caused by the formation of ICP-BSA complex at ground state and belonged to static quenching mechanism. The binding constants, the number of binding sites, enthalpy change (ΔHθ), Gibbs free energy change (ΔGθ) and entropy change (ΔSθ) were calculated at four different temperatures according to Scatchard model and thermodynamic equations. To identify the binding location, fluorescence probe techniques were used. The results showed that warfarin, an acknowledged site marker for BSA, could be partially replaced by ICP when ICP was added to warfarin-BSA systems, which demonstrated that ICP primarily bound on Sudlow's site I in domain IIA of BSA molecule. The distance r (3.06 nm) between donor (Trp-212) and acceptor (ICP) was obtained based on Förster's non-radiation fluorescence resonance energy transfer (FRET) theory. Furthermore, the CD spectral results indicated that the secondary structure of BSA was changed in presence of ICP. The study is helpful to evaluating the toxicology of ICP and understanding its effects on the function of protein during the blood transportation process.

In vitro DNA binding studies of lenalidomide using spectroscopic in combination with molecular docking techniques

NASA Astrophysics Data System (ADS)

Xu, Liang; Hu, Yan-Xi; Li, Yan-Cheng; Zhang, Li; Ai, Hai-Xin; Liu, Yu-Feng; Liu, Hong-Sheng

2018-02-01

In the present work, the binding interaction between lenalidomide (LEN) and calf thymus DNA (ct-DNA) was systematically studied by using fluorescence, ultraviolet-visible (UV-vis) absorption, circular dichroism (CD) spectroscopies under imitated physiological conditions (pH = 7.4) coupled with molecular docking. It was found that LEN was bound to ct-DNA with high binding affinity (Ka = 2.308 × 105 M-1 at 283 K) through groove binding as evidenced by a slight decrease in the absorption intensity in combination with CD spectra. Thermodynamic parameters (ΔG < 0, ΔH > 0 and ΔS < 0) of the LEN-DNA system obtained at three different temperatures suggested that the binding process was spontaneous and was primarily driven by hydrogen bonds and hydrophobic interaction. Furthermore, competitive binding experiments with ethidium bromide and 4‧, 6-dia-midino-2-phenylindoleas probes showed that LEN could preferentially bind in the minor groove of double-stranded DNA. The average lifetime of LEN was calculated to be 7.645 ns. The φ of LEN was measured as 0.09 and non-radiation energy transfer between LEN and DNA had occurred. The results of the molecular docking were consistent with the experimental results. This study explored the potential applicability of the spectroscopic properties of LEN and also investigated its interactions with relevant biological targets. In addition, it will provide some theoretical references for the deep research of simultaneous administration of LEN with other drugs.

Spectroscopic Studies on Unfolding Processes of Apo-Neuroglobin Induced by Guanidine Hydrochloride and Urea

PubMed Central

Zhang, Cui; Gao, Chaohui; Qiu, Zhanglei

2013-01-01

Neuroglobin (Ngb), a recently discovered globin, is predominantly expressed in the brain, retina, and other nerve tissues of vertebrates. The unfolding processes of apo-neuroglobin (apoNgb) induced by guanidine hydrochloride (GdnHCl) and urea were investigated by spectroscopic methods. In the unfolding processes, apoNgb's tertiary structural transition was monitored by the changes of intrinsic fluorescence emission spectra, and its secondary structural transition was measured by the changes of far-ultraviolet circular dichroism (CD) spectra. In addition, 8-anilino-1-naphthalenesulfonic acid (ANS), a hydrophobic cluster binding dye, was also used to monitor the unfolding process of apoNgb and to explore its intermediates. Results showed that GdnHCl-induced unfolding of apoNgb was via a three-state pathway, that is, Native state (N) → Intermediate state (I) → Unfolded state (U), during which the intermediate was inferred by an increase in fluorescence intensity and the change of CD value. Gibbs free energy changes are 10.2 kJ·mol−1 for the first unfolding transition and 14.0 kJ·mol−1 for the second transition. However, urea-induced unfolding of apoNgb only underwent a two-state transition: Native state (N) → Partially unfolded state (P). The result showed that GdnHCl can efficiently affect the conformational states of apoNgb compared with those of urea. The work will benefit to have an understanding of the unfolding mechanism of apoNgb induced by GdnHCl and urea. PMID:23984347

A spectroscopic and thermodynamic study of porphyrin/DNA supramolecular assemblies.

PubMed Central

Pasternack, R F; Goldsmith, J I; Szép, S; Gibbs, E J

1998-01-01

Assemblies of trans-bis(N-methylpyridinium-4-yl)diphenylporphine ions on the surface of calf thymus DNA have been studied using several spectroscopic techniques: absorbance, circular dichroism, and resonance light scattering. The aggregation equilibrium can be treated as a two-state system-monomer and assembly-each bound to the nucleic acid template. The aggregate absorption spectrum in the Soret region is resolved into two bands of Lorentzian line shape, while the DNA-bound monomer spectrum in this region is composed of two Gaussian bands. The Beer-Lambert law is obeyed by both porphyrin forms. The assembly is also characterized by an extremely large, bisignate induced circular dichroism (CD) profile and by enhanced resonance light scattering (RLS). Both the CD and RLS intensities depend linearly on aggregate concentration. The RLS result is consistent with a model for the aggregates as being either of a characteristic size or of a fixed distribution of sizes, independent of total porphyrin concentration or ionic strength. Above threshold values of concentration and ionic strength, the mass action expression for the equilibrium has a particularly simple form: K' = cac-1; where cac is defined as the "critical assembly concentration."offe dependence of the cac upon temperature and ionic strength (NaCl) has been investigated at a fixed DNA concentration. The value of the cac scales as the inverse square of the sodium chloride concentration and, from temperature dependence studies, the aggregation process is shown to be exothermic. PMID:9675203

Investigation on the interaction of Rutin with serum albumins: Insights from spectroscopic and molecular docking techniques.

PubMed

Sengupta, Priti; Sardar, Pinki Saha; Roy, Pritam; Dasgupta, Swagata; Bose, Adity

2018-06-01

The binding interaction of Rutin, a flavonoid, with model transport proteins, bovine serum albumin (BSA) and human serum albumin (HSA), were investigated using different spectroscopic techniques, such as fluorescence, time-resolved single photon counting (TCSPC) and circular dichroism (CD) spectroscopy as well as molecular docking method. The emission studies revealed that the fluorescence quenching of BSA/HSA by Rutin occurred through a simultaneous static and dynamic quenching process, and we have evaluated both the quenching constants individually. The binding constants of Rutin-BSA and Rutin-HSA system were found to be 2.14 × 10 6  M -1 and 2.36 × 10 6  M -1 at 298 K respectively, which were quite high. Further, influence of some biologically significant metal ions (Ca 2+ , Zn 2+ and Mg 2+ ) on binding of Rutin to BSA and HSA were also investigated. Thermodynamic parameters justified the involvement of hydrogen bonding and weak van der Waals forces in the interaction of Rutin with both BSA and HSA. Further a site-marker competitive experiment was performed to evaluate Rutin binding site in the albumins. Additionally, the CD spectra of BSA and HSA revealed that the secondary structure of the proteins was perturbed in the presence of Rutin. Finally protein-ligand docking studies have also been performed to determine the probable location of the ligand molecule. Copyright © 2018 Elsevier B.V. All rights reserved.

Exploring the affinity binding of alkylmaltoside surfactants to bovine serum albumin and their effect on the protein stability: A spectroscopic approach.

PubMed

Hierrezuelo, J M; Carnero Ruiz, C

2015-08-01

Steady-state and time-resolved fluorescence together with circular dichroism (CD) spectroscopic studies was performed to examine the interactions between bovine serum albumin (BSA) and two alkylmaltoside surfactants, i.e. n-decyl-β-D-maltoside (β-C10G2) and n-dodecyl-β-D-maltoside (β-C12G2), having identical structures but different tail lengths. Changes in the intrinsic fluorescence of BSA from static as well as dynamic measurements revealed a weak protein-surfactant interaction and gave the corresponding binding curves, suggesting that the binding mechanism of surfactants to protein is essentially cooperative in nature. The behavior of both surfactants is similar, so that the differences detected were attributed to the more hydrophobic nature of β-C12G2, which favors the adsorption of micelle-like aggregates onto the protein surface. These observations were substantially demonstrated by data derived from synchronous, three-dimensional and anisotropy fluorescence experiments. Changes in the secondary structure of the protein induced by the interaction with surfactants were analyzed by CD to determine the contents of α-helix and β-strand. It was noted that whereas the addition of β-C10G2 appears to stabilize the secondary structure of the protein, β-C12G2 causes a marginal denaturation of BSA for a protein:surfactant molar ratio as high as 1 to 100. Copyright © 2015 Elsevier B.V. All rights reserved.

Apparatus and method for spectroscopic analysis of scattering media

DOEpatents

Strobl, Karlheinz; Bigio, Irving J.; Loree, Thomas R.

1994-01-01

Apparatus and method for spectroscopic analysis of scattering media. Subtle differences in materials have been found to be detectable from plots of intensity as a function of wavelength of collected emitted and scattered light versus wavelength of excitation light.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genest-Beaulieu, C.; Bergeron, P., E-mail: genest@astro.umontreal.ca, E-mail: bergeron@astro.umontreal.ca

We present a comparative analysis of atmospheric parameters obtained with the so-called photometric and spectroscopic techniques. Photometric and spectroscopic data for 1360 DA white dwarfs from the Sloan Digital Sky Survey (SDSS) are used, as well as spectroscopic data from the Villanova White Dwarf Catalog. We first test the calibration of the ugriz photometric system by using model atmosphere fits to observed data. Our photometric analysis indicates that the ugriz photometry appears well calibrated when the SDSS to AB{sub 95} zeropoint corrections are applied. The spectroscopic analysis of the same data set reveals that the so-called high-log g problem canmore » be solved by applying published correction functions that take into account three-dimensional hydrodynamical effects. However, a comparison between the SDSS and the White Dwarf Catalog spectra also suggests that the SDSS spectra still suffer from a small calibration problem. We then compare the atmospheric parameters obtained from both fitting techniques and show that the photometric temperatures are systematically lower than those obtained from spectroscopic data. This systematic offset may be linked to the hydrogen line profiles used in the model atmospheres. We finally present the results of an analysis aimed at measuring surface gravities using photometric data only.« less

Insight into the biochemical, kinetic and spectroscopic characterization of garlic (Allium sativum) phytocystatin: Implication for cardiovascular disease.

PubMed

Siddiqui, Mohd Faizan; Ahmed, Azaj; Bano, Bilqees

2017-02-01

Phytocystatins are cysteine proteinase inhibitors present in plants. They play crucial role in maintaining protease-anti protease balance and are involved in various endogenous processes. Thus, they are suitable and convenient targets for genetic engineering which makes their isolation and characterisation from different sources the need of the hour. In the present study a phytocystatin has been isolated from garlic (Allium sativum) by a simple two-step process using ammonium sulphate fractionation and gel filtration chromatography on Sephacryl S-100HR with a fold purification of 152.6 and yield 48.9%. A single band on native gel electrophoresis confirms the homogeneity of the purified inhibitor. The molecular weight of the purified inhibitor was found to be 12.5kDa as determined by SDS-PAGE and gel filtration chromatography. The garlic phytocystatin was found to be stable under broad range of pH (6-8) and temperature (30°C-60°C). Kinetic studies suggests that garlic phytocystatins are reversible and non-competitive inhibitors having highest affinity for papain followed by ficin and bromelain. UV and fluorescence spectroscopy revealed significant conformational change upon garlic phytocystatin-papain complex formation. Secondary structure analysis was performed using CD and FTIR. Garlic phytocystatin possesses 33.9% alpha-helical content as assessed by CD spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

Spectroscopic studies of the interaction between pirimicarb and calf thymus DNA.

PubMed

Zhang, Guowen; Hu, Xing; Pan, Junhui

2011-02-01

The interaction between pirimicarb and calf thymus DNA in physiological buffer (pH 7.4) was investigated with the use of Neutral Red (NR) dye as a spectral probe by UV-vis absorption, fluorescence and circular dichroism (CD) spectroscopy, as well as viscosity measurements and DNA melting techniques. The results revealed that an intercalation binding should be the interaction mode of pirimicarb to DNA. CD spectra indicated that pirimicarb induced conformational changes of DNA. The binding constants of pirimicarb with DNA were obtained by the fluorescence quenching method. The thermodynamic parameters, enthalpy change (ΔHθ) and entropy change (ΔSθ) were calculated to be -52.13±2.04 kJ mol(-1) and -108.8±6.72 J mol(-1) K(-1) according to the van't Hoff equation, which suggested that hydrogen bonds and van der Waals forces might play a major role in the binding of pirimicarb to DNA. Further, the alternative least squares (ALS) method was applied to resolve a complex two-way array of the absorption spectra data, which provided simultaneously the concentration information for the three reaction components, pirimicarb, NR and DNA-NR. This ALS analysis indicated that the intercalation of pirimicarb into the DNA by substituting for NR in the DNA-NR complex. Copyright © 2010 Elsevier B.V. All rights reserved.

Syntheses, spectroscopic and thermal analyses of cyanide bridged heteronuclear polymeric complexes: [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine or N-ethylethylenediamine; Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II))

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla

2016-02-01

Polymeric tetracyanonickelate(II) complexes of the type [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine (men) or N-ethylethylenediamine (neen); Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II)) have been prepared and characterized by FT-IR, Raman spectroscopy, thermal and elemental analysis techniques. Additionally, FT-IR and Raman spectral analyses of men and neen have experimentally and theoretically investigated in the range of 4000-250 cm-1. The corresponding vibration assignments of men and neen are performed by using B3LYP density functional theory (DFT) method together with 6-31 G(d) basis set. The spectral features of the complexes suggest that the coordination environment of the M(II) ions are surrounded by the two symmetry related men and neen ligands and the two symmetry related N atom of cyanide groups, whereas the Ni(II) atoms are coordinated with a square-planar to four C atoms of the cyanide groups. Polymeric structures of the complexes consist of one dimensional alternative chains of [M(L)2]2+ and [Ni(CN)4]2- moieties. The thermal decompositions in the temperature range 30-700 °C of the complexes were investigated in the static air atmosphere.

Acetaminophen interacts with human hemoglobin: optical, physical and molecular modeling studies.

PubMed

Seal, Paromita; Sikdar, Jyotirmoy; Roy, Amartya; Haldar, Rajen

2017-05-01

Acetaminophen, a widely used analgesic and antipyretic drug has ample affinity to bind globular proteins. Here, we have illustrated a substantive study pertaining to the interaction of acetaminophen with human hemoglobin (HHb). Different spectroscopic (absorption, fluorescence, and circular dichroism (CD) spectroscopy), calorimetric, and molecular docking techniques have been employed in this study. Acetaminophen-induced graded alterations in absorbance and fluorescence of HHb confirm their interaction. Analysis of fluorescence quenching at different temperature and data obtained from isothermal titration calorimetry indicate that the interaction is static and the HHb has one binding site for the drug. The negative values of Gibbs energy change (ΔG 0 ) and enthalpy changes (ΔH 0 ) and positive value of entropy change (ΔS 0 ) strongly suggest that it is entropy-driven spontaneous and exothermic reaction. The reaction involves hydrophobic pocket of the protein which is further stabilized by hydrogen bonding as evidenced from ANS and sucrose binding studies. These findings were also supported by molecular docking simulation study using AutoDock 4.2. The interaction influences structural integrity as well as functional properties of HHb as evidenced by CD spectroscopy, increased rate of co-oxidation and decreased esterase activity of HHb. So, from these findings, we may conclude that acetaminophen interacts with HHb through hydrophobic and hydrogen bonding, and the interaction perturbs the structural and functional properties of HHb.

Molecular spectroscopic and thermodynamic studies on the interaction of anti-platelet drug ticlopidine with calf thymus DNA

NASA Astrophysics Data System (ADS)

Afrin, Shumaila; Rahman, Yusra; Sarwar, Tarique; Husain, Mohammed Amir; Ali, Abad; Shamsuzzaman; Tabish, Mohammad

2017-11-01

Ticlopidine is an anti-platelet drug which belongs to the thienopyridine structural family and exerts its effect by functioning as an ADP receptor inhibitor. Ticlopidine inhibits the expression of TarO gene in S. aureus and may provide protection against MRSA. Groove binding agents are known to disrupt the transcription factor DNA complex and consequently inhibit gene expression. Understanding the mechanism of interaction of ticlopidine with DNA can prove useful in the development of a rational drug designing system. At present, there is no such study on the interaction of anti-platelet drugs with nucleic acids. A series of biophysical experiments were performed to ascertain the binding mode between ticlopidine and calf thymus DNA. UV-visible and fluorescence spectroscopic experiments confirmed the formation of a complex between ticlopidine and calf thymus DNA. Moreover, the values of binding constant were found to be in the range of 103 M- 1, which is indicative of groove binding between ticlopidine and calf thymus DNA. These results were further confirmed by studying the effect of denaturation on double stranded DNA, iodide quenching, viscometric studies, thermal melting profile as well as CD spectral analysis. The thermodynamic profile of the interaction was also determined using isothermal titration calorimetric studies. The reaction was found to be endothermic and the parameters obtained were found to be consistent with those of known groove binders. In silico molecular docking studies further corroborated well with the experimental results.

Synthesis and spectroscopic study of CdS nanoparticles using hydrothermal method

NASA Astrophysics Data System (ADS)

AL-Mamoori, Mohammed H. K.; Mahdi, Dunia K.; Al-Shrefi, Saif M.

2018-05-01

In this work, cadmium sulfide nanoparticles (powder) with diameter 50.8 nm was prepared using hydrothermal method. The structural and optical properties of CdS nanoparticles was studied by X-ray diffraction, FESEM, EDS, FTIR, UV-Diffuse Reflectance spectroscopy and Photoluminance spectrum. X-ray diffraction reveal the formation the purity of prepared phase of CdS particles with hexagonal wurtzite structure with particle size 31.8nm by using sheerer equation. The energy dispersion scattering (EDS) examination explains that the sample is composed of a large amount of Cd and S which are exactly CdS nanoparticles and there is a very small trace of (Zn) and (O) element observed because of there is a small pollutions in the measurement place of samples. FESEM shows the spherical shape of nanoparticles with around 50.8 nm diameter. The optical absorption spectral study identified the red shift of the sample in comparison to bulk ZnO in three dimensions. Photoluminance spectrum (PL) at room temperature showed that there are two luminescence peaks at 433.14 nm and 518.21nm. Samples demonstrate a sharp emission band at around 433.18 nm, which is attributed to the typical exciton luminescence. The broad band at 518.21nm which were attributed to the trapped luminescence. The green emission band at 518.21 nm was associated with the emission due to electronic transition from the conduction band to an accepter level due to interstitial sulphur ion.

Effect of deuteration on hydrogen bonding: A comparative concentration dependent Raman and DFT study of pyridine in CH3OH and CD3OD and pyrimidine in H2O and D2O

NASA Astrophysics Data System (ADS)

Singh, Anurag; Gangopadhyay, Debraj; Popp, Jürgen; Singh, Ranjan K.

2012-12-01

The relative effect of hydrogen bonding of pyrimidine (Pyr) in H2O/D2O and pyridine (Py) in CH3OH/CD3OD has been analyzed using Raman Difference Spectroscopic (RDS) technique and DFT calculations. This study is focused on analyzing the concentration dependent variation of linewidth, peak position and intensity of ring breathing mode of Py and Pyr. The ring breathing mode of Pyr in H2O and D2O has three components; due to free Pyr, lighter complexes of mPyr + nH2O/D2O and heavier complexes of mPyr + nH2O/D2O. The pyridine molecules, however, show only two components in CH3OH and CD3OD. Of these two components, one corresponds to free Py and the other inhomogeneously broadened profile corresponds to all mPy + nCH3OH/CD3OD complexes. The variation of peak position and linewidth establishes the role of dipole moment of complexes and the diffusion in the mixture. In case of CD3OD solution splitting was observed in ˜1030 cm-1 band of Py, where an additional band at ˜1034 cm-1 appears at x(Py) ⩽ 0.4. However, this band remains single at all concentrations in case of CH3OH solvent.

Measuring Te inclusion uniformity over large areas for CdTe/CZT imaging and spectrometry sensors

NASA Astrophysics Data System (ADS)

Bolke, Joe; O'Brien, Kathryn; Wall, Peter; Spicer, Mike; Gélinas, Guillaume; Beaudry, Jean-Nicolas; Alexander, W. Brock

2017-09-01

CdTe and CZT materials are technologies for gamma and x-ray imaging for applications in industry, homeland security, defense, space, medical, and astrophysics. There remain challenges in uniformity over large detector areas (50 75 mm) due to a combination of material purity, handling, growth process, grown in defects, doping/compensation, and metal contacts/surface states. The influence of these various factors has yet to be explored at the large substrate level required for devices with higher resolution both spatially and spectroscopically. In this study, we looked at how the crystal growth processes affect the size and density distributions of microscopic Te inclusion defects. We were able to grow single crystals as large as 75 mm in diameter and spatially characterize three-dimensional defects and map the uniformity using IR microscopy. We report on the pattern of observed defects within wafers and its relation to instabilities at the crystal growth interface.

Spectroscopic characterization of furosemide binding to human carbonic anhydrase II.

PubMed

Ranjbar, Samira; Ghobadi, Sirous; Khodarahmi, Reza; Nemati, Houshang

2012-05-01

This study reports the interaction between furosemide and human carbonic anhydrase II (hCA II) using fluorescence, UV-vis and circular dichroism (CD) spectroscopy. Fluorescence data indicated that furosemide quenches the intrinsic fluorescence of the enzyme via a static mechanism and hydrogen bonding and van der Walls interactions play the major role in the drug binding. The binding average distance between furosemide and hCA II was estimated on the basis of the theory of Förster energy transfer. Decrease of protein surface hydrophobicity was also documented upon furosemide binding. Chemical modification of hCA II using N-bromosuccinimide indicated decrease of the number of accessible tryptophans in the presence of furosemide. CD results suggested the occurance of some alterations in α-helical content as well as tertiary structure of hCA II upon drug binding. Copyright © 2012 Elsevier B.V. All rights reserved.

Non-intercalative, deoxyribose binding of boric acid to calf thymus DNA.

PubMed

Ozdemir, Ayse; Gursaclı, Refiye Tekiner; Tekinay, Turgay

2014-05-01

The present study characterizes the effects of the boric acid binding on calf thymus DNA (ct-DNA) by spectroscopic and calorimetric methods. UV-Vis absorbance spectroscopy, circular dichroism (CD) spectroscopy, transmission electron microscopy (TEM), isothermal titration calorimetry (ITC), and Fourier transform infrared (FT-IR) spectroscopy were employed to characterize binding properties. Changes in the secondary structure of ct-DNA were determined by CD spectroscopy. Sizes and morphologies of boric acid-DNA complexes were determined by transmission electron microscopy (TEM). The kinetics of boric acid binding to calf thymus DNA (ct-DNA) was investigated by isothermal titration calorimetry (ITC). ITC results revealed that boric acid exhibits a moderate affinity to ct-DNA with a binding constant (K a) of 9.54 × 10(4) M(-1). FT-IR results revealed that boric acid binds to the deoxyribose sugar of DNA without disrupting the B-conformation at tested concentrations.

The Inhomogeneous Centers of Cooling Flows in Galaxy Clusters

NASA Astrophysics Data System (ADS)

Sharma, Mangala

2004-04-01

The intracluster medium (ICM) in the centers of galaxy clusters is cool, dense and may be imhomogeneous. We present Chandra X-ray Observatory imaging spectroscopic data on two galaxy clusters, Abell 1991 and MS 0839.8+2938, that have cooling flows in their central few hundred kpc. Their cD galaxies show current star formation, and host compact radio sources. The hot ICM at both their centers has nonhomogeneities on kiloparsec scales. These finer structures are likely to be signatures of the formation of clusters through infall of smaller, cooler subclusters.

VizieR Online Data Catalog: Spectroscopic analysis of 348 red giants (Zielinski+, 2012)

NASA Astrophysics Data System (ADS)

Zielinski, P.; Niedzielski, A.; Wolszczan, A.; Adamow, M.; Nowak, G.

2012-10-01

The atmospheric parameters were derived using a strictly spectroscopic method based on the LTE analysis of equivalent widths of FeI and FeII lines. With existing photometric data and the Hipparcos parallaxes, we estimated stellar masses and ages via evolutionary tracks fitting. The stellar radii were calculated from either estimated masses and the spectroscopic logg or from the spectroscopic Teff and estimated luminosities. The absolute radial velocities were obtained by cross-correlating spectra with a numerical template. Our high-quality, high-resolution optical spectra have been collected since 2004 with the Hobby-Eberly Telescope (HET), located in the McDonald Observatory. The telescope was equipped with the High Resolution Spectrograph (HRS; R~60000 resolution). (2 data files).

Terahertz Spectroscopy of Deuterated Methylene Bi-Radical CD_2

NASA Astrophysics Data System (ADS)

Ozeki, Hiroyuki; Bailleux, Stephane

2015-06-01

Methylene, the parent of the carbene compounds, plays a crucial role in many chemical reactions. This bi-radical is a known interstellar molecule that has been detected towards hot cores in dense interstellar clouds. CH_2 is also thought to be present in cometary atmospheres. In the gas phase chemical models of both dense and diffuse molecular clouds, CH_2 is a key intermediate in interstellar carbon chemistry which is produced primarily by dissociative recombination of the methyl ion, CH^+_3. Recently tentative detection of the mono-deuterated methyl ion, CH_2D^+ has been reported toward an infrared source in the vicinity of Orion. Deuterated methylene CHD and CD_2 can be produced from this ion or its counterpart CHD^+_2 by dissociative recombination with an electron: CH2D+ + e- → CHD+ H or {CH2 + D}, CHD2+ ~+ e- → CHD+ D or CD2 + H. Thus, both CHD and CD_2 can be observed in warm interstellar clouds, where the deuterium fractionation process is important. Precise laboratory reference data are desirable for radioastronomical observation of these molecules. Here we report on our high-resolution spectroscopic investigation on the deuterated methylene radical, CD_2 (X ^3B_1) up to 1.45 THz. At present time, eleven out of the twelve fine-structure components of four pure rotational transitions have been newly recorded, and these measurements double the number of previously observed transitions. CD_2 was generated in a discharge in CD_2CO which was obtained from the flash pyrolysis of acetic anhydride-d6 ((CD_3CO)_2O). Effort is currently made to measure the astronomically important 111 - 000 transition whose fine-structure components are predicted to occur at 1.224,1.228 and 1.234 THz. D. C. Lis, P. F. Goldsmith, E. A. Bergin et al. 2009, in Submillimeter Astrophysics and Technology, ASP Conf. Ser., 417, 23. H. Ozeki and S. Saito J. Chem. Phys. 1996, 104, 2167.

Transition Metal Nanomaterials by Bacterial Precipitation: Synthesis and Characterization of Cadmium Sulfide Quantum Dots

NASA Astrophysics Data System (ADS)

Marusak, Katherine Elizabeth

We present a new method to fabricate semiconducting, transition metal nanoparticles (NPs) with tunable bandgap energies using engineered Escherichia coli. These bacteria overexpress the Treponema denticola cysteine desulfhydrase gene to facilitate precipitation of cadmium sulfide (CdS) NPs. Multiple characterization techniques reveal that the bacterially precipitated NPs are agglomerates of mostly quantum dots, with diameters that can range from 3 to 15 nm, embedded in a carbon-rich matrix. Notably, the measured photoelectrochemical current generated by these NPs is comparable to values reported in the literature and higher than that of synthesized chemical bath deposited CdS NPs. We showed that we can manipulate the bandgap energy of the NPs by controlling their size through varying the precursor concentrations. Our calculated bandgap energies ranged between 2.67 eV (i.e., quantum confined CdS) to 2.36 eV ( i.e., bulk CdS). By adding the CdCl2 precursor at a specific stage of the bacterial growth cycle, we were able to induce extracellular CdS NP precipitation. Additionally, we adapted extracellular precipitation strategies to form CdS NPs on surfaces as bacterial/PC membrane composites and characterized them by spectroscopic and imaging methods, including energy dispersive spectroscopy, and scanning and transmission electron microscopy. This method allowed us to control the localization of NP precipitation throughout the layered bacterial/membrane composite, by varying the timing of the cadmium precursor addition. Additionally, we demonstrated the photodegradation of methyl orange using the CdS functionalized porous membranes, thus confirming the photocatalytic properties of our composites for eventual translation to device development. We finally also explored the precipitation of other metallic NPs using our bacterial system, using enzyme extracted from our bacterial system, and using commercially available, his-tagged enzyme. We hope to extend this research to tethering enzymes on surfaces to direct NP precipitation. Taken all together, our results show the great promise bacteria have for the fabrication of tunable, transition metal NPs with useful electronic properties.

An Ab Initio Description of the Excitonic Properties of LH2 and Their Temperature Dependence.

PubMed

Cupellini, Lorenzo; Jurinovich, Sandro; Campetella, Marco; Caprasecca, Stefano; Guido, Ciro A; Kelly, Sharon M; Gardiner, Alastair T; Cogdell, Richard; Mennucci, Benedetta

2016-11-10

The spectroscopic properties of light-harvesting (LH) antennae in photosyntehtic organisms represent a fingerprint that is unique for each specific pigment-protein complex. Because of that, spectroscopic observations are generally combined with structural data from X-ray crystallography to obtain an indirect representation of the excitonic properties of the system. Here, an alternative strategy is presented which goes beyond this empirical approach and introduces an ab initio computational description of both structural and electronic properties and their dependence on the temperature. The strategy is applied to the peripheral light-harvesting antenna complex (LH2) present in purple bacteria. By comparing this model with the one based on the crystal structure, a detailed, molecular level explanation of the absorption and circular dichroism (CD) spectra and their temperature dependence is achieved. The agreement obtained with the experiments at both low and room temperature lays the groundwork for an atomistic understanding of the excitation dynamics in the LH2 system.

Velocity Curve Analysis of Spectroscopic Binary Stars AI Phe, GM Dra, HD 93917 and V502 Oph by Nonlinear Regression

NASA Astrophysics Data System (ADS)

Karami, K.; Mohebi, R.

2007-08-01

We introduce a new method to derive the orbital parameters of spectroscopic binary stars by nonlinear least squares of (o-c). Using the measured radial velocity data of the four double lined spectroscopic binary systems, AI Phe, GM Dra, HD 93917 and V502 Oph, we derived both the orbital and combined spectroscopic elements of these systems. Our numerical results are in good agreement with the those obtained using the method of Lehmann-Filhé.

Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile

Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, andmore » XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.« less

Covalent functionalization of MoS2 nanosheets synthesized by liquid phase exfoliation to construct electrochemical sensors for Cd (II) detection.

PubMed

Gan, Xiaorong; Zhao, Huimin; Wong, Kwok-Yin; Lei, Dang Yuan; Zhang, Yaobin; Quan, Xie

2018-05-15

Surface functionalization is an effective strategy in the precise control of electronic surface states of two-dimensional materials for promoting their applications. In this study, based on the strong coordination interaction between the transition-metal centers and N atoms, the surface functionalization of few-layer MoS 2 nanosheets was successfully prepared by liquid phase exfoliation method in N, N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone, and formamide. The cytotoxicity of surface-functionalized MoS 2 nanosheets was for the first time evaluated by the methylthiazolyldiphenyl-tetrazoliumbromide assays. An electrochemical sensor was constructed based on glass carbon electrode (GCE) modified by MoS 2 nanosheets obtained in DMF, which exhibits relatively higher sensitivity to Cd 2+ detection and lower cytotoxicity against MCF-7 cells. The mechanisms of surface functionalization and selectively detecting Cd 2+ were investigated by density functional theory calculations together with various spectroscopic measurements. It was found that surface-functionalized MoS 2 nanosheets could be generated through Mo-N covalent bonds due to the orbital hybridization between the 5 s orbitals of Mo atoms and the 2p orbitals of N atoms of the solvent molecules. The high selectivity of the sensor is attributed to the coordination reaction between Cd 2+ and O donor atoms of DMF adsorbed on MoS 2 nanosheets. The robust anti-interference is ascribed to the strong binding energy of Cd 2+ and O atoms of DMF. Under the optimum conditions, the electrochemical sensor exhibits highly sensitive and selective assaying of Cd 2+ with a measured detection limit of 0.2 nM and a linear range from 2 nM to 20 μM. Copyright © 2018 Elsevier B.V. All rights reserved.

Novel dihydro-beta-agarofuran sesquiterpenes as potent modulators of human P-glycoprotein dependent multidrug resistance.

PubMed

Torres-Romero, David; Muñoz-Martínez, Francisco; Jiménez, Ignacio A; Castanys, Santiago; Gamarro, Francisco; Bazzocchi, Isabel L

2009-12-21

P-Glycoprotein (Pgp) overexpression is one factor contributing to multidrug resistance (MDR) in cancer cells and represents one drawback in the treatment of cancer. In an attempt to find more specific and less toxic anticancer MDR-reversal agents, we report herein the isolation, structure elucidation and biological activity of nine new (, and ) and seven known (, and ) dihydro-beta-agarofuran sesquiterpenes from the leaves of Celastrus vulcanicola. Their stereostructures were elucidated on the basis of spectroscopic analysis, including 1D and 2D NMR techniques, CD studies and biogenetic means. All the compounds were assayed on human MDR1-transfected NIH-3T3 cells, in order to determine their ability to reverse the MDR phenotype due to Pgp overexpression. Six compounds from these series (, , , , and ) showed an effectiveness that was similar to (or higher than) the classical Pgp reversal agent verapamil for the reversal of resistance to daunomycin and vinblastine. The structure-activity relationships are discussed.

Merocyclophanes A and B, antiproliferative cyclophanes from the cultured terrestrial Cyanobacterium Nostoc sp.

PubMed

Kang, Hahk-Soo; Santarsiero, Bernard D; Kim, Hyunjung; Krunic, Aleksej; Shen, Qi; Swanson, Steven M; Chai, Heebyung; Kinghorn, A Douglas; Orjala, Jimmy

2012-07-01

The cell extract of a cultured terrestrial Nostoc sp. (UIC 10062), obtained from a sample collected at Grand Mere State Park in Michigan, displayed antiproliferative activity against the HT-29 human colon cancer cell line. Bioactivity-guided fractionation of the cell extract, combined with LC-MS analysis, led to the isolation of two cyclophanes, named merocyclophanes A and B (1 and 2). Their structures were determined by various spectroscopic techniques including HRESIMS, and 1D and 2D NMR analyses. The stereoconfiguration was assigned on the basis of X-ray crystallographic and CD analyses. The structures of merocyclophanes A and B (1 and 2) established a hitherto unknown [7.7]paracyclophane skeleton in nature, as characterized by α-branched methyls at C-1/14. Merocyclophanes A and B (1 and 2) displayed antiproliferative activity against the HT-29 human colon cancer cell line with IC₅₀ values of 3.3 and 1.7 μM, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Merocyclophanes A and B, Antiproliferative Cyclophanes from the Cultured Terrestrial Cyanobacterium Nostoc sp

PubMed Central

Kang, Hahk-Soo; Santarsiero, Bernard D.; Kim, Hyunjung; Krunic, Aleksej; Shen, Qi; Swanson, Steven M.; Chai, Heebyung; Kinghorn, A. Douglas; Orjala, Jimmy

2012-01-01

The cell extract of a cultured terrestrial Nostoc sp. (UIC 10062), obtained from a sample collected at Grand Mere State Park in Michigan, displayed antiproliferative activity against the HT-29 human colon cancer cell line. Bioactivity-guided fractionation of the cell extract, combined with LC-MS analysis, led to the isolation of two cyclophanes, named merocyclophanes A and B (1 and 2). Their structures were determined by various spectroscopic techniques including HRESIMS, and 1D and 2D NMR analyses. The stereoconfiguration was assigned on the basis of X-ray crystallographic and CD analyses. The structures of merocyclophanes A and B (1 and 2) established a hitherto unknown [7.7]paracyclophane skeleton in nature, as characterized by α-branched methyls at C-1/14. Merocyclophanes A and B (1 and 2) displayed antiproliferative activity against the HT-29 human colon cancer cell line with IC50 values of 3.3 and 1.7 µM, respectively. PMID:22571940

PEG and mPEG-anthracene induce DNA condensation and particle formation.

PubMed

Froehlich, E; Mandeville, J S; Arnold, D; Kreplak, L; Tajmir-Riahi, H A

2011-08-18

In this study, we investigated the binding of DNA with poly(ethylene glycol) (PEG) of different sizes and compositions such as PEG 3350, PEG 6000, and mPEG-anthracene in aqueous solution at physiological conditions. The effects of size and composition on DNA aggregation and condensation as well as conformation were determined using Fourier transform infrared (FTIR), UV-visible, CD, fluorescence spectroscopic methods and atomic force microscopy (AFM). Structural analysis showed moderate complex formation for PEG 3350 and PEG 6000 and weaker interaction for mPE-anthracene-DNA adducts with both hydrophilic and hydrophobic contacts. The order of ± stability of the complexes formed is K(PEG 6000) = 1.5 (±0.4) × 10(4) M(-1) > K(PEG 3350) = 7.9 (±1) × 10(3) M(-1) > K(m(PEG-anthracene))= 3.6 (±0.8) × 10(3) M(-1) with nearly 1 bound PEG molecule per DNA. No B-DNA conformational changes were observed, while DNA condensation and particle formation occurred at high PEG concentration.

Computational, electrochemical, and spectroscopic studies of two mononuclear cobaloximes: the influence of an axial pyridine and solvent on the redox behaviour and evidence for pyridine coordination to cobalt(I) and cobalt(II) metal centres†

PubMed Central

Lawrence, Mark A. W.; Celestine, Michael J.; Artis, Edward T.; Joseph, Lorne S.; Esquivel, Deisy L.; Ledbetter, Abram J.; Cropek, Donald M.; Jarrett, William L.; Bayse, Craig A.; Brewer, Matthew I.; Holder, Alvin A.

2018-01-01

[Co(dmgBF2)2(H2O)2] 1 (where dmgBF2 = difluoroboryldimethylglyoximato) was used to synthesize [Co(dmgBF2)2(H2O)(py)]·0.5(CH3)2CO 2 (where py = pyridine) in acetone. The formulation of complex 2 was confirmed by elemental analysis, high resolution MS, and various spectroscopic techniques. The complex [Co(dmgBF2)2(solv)(py)] (where solv = solvent) was readily formed in situ upon the addition of pyridine to complex 1. A spectrophotometric titration involving complex 1 and pyridine proved the formation of such a species, with formation constants, log K = 5.5, 5.1, 5.0, 4.4, and 3.1 in 2-butanone, dichloromethane, acetone, 1,2-difluorobenzene/acetone (4 : 1, v/v), and acetonitrile, respectively, at 20 °C. In strongly coordinating solvents, such as acetonitrile, the lower magnitude of K along with cyclic voltammetry, NMR, and UV-visible spectroscopic measurements indicated extensive dissociation of the axial pyridine. In strongly coordinating solvents, [Co(dmgBF2)2(solv)(py)] can only be distinguished from [Co(dmgBF2)2(solv)2] upon addition of an excess of pyridine, however, in weakly coordinating solvents the distinctions were apparent without the need for excess pyridine. The coordination of pyridine to the cobalt(II) centre diminished the peak current at the Epc value of the CoI/0 redox couple, which was indicative of the relative position of the reaction equilibrium. Herein we report the first experimental and theoretical 59Co NMR spectroscopic data for the formation of Co(I) species of reduced cobaloximes in the presence and absence of py (and its derivatives) in CD3CN. From spectroelectrochemical studies, it was found that pyridine coordination to a cobalt(I) metal centre is more favourable than coordination to a cobalt(II) metal centre as evident by the larger formation constant, log K = 4.6 versus 3.1, respectively, in acetonitrile at 20 °C. The electrosynthesis of hydrogen by complexes 1 and 2 in various solvents demonstrated the dramatic effects of the axial ligand and the solvent on the turnover number of the respective catalyst. PMID:27244471

Preliminary Understanding of Surface Plasmon-Enhanced Circular Dichroism Spectroscopy by Single Particle Imaging

NASA Astrophysics Data System (ADS)

Zhan, Kangshu

Monitoring chiral optical signals of biomolecules as their conformation changes is an important means to study their structures, properties, and functions. Most measurements, however, are ensemble measurements because chiral optical signals from a single biomolecule is often too weak to be detected. In this dissertation, I present my early attempts to study conformational changes of adsorbed proteins by taking advantage of the enhanced electromagnetic (EM) field around a well-designed plasmonic nanofeature. In particular, I discuss the detection of protein adsorption and denaturation on metallic nanoparticles using single particle scattering and CD spectroscopic imaging. Particles of two distinctively different sizes were compared and two different sample protein molecules were studied. A combination of experimental and computational tools was used to simulate and interpret the collected scattering and CD results. The first chapter provides a brief overview of the state-of-art research in CD spectroscopic studies at the single particle level. Three different means to make particles capable of chiral detection are discussed. Various applications beyond single particle imaging are presented to showcase the potential of the described research project, beyond our immediate goals. The second chapter describes my initial characterization of large, metallic, anisotropic nanorods and the establishment of experimental procedures used later for spectrum reconstruction, data visualization and analysis. The physical shape and structure of the particles were imaged by scanning electron microscopy (SEM), the chemical composition by energy dispersive X-ray Spectroscopy (EDS), and the optical properties by darkfield microscopy. An experimental protocol was developed to connect information collected from separate techniques for the same particle, with the aims of discovering any possible structural-property correlation. The reproducibility of the single particle imaging method was evaluated. Full spectrum reconstruction using a set of selected optical filters was carried out and data visualization using a Matlab based 3D mapping method was demonstrated. The third chapter describes the introduction of biomolecules in chiral particle studies. By measuring the circular dichroism spectrum and image of nanorods during lysozyme adsorption and denaturation, I was able to monitor the conformation change of proteins on large gapped nanorods. Experiment results suggested that the conformational change of absorbed protein could lead to the change of chiral signal of nanoparticles, suggesting the potentials of detecting biomolecular structural changes at the single nanoparticle level, though much uncertainty still present. The inherent high background of large, gapped nanoparticles when they interact with biomolecules led to the research described in the 4th chapter where I studied small palladium-silver coreshell nanoparticle properties and its interaction with proteins. SEM was used to characterize particles structures; UV-Vis and darkfield microscopy was used to capture particles' optical responses; and the finite-difference time-domain (FDTD) method was used to simulate resulting spectra and to compare with experimental outcomes. Lysozyme and bovine serum albumin (BSA) were used as the model molecules to study their conformational changes after being adsorbed onto particles. Last but the least, the 5th chapter is dedicated to FDTD simulation of a pair of perfectly shaped triangle nanoprisms to illustrate possible CD responses to be expected from extreme particles with sharp corners and much concentrated local EM field. Different coupling modes of triangle nanoprism were analyzed. It is found that many factors, such as particle orientation, spacing, and their relative position, could lead to significantly different coupling efficient, for both homodimers and heterodimers. The modeling data suggested interesting potentials of nanoparticles of extreme geometric features for high sensitivity surface plasmon-enhanced CD imaging at the signal particle level.

The CD4+/CD8+ Ratio in Pulmonary Tuberculosis: Systematic and Meta-Analysis Article.

PubMed

Yin, Yongmei; Qin, Jie; Dai, Yaping; Zeng, Fanwei; Pei, Hao; Wang, Jun

2015-02-01

The ratio of CD4+/CD8+ has been used as a clinically index to evaluate patients' immunity. Numerous researchers have studied CD4+/CD8+ ratio in pulmonary tuberculosis (PTB) patients. However, the change of CD4+/CD8+ ratio remains controversial. We present a meta-analysis of 15 case-control studies to identify the change of CD4+/CD8+ ratio in PTB patients. We assessed heterogeneity of effect estimates within each group using I(2) test. Subgroup analysis was performed to explore the potential source of heterogeneity. To investigate further the potential publication bias, we visually examined the funnel plots. For robustness of results, we performed sensitivity analysis by removing studies. Data entry and analyses were carried out with RevMan 5.2 (The Nordic Cochrane Centre). Twelve peripheral blood studies were categorized into two subgroups. Eight studies presented a significant decrease of CD4+/CD8+ ratio in PTB cases compared to healthy subjects (SMD: -0.45; 95% CI -0.65--0.25; I(2) = 7%). Other four studies researched on the newly diagnosed patients presented a more seriously and significantly decrease (SMD: -2.17; 95% CI -2.61--1.74; I(2) = 37%). The pooled analysis of bronchoalveolar lavage fluid (BALF) studies showed a significant increase of CD4+/CD8+ ratio using Flow Cytometry (FCM) (SMD: 4.75; 95% CI 3.44-6.05; I(2) =0%). The present meta-analysis indicated that there was a synthetic evidence for the reduced CD4+/CD8+ ratio in peripheral blood of PTB patients, especially newly diagnosed cases. However, the CD4+/CD8+ ratio in BALF was increased using method of FCM.

Photophysical and redox properties of molecule-like CdSe nanoclusters.

PubMed

Dolai, Sukanta; Dass, Amala; Sardar, Rajesh

2013-05-21

Advancing our understanding of the photophysical and electrochemical properties of semiconductor nanoclusters with a molecule-like HOMO-LUMO energy level will help lead to their application in photovoltaic devices and photocatalysts. Here we describe an approach to the synthesis and isolation of molecule-like CdSe nanoclusters, which displayed sharp transitions at 347 nm (3.57 eV) and 362 nm (3.43 eV) in the optical spectrum with a lower energy band extinction coefficient of ~121,000 M(-1) cm(-1). Mass spectrometry showed a single nanocluster molecular weight of 8502. From this mass and various spectroscopic analyses, the nanoclusters are determined to be of the single molecular composition Cd34Se20(SPh)28, which is a new nonstiochiometric nanocluster. Their reversible electrochemical band gap determined in Bu4NPF6/CH3CN was found to be 4.0 V. There was a 0.57 eV Coulombic interaction energy of the electron-hole pair involved. The scan rate dependent electrochemistry suggested diffusion-limited transport of nanoclusters to the electrode. The nanocluster diffusion coefficient (D = 5.4 × 10 (-4) cm(2)/s) in acetonitrile solution was determined from cyclic voltammetry, which suggested Cd34Se20(SPh)28 acts as a multielectron donor or acceptor. We also present a working model of the energy level structure of the newly discovered nanocluster based on its photophysical and redox properties.

Optical biopsy fiber-based fluorescence spectroscopy instrumentation

NASA Astrophysics Data System (ADS)

Katz, Alvin; Ganesan, Singaravelu; Yang, Yuanlong; Tang, Gui C.; Budansky, Yury; Celmer, Edward J.; Savage, Howard E.; Schantz, Stimson P.; Alfano, Robert R.

1996-04-01

Native fluorescence spectroscopy of biomolecules has emerged as a new modality to the medical community in characterizing the various physiological conditions of tissues. In the past several years, many groups have been working to introduce the spectroscopic methods to diagnose cancer. Researchers have successfully used native fluorescence to distinguish cancerous from normal tissue samples in rat and human tissue. We have developed three generations of instruments, called the CD-scan, CD-ratiometer and CD-map, to allow the medical community to use optics for diagnosing tissue. Using ultraviolet excitation and emission spectral measurements on both normal and cancerous tissue of the breast, gynecology, colon, and aerodigestive tract can be separated. For example, from emission intensities at 340 nm to 440 nm (300 nm excitation), a statistically consistent difference between malignant tissue and normal or benign tissue is observed. In order to utilize optical biopsy techniques in a clinical setting, the CD-scan instrument was developed, which allows for rapid and reliable in-vitro and in-vivo florescence measurements of the aerodigestive tract with high accuracy. The instrumentation employs high sensitivity detection techniques which allows for lamp excitation, small diameter optical fiber probes; the higher spatial resolution afforded by the small diameter probes can increase the ability to detect smaller tumors. The fiber optic probes allow for usage in the aerodigestive tract, cervix and colon. Needle based fiber probes have been developed for in-vivo detection of breast cancer.

Interactions between N-acetyl-L-cysteine protected CdTe quantum dots and doxorubicin through spectroscopic method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Xiupei, E-mail: xiupeiyang@163.com; College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637000; Lin, Jia

2015-06-15

Highlights: • CdTe quantum dots with the diameter of 3–5 nm were synthesized in aqueous solution. • The modified CdTe quantum dots showed well fluorescence properties. • The interaction between the CdTe quantum dots and doxorubicin (DR) was investigated. - Abstract: N-acetyl-L-cysteine protected cadmium telluride quantum dots with a diameter of 3–5 nm were synthesized in aqueous solution. The interaction between N-acetyl-L-cysteine/cadmium telluride quantum dots and doxorubicin was investigated by ultraviolet–visible absorption and fluorescence spectroscopy at physiological conditions (pH 7.2, 37 °C). The results indicate that electron transfer has occurred between N-acetyl-L-cysteine/cadmium telluride quantum dots and doxorubicin under light illumination.more » The quantum dots react readily with doxorubicin to form a N-acetyl-L-cysteine/cadmium telluride-quantum dots/doxorubicin complex via electrostatic attraction between the −NH{sub 3}{sup +} moiety of doxorubicin and the −COO{sup −} moiety of N-acetyl-L-cysteine/cadmium telluride quantum dots. The interaction of N-acetyl-L-cysteine/cadmium telluride-quantum dots/doxorubicin complex with bovine serum albumin was studied as well, showing that the complex might induce the conformation change of bovine serum due to changes in microenvironment of bovine serum.« less

Spectroscopic, Structural, and Functional Characterization of the Alternative Low-Spin State of Horse Heart Cytochrome c

PubMed Central

Mugnol, Katia C. U.; Ando, Rômulo A.; Nagayasu, Rafael Y.; Faljoni-Alario, Adelaide; Brochsztain, Sergio; Santos, Paulo S.; Nascimento, Otaciro R.; Nantes, Iseli L.

2008-01-01

The alternative low-spin states of Fe3+ and Fe2+ cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met80 by another strong field ligand at the sixth heme iron coordination position, Fe3+ ALSScytc exhibited 1-nm Soret band blue shift and ɛ enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe3+ and Fe2+ ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp59 fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His33 and His26 carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His33 replaced by Asn) pointing out Lys79 as the probable heme iron ligand. Fe3+ ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential ∼200 mV lower than the wild-type protein (+220 mV) and was more susceptible to the attack of free radicals. PMID:18227133

An empirical evaluation of three vibrational spectroscopic methods for detection of aflatoxins in maize.

PubMed

Lee, Kyung-Min; Davis, Jessica; Herrman, Timothy J; Murray, Seth C; Deng, Youjun

2015-04-15

Three commercially available vibrational spectroscopic techniques, including Raman, Fourier transform near infrared reflectance (FT-NIR), and Fourier transform infrared (FTIR) were evaluated to help users determine the spectroscopic method best suitable for aflatoxin analysis in maize (Zea mays L.) grain based on their relative efficiency and predictive ability. Spectral differences of Raman and FTIR spectra were more marked and pronounced among aflatoxin contamination groups than those of FT-NIR spectra. From the observations and findings in our current and previous studies, Raman and FTIR spectroscopic methods are superior to FT-NIR method in terms of predictive power and model performance for aflatoxin analysis and they are equally effective and accurate in predicting aflatoxin concentration in maize. The present study is considered as the first attempt to assess how spectroscopic techniques with different physical processes can influence and improve accuracy and reliability for rapid screening of aflatoxin contaminated maize samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

Infrared spectroscopy and spectroscopic imaging in forensic science.

PubMed

Ewing, Andrew V; Kazarian, Sergei G

2017-01-16

Infrared spectroscopy and spectroscopic imaging, are robust, label free and inherently non-destructive methods with a high chemical specificity and sensitivity that are frequently employed in forensic science research and practices. This review aims to discuss the applications and recent developments of these methodologies in this field. Furthermore, the use of recently emerged Fourier transform infrared (FT-IR) spectroscopic imaging in transmission, external reflection and Attenuated Total Reflection (ATR) modes are summarised with relevance and potential for forensic science applications. This spectroscopic imaging approach provides the opportunity to obtain the chemical composition of fingermarks and information about possible contaminants deposited at a crime scene. Research that demonstrates the great potential of these techniques for analysis of fingerprint residues, explosive materials and counterfeit drugs will be reviewed. The implications of this research for the examination of different materials are considered, along with an outlook of possible future research avenues for the application of vibrational spectroscopic methods to the analysis of forensic samples.

A comparative study on the interaction of acridine and synthetic bis-acridine with G-quadruplex structure.

PubMed

Nagesh, Narayana; Krishnaiah, Abburi

2003-07-31

DNA from the telomeres contains a stretch of simple tandemly repeated sequences in which clusters of G residues alternate with clusters of T/A sequences along one DNA strand. Model telomeric G-clusters form four-stranded structures in presence of Na(I), K(I) and NH(4)(I) ions. Electrophoretic and spectroscopic studies were made with the telomeric related sequences d(T6G16) or d(G4T2G4T2G4T2G4). It was noticed earlier that G-quadruplex may either be inter-molecular, or intra-molecular, or a mixture of both. CD spectral characteristics of various G-quadruplex DNA suggests that the CD maximum at 293 nm corresponds to that of an intra-molecular G-quadruplex structure or hairpin dimers. Fluorescence titration studies also show that acridine and the bis-acridine are interacting with G-quadruplex DNA and destabilize the K(I)-quadruplex structure more efficiently than the quadruplex formed by NH(4)(I) ion. Among the two drugs studied, acridine is more capable of breaking the G-quadruplex structure than bis-acridine. This result is further confirmed by the CD experiments.

Spectroscopic and Mechanistic Studies of Heterodimetallic Forms of Metallo-β-lactamase NDM-1

PubMed Central

2015-01-01

In an effort to characterize the roles of each metal ion in metallo-β-lactamase NDM-1, heterodimetallic analogues (CoCo-, ZnCo-, and CoCd-) of the enzyme were generated and characterized. UV–vis, 1H NMR, EPR, and EXAFS spectroscopies were used to confirm the fidelity of the metal substitutions, including the presence of a homogeneous, heterodimetallic cluster, with a single-atom bridge. This marks the first preparation of a metallo-β-lactamase selectively substituted with a paramagnetic metal ion, Co(II), either in the Zn1 (CoCd-NDM-1) or in the Zn2 site (ZnCo-NDM-1), as well as both (CoCo-NDM-1). We then used these metal-substituted forms of the enzyme to probe the reaction mechanism, using steady-state and stopped-flow kinetics, stopped-flow fluorescence, and rapid-freeze-quench EPR. Both metal sites show significant effects on the kinetic constants, and both paramagnetic variants (CoCd- and ZnCo-NDM-1) showed significant structural changes on reaction with substrate. These changes are discussed in terms of a minimal kinetic mechanism that incorporates all of the data. PMID:24754678

Modeling and Measuring Charge-Sharing in Hard X-ray Imagers Using HEXITEC CdTe Detectors

NASA Technical Reports Server (NTRS)

Ryan, Daniel F.; Christe, Steven D.; Shih, Albert Y.; Baumgartner, Wayne H.; Wilson, Matthew D.; Seller, Paul; Gaskin, Jessica A.; Inglis, Andrew

2017-01-01

The Rutherford Appleton Laboratory's HEXITEC ASIC has been designed to provide fine pixelated X-ray spectroscopic imaging in combination with a CdTe or CZT detector layer. Although HEXITEC's small pixels enable higher spatial resolution as well as higher spectral resolution via the small-pixel effect, they also increase the probability of charge sharing, a process which degrades spectral performance by dividing the charge induced by a single photon among multiple pixels. In this paper, we investigate the effect of this process on a continuum X-ray spectrum below the Cd and Te fluorescence energies (23 keV). This is done by comparing laboratory measurements with simulations performed with a custom designed model of the HEXITEC ASIC. We find that the simulations closely match the observations implying that we have an adequate understanding of both charge sharing and the HEXITEC ASIC itself. These results can be used to predict the distortion of a spectrum measured with HEXITEC and will help determine to what extent it can be corrected. They also show that models like this one are important tools in developing and interpreting observations from ASICs like HEXITEC.

Biophysical influence of isocarbophos on bovine serum albumin: spectroscopic probing.

PubMed

Zhang, Hua-xin; Zhou, Ying; Liu, E

2012-06-15

Isocarbophos (ICP) is a phosphorous pesticide with high toxicity. It has been detected in several kinds of food and therefore can enter human body. In this paper, spectroscopic approaches including three-dimensional fluorescence (3D-FL) spectroscopy, UV-visible absorption spectroscopy and circular dichroism (CD) spectroscopy were employed to explore the binding of ICP to bovine serum albumin (BSA) at simulated physiological conditions. It was found that the fluorescence quenching of BSA was caused by the formation of ICP-BSA complex at ground state and belonged to static quenching mechanism. The binding constants, the number of binding sites, enthalpy change (ΔH(θ)), Gibbs free energy change (ΔG(θ)) and entropy change (ΔS(θ)) were calculated at four different temperatures according to Scatchard model and thermodynamic equations. To identify the binding location, fluorescence probe techniques were used. The results showed that warfarin, an acknowledged site marker for BSA, could be partially replaced by ICP when ICP was added to warfarin-BSA systems, which demonstrated that ICP primarily bound on Sudlow's site I in domain IIA of BSA molecule. The distance r (3.06 nm) between donor (Trp-212) and acceptor (ICP) was obtained based on Förster's non-radiation fluorescence resonance energy transfer (FRET) theory. Furthermore, the CD spectral results indicated that the secondary structure of BSA was changed in presence of ICP. The study is helpful to evaluating the toxicology of ICP and understanding its effects on the function of protein during the blood transportation process. Copyright © 2012 Elsevier B.V. All rights reserved.

Resolving Spectral Lines with a Periscope-Type DVD Spectroscope

ERIC Educational Resources Information Center

Wakabayashi, Fumitaka

2008-01-01

A new type of DVD spectroscope, the periscope type, is described and the numerical analysis of the observed emission and absorption spectra is demonstrated. A small and thin mirror is put inside and an eighth part of a DVD is used as a grating. Using this improved DVD spectroscope, one can observe and photograph visible spectra more easily and…

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Lane, Arthur L. (Inventor); Bhartia, Rohit (Inventor); Reid, Ray D. (Inventor)

2017-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Lane, Arthur L. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor)

2018-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

High-Resolution Study of the C-D Stretching Bands of 12C 6D 6 and 13C 6D 6

NASA Astrophysics Data System (ADS)

Pliva, J.; Johns, J. W. C.; Goodman, L.

1994-01-01

The perpendicular C-D stretching bands ν 12 (species E1 u) were measured for two isotopomers of benzene with D6 h symmetry. 12C 6D 6 and 13C 6D 6, on a high-resolution Fourier transform spectrometer. Both bands show effects of fairly strong perturbations by states resulting from combinations of low-frequency vibrations. The ν 12 state of 12C 6D 6 is in Fermi resonance with the combination ν 2 + ν 3 whose pP lines, enhanced by the resonance, are observed just below the pP branches of ν 12. An x, y-type Coriolis interaction with an unidentified state of symmetry E2 u, and another anharmonic interaction with an unknown E1 u state, have also been detected in the spectrum. These interactions were included, along with the Fermi resonance and the rotational l-resonance and -doubling, in the Hamiltonian used in the analysis of this band. For the ν 12 band of the 13C 6D 6 isotopomer, a strong perturbation by an anharmonic resonance with the E1 u state ν 7 + ν 11 + ν 14 and a much weaker perturbation. presumably by a z-type Coriolis interaction with an unidentified perturber, have been observed and taken into account in the analysis. Spectroscopic constants are reported for the ν 12 states of the two isotopic species, and parameters obtained for the various perturbers and coupling constants are also listed. It is found that the ζ sum for the E1 u vibrations of all D6 h isotopomers of benzene differs slightly from the theoretical value of ∑ζ t = -1.

Raman spectroscopic investigations of Hg-Cd-Te melts

NASA Technical Reports Server (NTRS)

Morrobel-Sosa, Anny

1987-01-01

Raman scattering measurements are reported for a series of Hg sub1-xCd subxTe (with x less than or =0.2) materials from 295 K (room temperature) to 1126K (up to and above their liquidus temperatures), and for Hg sub1-xCd subxTe (x=0.3) at 285K. The samples were contained in high-temperature optically-flat fused silica cell. Variable temperature measurements were effected in a three-zone, high-temperature furnace equipped with optical windows, and monitored externally by three independently programmable temperature controllers. All studies were made in the backscattering geometry using the 5145 A line of an Ar+ ion laser, with incident power less than 250 mW, as the excitiation source. An intensity enhancement is observed for a mode in each of the compositions studied. The frequency of this mode varies with composition, 142/cm for HgTe, and 128/cm for both the Hg sub1-xCd subxTe (x=0.053 and 0.204) samples. In addition, a shift to lower frequency as a function of temperature is observed in all samples. This shift is most prominent for the x=0.053 sample. The temperature dependence of these modes as the liquidus temperatures are achieved and surpassed for these samples is presented as being associated with a structural transition in the Hg-rich compositions of the Hg sub1-xCd subxTe series. To our knowledge, this is the first reported study of Raman scattering by phonons in the melts of these materials.

PRISM: Processing routines in IDL for spectroscopic measurements (installation manual and user's guide, version 1.0)

USGS Publications Warehouse

Kokaly, Raymond F.

2011-01-01

This report describes procedures for installing and using the U.S. Geological Survey Processing Routines in IDL for Spectroscopic Measurements (PRISM) software. PRISM provides a framework to conduct spectroscopic analysis of measurements made using laboratory, field, airborne, and space-based spectrometers. Using PRISM functions, the user can compare the spectra of materials of unknown composition with reference spectra of known materials. This spectroscopic analysis allows the composition of the material to be identified and characterized. Among its other functions, PRISM contains routines for the storage of spectra in database files, import/export of ENVI spectral libraries, importation of field spectra, correction of spectra to absolute reflectance, arithmetic operations on spectra, interactive continuum removal and comparison of spectral features, correction of imaging spectrometer data to ground-calibrated reflectance, and identification and mapping of materials using spectral feature-based analysis of reflectance data. This report provides step-by-step instructions for installing the PRISM software and running its functions.

Effect of pH on the structure, function, and stability of human calcium/calmodulin-dependent protein kinase IV: combined spectroscopic and MD simulation studies.

PubMed

Naz, Huma; Shahbaaz, Mohd; Bisetty, Krishna; Islam, Asimul; Ahmad, Faizan; Hassan, Md Imtaiyaz

2016-06-01

Human calcium/calmodulin-dependent protein kinase IV (CAMKIV) is a member of Ser/Thr protein kinase family. It is regulated by the calcium-calmodulin dependent signal through a secondary messenger, Ca(2+), which leads to the activation of its autoinhibited form. The over-expression and mutation in CAMKIV as well as change in Ca(2+) concentration is often associated with numerous neurodegenerative diseases and cancers. We have successfully cloned, expressed, and purified a functionally active kinase domain of human CAMKIV. To observe the effect of different pH conditions on the structural and functional properties of CAMKIV, we have used spectroscopic techniques such as circular diachroism (CD) absorbance and fluorescence. We have observed that within the pH range 5.0-11.5, CAMKIV maintained both its secondary and tertiary structures, along with its function, whereas significant aggregation was observed at acidic pH (2.0-4.5). We have also performed ATPase activity assays under different pH conditions and found a significant correlation between the structure and enzymatic activities of CAMKIV. In-silico validations were further carried out by modeling the 3-dimensional structure of CAMKIV and then subjecting it to molecular dynamics (MD) simulations to understand its conformational behavior in explicit water conditions. A strong correlation between spectroscopic observations and the output of molecular dynamics simulation was observed for CAMKIV.

Advanced glycation end products induce differential structural modifications and fibrillation of albumin

NASA Astrophysics Data System (ADS)

Awasthi, Saurabh; Sankaranarayanan, Kamatchi; Saraswathi, N. T.

2016-06-01

Glycation induced amyloid fibrillation is fundamental to the development of many neurodegenerative and cardiovascular complications. Excessive non-enzymatic glycation in conditions such as hyperglycaemia results in the increased accumulation of advanced glycation end products (AGEs). AGEs are highly reactive pro-oxidants, which can lead to the activation of inflammatory pathways and development of oxidative stress. Recently, the effect of non-enzymatic glycation on protein structure has been the major research area, but the role of specific AGEs in such structural alteration and induction of fibrillation remains undefined. In this study, we determined the specific AGEs mediated structural modifications in albumin mainly considering carboxymethyllysine (CML), carboxyethyllysine (CEL), and argpyrimidine (Arg-P) which are the major AGEs formed in the body. We studied the secondary structural changes based on circular dichroism (CD) and spectroscopic analysis. The AGEs induced fibrillation was determined by Congo red binding and examination of scanning and transmission electron micrographs. The amyloidogenic regions in the sequence of BSA were determined using FoldAmyloid. It was observed that CEL modification of BSA leads to the development of fibrillar structures, which was evident from both secondary structure changes and TEM analysis.

Geranylated 2-arylbenzofurans from Morus alba var. tatarica and their α-glucosidase and protein tyrosine phosphatase 1B inhibitory activities.

PubMed

Zhang, Ya-Long; Luo, Jian-Guang; Wan, Chuan-Xing; Zhou, Zhong-Bo; Kong, Ling-Yi

2014-01-01

Ten new geranylated 2-arylbenzofuran derivatives, including two monoterpenoid 2-arylbenzofurans (1 and 2), two geranylated 2-arylbenzofuran enantiomers (3a and 3b), and six geranylated 2-arylbenzofurans (4-9), along with four known 2-arylbenzofurans (10-13) were isolated from the root bark of Morus alba var. tatarica. Their structures and relative configurations were established on the basis of spectroscopic data analysis. Compounds 3-7 with one asymmetric carbon at C-7″ were supposed to be enantiomeric mixtures confirmed by chiral HPLC analysis, and the absolute configurations of each enantiomer in 3-7 were determined by Rh2(OCOCF3)4-induced CD and Snatzke's method. The enantiomers with the substituting group at C-2' exhibited better resolutions on a Chiralpak AD-H column than those with the substituting group at C-4'. Compounds 1-7, 10, 11 and 13, showed α-glucosidase inhibitory activities with IC50 values of 11.9-131.9 μM, and compounds 1 and 9-13 inhibited protein tyrosine phosphatase 1B (PTP1B) with IC50 values of 7.9-38.1 μM. Copyright © 2013 Elsevier B.V. All rights reserved.

Two low-cost digital camera-based platforms for quantitative creatinine analysis in urine.

PubMed

Debus, Bruno; Kirsanov, Dmitry; Yaroshenko, Irina; Sidorova, Alla; Piven, Alena; Legin, Andrey

2015-10-01

In clinical analysis creatinine is a routine biomarker for the assessment of renal and muscular dysfunctions. Although several techniques have been proposed for a fast and accurate quantification of creatinine in human serum or urine, most of them require expensive or complex apparatus, advanced sample preparation or skilled operators. To circumvent these issues, we propose two home-made platforms based on a CD Spectroscope (CDS) and Computer Screen Photo-assisted Technique (CSPT) for the rapid assessment of creatinine level in human urine. Both systems display a linear range (r(2) = 0.9967 and 0.9972, respectively) from 160 μmol L(-1) to 1.6 mmol L(-1) for standard creatinine solutions (n = 15) with respective detection limits of 89 μmol L(-1) and 111 μmol L(-1). Good repeatability was observed for intra-day (1.7-2.9%) and inter-day (3.6-6.5%) measurements evaluated on three consecutive days. The performance of CDS and CSPT was also validated in real human urine samples (n = 26) using capillary electrophoresis data as reference. Corresponding Partial Least-Squares (PLS) regression models provided for mean relative errors below 10% in creatinine quantification. Copyright © 2015 Elsevier B.V. All rights reserved.

Infrared Spectroscopic Imaging of Latent Fingerprints and Associated Forensic Evidence

PubMed Central

Chen, Tsoching; Schultz, Zachary D.; Levin, Ira W.

2011-01-01

Fingerprints reflecting a specific chemical history, such as exposure to explosives, are clearly distinguished from overlapping, and interfering latent fingerprints using infrared spectroscopic imaging techniques and multivariate analysis. PMID:19684917

Strong-lensing analysis of A2744 with MUSE and Hubble Frontier Fields images

NASA Astrophysics Data System (ADS)

Mahler, G.; Richard, J.; Clément, B.; Lagattuta, D.; Schmidt, K.; Patrício, V.; Soucail, G.; Bacon, R.; Pello, R.; Bouwens, R.; Maseda, M.; Martinez, J.; Carollo, M.; Inami, H.; Leclercq, F.; Wisotzki, L.

2018-01-01

We present an analysis of Multi Unit Spectroscopic Explorer (MUSE) observations obtained on the massive Frontier Fields (FFs) cluster A2744. This new data set covers the entire multiply imaged region around the cluster core. The combined catalogue consists of 514 spectroscopic redshifts (with 414 new identifications). We use this redshift information to perform a strong-lensing analysis revising multiple images previously found in the deep FF images, and add three new MUSE-detected multiply imaged systems with no obvious Hubble Space Telescope counterpart. The combined strong-lensing constraints include a total of 60 systems producing 188 images altogether, out of which 29 systems and 83 images are spectroscopically confirmed, making A2744 one of the most well-constrained clusters to date. Thanks to the large amount of spectroscopic redshifts, we model the influence of substructures at larger radii, using a parametrization including two cluster-scale components in the cluster core and several group scale in the outskirts. The resulting model accurately reproduces all the spectroscopic multiple systems, reaching an rms of 0.67 arcsec in the image plane. The large number of MUSE spectroscopic redshifts gives us a robust model, which we estimate reduces the systematic uncertainty on the 2D mass distribution by up to ∼2.5 times the statistical uncertainty in the cluster core. In addition, from a combination of the parametrization and the set of constraints, we estimate the relative systematic uncertainty to be up to 9 per cent at 200 kpc.

Note: Small anaerobic chamber for optical spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chauvet, Adrien A. P., E-mail: adrien.chauvet@gmail.com; Chergui, Majed; Agarwal, Rachna

2015-10-15

The study of oxygen-sensitive biological samples requires an effective control of the atmosphere in which they are housed. In this aim however, no commercial anaerobic chamber is adequate to solely enclose the sample and small enough to fit in a compact spectroscopic system with which analysis can be performed. Furthermore, spectroscopic analysis requires the probe beam to pass through the whole chamber, introducing a requirement for adequate windows. In response to these challenges, we present a 1 l anaerobic chamber that is suitable for broad-band spectroscopic analysis. This chamber has the advantage of (1) providing access, via a septum, tomore » the sample and (2) allows the sample position to be adjusted while keeping the chamber fixed and hermetic during the experiment.« less

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Reid, Ray D. (Inventor)

2009-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Reid, Ray D. (Inventor); Hug, William F. (Inventor)

2010-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Investigating the interaction of anticancer drug temsirolimus with human transferrin: Molecular docking and spectroscopic approach.

PubMed

Shamsi, Anas; Ahmed, Azaj; Khan, Mohd Shahnawaz; Husain, Fohad Mabood; Amani, Samreen; Bano, Bilqees

2018-05-16

In our present study, binding between an important anti renal cancer drug temsirolimus and human transferrin (hTF) was investigated employing spectroscopic and molecular docking approach. In the presence of temsirolimus, hyper chromaticity is observed in hTF in UV spectroscopy suggestive of complex formation between hTF and temsirolimus. Fluorescence spectroscopy revealed the occurrence of quenching in hTF in the presence of temsirolimus implying complex formation taking place between hTF and temsirolimus. Further, the mode of interaction between hTF and temsirolimus was revealed to be static by fluorescence quenching analysis at 3 different temperatures. Binding constant values obtained employing fluorescence spectroscopy depicts strong interaction between hTF and temsirolimus; temsirolimus binds to hTF at 298 K with a binding constant of .32 × 10 4  M -1 implying the strength of this interaction. The negative Gibbs free energy obtained through quenching experiments is evident of the fact that the binding is spontaneous. CD spectra of hTF also showed a downward shift in the presence of temsirolimus as compared with free hTF implying complex formation between hTF and temsirolimus. Molecular docking was performed with a view to find out which residues are key players in this interaction. The importance of our study stems from the fact it will provide an insight into binding pattern of commonly administered renal cancer drug with an important protein that plays a pivotal role in many physiological processes. Copyright © 2018 John Wiley & Sons, Ltd.

Spectral Characterization and 3D Molecular Modeling Studies of Metal Complexes Involving the O, N-Donor Environment of Quinazoline-4(3H)-one Schiff Base and Their Biological Studies

PubMed Central

Siddappa, Kuruba; Mane, Sunilkumar B.

2014-01-01

A simple condensation of 3-amino-2-methylquinazoline-4-one with 2-hydroxy-1-naphthaldehyde produced new tridentate ONO donor Schiff base ligand with efficient yield. The structural characterization of ligand and its Cu(II), Ni(II), Co(II), Mn(II), Zn(II), and Cd(II) complexes were achieved by the aid of elemental analysis, spectral characterization such as (UV-visible, IR, NMR, mass, and ESR), and magnetic data. The analytical and spectroscopic studies suggest the octahedral geometries of Cu(II), Co(II), Ni(II) and Mn(II) complexes and tetrahedral geometry of Zn(II) and Cd(II) complexes with the tridentate ONO Schiff base ligand. Furthermore, the conclusions drawn from these studies afford further support to the mode of bonding discussed on the basis of their 3D molecular modeling studies by considering different bond lengths, bond angles, and bond distance. The ligand and its metal complexes evaluated for their antimicrobial activity against Staphylococcus aureus (MTCC number 7443), Bacillus subtilis (MTCC number 9878), Escherichia coli (MTCC number 1698), Aspergillus niger (MTCC number 281), and Aspergillus flavus (MTCC number 277). The MIC of these compounds was found to be most active at 10 μg/mL concentration in inhibiting the growth of the tested organisms. The DNA cleavage activity of all the complexes was studied by gel electrophoresis method. PMID:24678278

Interaction of promethazine and adiphenine to human hemoglobin: A comparative spectroscopic and computational analysis

NASA Astrophysics Data System (ADS)

Maurya, Neha; ud din Parray, Mehraj; Maurya, Jitendra Kumar; Kumar, Amit; Patel, Rajan

2018-06-01

The binding nature of amphiphilic drugs viz. promethazine hydrochloride (PMT) and adiphenine hydrochloride (ADP), with human hemoglobin (Hb) was unraveled by fluorescence, absorbance, time resolved fluorescence, fluorescence resonance energy transfer (FRET) and circular dichroism (CD) spectral techniques in combination with molecular docking and molecular dynamic simulation methods. The steady state fluorescence spectra indicated that both PMT and ADP quenches the fluorescence of Hb through static quenching mechanism which was further confirmed by time resolved fluorescence spectra. The UV-Vis spectroscopy suggested ground state complex formation. The activation energy (Ea) was observed more in the case of Hb-ADP than Hb-PMT interaction system. The FRET result indicates the high probability of energy transfer from β Trp37 residue of Hb to the PMT (r = 2.02 nm) and ADP (r = 2.33 nm). The thermodynamic data reveal that binding of PMT with Hb are exothermic in nature involving hydrogen bonding and van der Waal interaction whereas in the case of ADP hydrophobic forces play the major role and binding process is endothermic in nature. The CD results show that both PMT and ADP, induced secondary structural changes of Hb and unfold the protein by losing a large helical content while the effect is more pronounced with ADP. Additionally, we also utilized computational approaches for deep insight into the binding of these drugs with Hb and the results are well matched with our experimental results.

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cances, Benjamin; Benedetti, Marc; Farges, Francois

2007-02-02

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands atmore » pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cances, Benjamin; /Marne La Vallee U.; Benedetti, Marc

2006-12-13

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxyhydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au L{sub III}-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl){sub 4}), with dominantly OHmore » ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution--Multi Site Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Interaction of promethazine and adiphenine to human hemoglobin: A comparative spectroscopic and computational analysis.

PubMed

Maurya, Neha; Ud Din Parray, Mehraj; Maurya, Jitendra Kumar; Kumar, Amit; Patel, Rajan

2018-06-15

The binding nature of amphiphilic drugs viz. promethazine hydrochloride (PMT) and adiphenine hydrochloride (ADP), with human hemoglobin (Hb) was unraveled by fluorescence, absorbance, time resolved fluorescence, fluorescence resonance energy transfer (FRET) and circular dichroism (CD) spectral techniques in combination with molecular docking and molecular dynamic simulation methods. The steady state fluorescence spectra indicated that both PMT and ADP quenches the fluorescence of Hb through static quenching mechanism which was further confirmed by time resolved fluorescence spectra. The UV-Vis spectroscopy suggested ground state complex formation. The activation energy (E a ) was observed more in the case of Hb-ADP than Hb-PMT interaction system. The FRET result indicates the high probability of energy transfer from β Trp37 residue of Hb to the PMT (r=2.02nm) and ADP (r=2.33nm). The thermodynamic data reveal that binding of PMT with Hb are exothermic in nature involving hydrogen bonding and van der Waal interaction whereas in the case of ADP hydrophobic forces play the major role and binding process is endothermic in nature. The CD results show that both PMT and ADP, induced secondary structural changes of Hb and unfold the protein by losing a large helical content while the effect is more pronounced with ADP. Additionally, we also utilized computational approaches for deep insight into the binding of these drugs with Hb and the results are well matched with our experimental results. Copyright © 2018 Elsevier B.V. All rights reserved.

Continued development of room temperature semiconductor nuclear detectors

NASA Astrophysics Data System (ADS)

Kim, Hadong; Cirignano, Leonard; Churilov, Alexei; Ciampi, Guido; Kargar, Alireza; Higgins, William; O'Dougherty, Patrick; Kim, Suyoung; Squillante, Michael R.; Shah, Kanai

2010-08-01

Thallium bromide (TlBr) and related ternary compounds, TlBrI and TlBrCl, have been under development for room temperature gamma ray spectroscopy due to several promising properties. Due to recent advances in material processing, electron mobility-lifetime product of TlBr is close to Cd(Zn)Te's value which allowed us to fabricate large working detectors. We were also able to fabricate and obtain spectroscopic results from TlBr Capacitive Frisch Grid detector and orthogonal strip detectors. In this paper we report on our recent TlBr and related ternary detector results and preliminary results from Cinnabar (HgS) detectors.

Spectroscopic studies on the interactions of 5-ethyl-6-phenyl-3,8-bis((3-aminoalkyl)propanamido)phenanthridin-5-ium derivatives with G-quadruplex DNA

NASA Astrophysics Data System (ADS)

Yalçın, Ergin; Duyar, Halil; Ihmels, Heiko; Seferoğlu, Zeynel

2018-05-01

An improved microwave-induced synthesis of five ethidium derivatives (Ethidium derivatives, 2a-d) is presented. As the derivatives 2a-d have been proposed previously to be telomerase inhibitors, the binding interactions of these ethidium derivatives with G-quadruplex DNA were evaluated by means of photometric and fluorimetric titration, thermal DNA denaturation, CD and 1H NMR spectroscopy. In particular, the compound bearing 3,8-bis(pyrrolidin-1-yl)propanamido substituent 2a exhibits high selectivity for G-quadruplex DNA relative to duplex DNA.

Three new 7.3',8.5'-connected bicyclo[3.2.1]octanoids and other neolignans from leaves of Nectandra amazonum NEES. (Lauraceae).

PubMed

Coy Barrera, Ericsson David; Cuca Suárez, Luis Enrique

2009-06-01

Three new 7.3',8.5'-connected (macrophyllin-type) bicyclo[3.2.1]octanoid neolignans (nectamazins A-C, 1-3) were isolated from leaves of Nectandra amazonum NEES., along with seven known neolignans (4-10). The structures of 1-3 were characterized by spectroscopic methods (1D, 2D NMR) and the absolute configuration was assigned on the basis of circular dichroism (CD) spectra supported by nuclear Overhauser effect spectroscopy (NOESY) correlations. The new compounds showed inhibition activity against platelet activating factor (PAF)-induced aggregation of rabbit platelets.

Flavonoids from the roots of Artocarpus heterophyllus.

PubMed

Yuan, Wen-Jun; Yuan, Jin-Bin; Peng, Jia-Bing; Ding, Yuan-Qing; Zhu, Ji-Xiao; Ren, Gang

2017-03-01

Four new flavonoids, artoheteroids A-D (1-4), together with six known ones (5-10), were isolated from the roots of Artocarpus heterophyllus. Their structures were elucidated by spectroscopic methods, including 1D and 2D NMR, UV, IR, CD, and HR-ESI-MS. All isolated compounds were screened for their inhibitory abilities against cathepsin K (CatK). Among them, compounds 1-2, 4-6, and 10 were found to have suppression capabilities against CatK with IC 50 values ranging from 1.4 to 93.9μM. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectroscopic Doppler analysis for visible-light optical coherence tomography

NASA Astrophysics Data System (ADS)

Shu, Xiao; Liu, Wenzhong; Duan, Lian; Zhang, Hao F.

2017-12-01

Retinal oxygen metabolic rate can be effectively measured by visible-light optical coherence tomography (vis-OCT), which simultaneously quantifies oxygen saturation and blood flow rate in retinal vessels through spectroscopic analysis and Doppler measurement, respectively. Doppler OCT relates phase variation between sequential A-lines to the axial flow velocity of the scattering medium. The detectable phase shift is between -π and π due to its periodicity, which limits the maximum measurable unambiguous velocity without phase unwrapping. Using shorter wavelengths, vis-OCT is more vulnerable to phase ambiguity since flow induced phase variation is linearly related to the center wavenumber of the probing light. We eliminated the need for phase unwrapping using spectroscopic Doppler analysis. We split the whole vis-OCT spectrum into a series of narrow subbands and reconstructed vis-OCT images to extract corresponding Doppler phase shifts in all the subbands. Then, we quantified flow velocity by analyzing subband-dependent phase shift using linear regression. In the phantom experiment, we showed that spectroscopic Doppler analysis extended the measurable absolute phase shift range without conducting phase unwrapping. We also tested this method to quantify retinal blood flow in rodents in vivo.

Hyphenation of Raman spectroscopy with gravimetric analysis to interrogate water-solid interactions in pharmaceutical systems.

PubMed

Gift, Alan D; Taylor, Lynne S

2007-01-04

A moisture sorption gravimetric analyzer has been combined with a Raman spectrometer to better understand the various modes of water-solid interactions relevant to pharmaceutical systems. A commercial automated moisture sorption balance was modified to allow non-contact monitoring of the sample properties by interfacing a Raman probe with the sample holder. This hybrid instrument allows for gravimetric and spectroscopic changes to be monitored simultaneously. The utility of this instrument was demonstrated by investigating different types of water-solid interactions including stoichiometric and non-stoichiometric hydrate formation, deliquescence, amorphous-crystalline transformation, and capillary condensation. In each of the model systems, sulfaguanidine, cromolyn sodium, ranitidine HCl, amorphous sucrose and silica gel, spectroscopic changes were observed during the time course of the moisture sorption profile. Analysis of spectroscopic data provided information about the origin of the observed changes in moisture content as a function of relative humidity. Furthermore, multivariate data analysis techniques were employed as a means of processing the spectroscopic data. Principle components analysis was found to be useful to aid in data processing, handling and interpretation of the spectral changes that occurred during the time course of the moisture sorption profile.

Preparation & in vitro evaluation of 90Y-DOTA-rituximab

PubMed Central

Kameswaran, Mythili; Pandey, Usha; Dash, Ashutosh; Samuel, Grace; Venkatesh, Meera

2016-01-01

Background & objectives: Radioimmunotherapy is extensively being used for the treatment of non-Hodgkin's lymphoma (NHL). Use of rituximab, a chimeric anti-CD20 antibody directed against the CD20 antigen in combination with suitable beta emitters is expected to result in good treatment response by its cross-fire and bystander effects. The present work involves the conjugation of p-isothiocyanatobenzyl DOTA (p-SCN-Bn-DOTA) to rituximab, its radiolabelling with 90Y and in vitro and in vivo evaluation to determine its potential as a radioimmunotherapeutic agent. Methods: Rituximab was conjugated with p-SCN-Bn-DOTA at 1:1 antibody: DOTA molar ratio. The number of DOTA molecules linked to one molecule of rituximab was determined by radioassay and spectroscopic assay. Radiolabelling of rituximab with 90Y was carried out and its in vitro stability was evaluated. In vitro cell binding studies were carried out in Raji cells expressing CD20 antigen. Biodistribution studies were carried out in normal Swiss mice. Results: Using both radioassay and spectroscopic method, it was determined that about five molecules of DOTA were linked to rituximab. Radiolabelling of the rituximab conjugate with 90Y and subsequent purification on PD-10 column gave a product with radiochemical purity (RCP) > 98 per cent which was retained at > 90 per cent up to 72 h when stored at 37°C. In vitro cell binding experiments of 90Y-DOTA-rituximab with Raji cells exhibited specific binding of 20.7 ± 0.1 per cent with 90Y-DOTA-rituximab which reduced to 15.5 ± 0.2 per cent when incubated with cold rituximab. The equilibrium constant Kd for 90Y-DOTA-Rituximab was determined to be 3.38 nM. Radiolabelled antibody showed clearance via hepatobiliary and renal routes and activity in tibia was found to be quite low indicating in vivo stability of 90Y-DOTA-rituximab. Interpretation & conclusions: p-SCN-Bn-DOTA was conjugated with rituximab and radiolabelling with 90Y was carried out. In vitro studies carried out in Raji cells showed the specificity of the radiolabelled conjugate suggesting the potential uitability of the formulation as a radiopharmaceutical for therapy of NHL. PMID:26997015

Preparation & in vitro evaluation of ⁹⁰Y-DOTA-rituximab.

PubMed

Kameswaran, Mythili; Pandey, Usha; Dash, Ashutosh; Samuel, Grace; Venkatesh, Meera

2016-01-01

Radioimmunotherapy is extensively being used for the treatment of non-Hodgkin's lymphoma (NHL). Use of rituximab, a chimeric anti-CD20 antibody directed against the CD20 antigen in combination with suitable beta emitters is expected to result in good treatment response by its cross-fire and bystander effects. The present work involves the conjugation of p-isothiocyanatobenzyl DOTA (p-SCN-Bn-DOTA) to rituximab, its radiolabelling with [90] Y and in vitro and in vivo evaluation to determine its potential as a radioimmunotherapeutic agent. Rituximab was conjugated with p-SCN-Bn-DOTA at 1:1 antibody: DOTA molar ratio. The number of DOTA molecules linked to one molecule of rituximab was determined by radioassay and spectroscopic assay. Radiolabelling of rituximab with 90 Y was carried out and its in vitro stability was evaluated. In vitro cell binding studies were carried out in Raji cells expressing CD20 antigen. Biodistribution studies were carried out in normal Swiss mice. Using both radioassay and spectroscopic method, it was determined that about five molecules of DOTA were linked to rituximab. Radiolabelling of the rituximab conjugate with [90] Y and subsequent purification on PD-10 column gave a product with radiochemical purity (RCP) > 98 per cent which was retained at > 90 per cent up to 72 h when stored at 37°C. In vitro cell binding experiments of 90 Y-DOTA-rituximab with Raji cells exhibited specific binding of 20.7 ± 0.1 per cent with [90] Y-DOTA-rituximab which reduced to 15.5 ± 0.2 per cent when incubated with cold rituximab. The equilibrium constant K d for 90 Y-DOTA-Rituximab was determined to be 3.38 nM. Radiolabelled antibody showed clearance via hepatobiliary and renal routes and activity in tibia was found to be quite low indicating in vivo stability of [90] Y-DOTA-rituximab. p-SCN-Bn-DOTA was conjugated with rituximab and radiolabelling with 90 Y was carried out. In vitro studies carried out in Raji cells showed the specificity of the radiolabelled conjugate suggesting the potential uitability of the formulation as a radiopharmaceutical for therapy of NHL.

Spectroscopic studies on the active site of hydroperoxide lyase; the influence of detergents on its conformation.

PubMed

Noordermeer, M A; Veldink, G A; Vliegenthart, J F

2001-02-02

Expression of high quantities of alfalfa hydroperoxide lyase in Escherichia coli made it possible to study its active site and structure in more detail. Circular dichroism (CD) spectra showed that hydroperoxide lyase consists for about 75% of alpha-helices. Electron paramagnetic resonance (EPR) spectra confirmed its classification as a cytochrome P450 enzyme. The positive influence of detergents on the enzyme activity is paralleled by a spin state transition of the heme Fe(III) from low to high spin. EPR and CD spectra showed that detergents induce a subtle conformational change, which might result in improved substrate binding. Because hydroperoxide lyase is thought to be a membrane bound protein and detergents mimic a membrane environment, the more active, high spin form likely represents the in vivo conformation. Furthermore, the spin state appeared to be temperature-dependent, with the low spin state favored at low temperature. Point mutants of the highly conserved cysteine in domain D indicated that this residue might be involved in heme binding.

Effects of γ-Irradiation on the Molecular Structures and Functions of Human Serum Albumin.

PubMed

Hu, Xinxin; Song, Wei; Li, Wei; Guo, Changying; Yu, Zehua; Liu, Rutao

2016-11-01

In this paper, we use spectroscopic methods (fluorescence spectroscopy, UV absorption spectroscopy, and circular dichroism (CD) spectroscopy) to elucidate the effects of reactive oxygen species generated by γ-irradiation on the molecular properties of human serum albumin (HSA). The results of fluorescence spectroscopy indicated that oxidation by γ-irradiation can lead to conformational changes of HSA. Data of CD spectra suggested that with the increase of radiation dose the percentage of α-helix in HSA has decreased. The determination of protein hydrophobicity showed that the effective hydrophobicity of HSA decreased up to 62% compared to the native HSA solution due to the exposure to the γ-irradiation. Furthermore, small changes in the esterase-like activity of HSA were introduced because of oxidation. The content of bityrosine increased markedly, suggesting that the oxidized HSA was aggregated. Moreover, there was no obvious change in the molecular properties of HSA with low γ-irradiation dose. Changes happened when the irradiation dose exceeded 200 Gy. © 2016 Wiley Periodicals, Inc.

Electric Field and Current Transport Mechanisms in Schottky CdTe X-ray Detectors under Perturbing Optical Radiation

PubMed Central

Cola, Adriano; Farella, Isabella

2013-01-01

Schottky CdTe X-ray detectors exhibit excellent spectroscopic performance but suffer from instabilities. Hence it is of extreme relevance to investigate their electrical properties. A systematic study of the electric field distribution and the current flowing in such detectors under optical perturbations is presented here. The detector response is explored by varying experimental parameters, such as voltage, temperature, and radiation wavelength. The strongest perturbation is observed under 850 nm irradiation, bulk carrier recombination becoming effective there. Cathode and anode irradiations evidence the crucial role of the contacts, the cathode being Ohmic and the anode blocking. In particular, under irradiation of the cathode, charge injection occurs and peculiar kinks, typical of trap filling, are observed both in the current-voltage characteristic and during transients. The simultaneous access to the electric field and the current highlights the correlation between free and fixed charges, and unveils carrier transport/collection mechanisms otherwise hidden. PMID:23881140

Insights into in vitro binding of parecoxib to human serum albumin by spectroscopic methods.

PubMed

Shang, Shujun; Liu, Qingling; Gao, Jiandong; Zhu, Yulin; Liu, Jingying; Wang, Kaiyan; Shao, Wei; Zhang, Shudong

2014-10-01

Herein, we report the effect of parecoxib on the structure and function of human serum albumin (HSA) by using fluorescence, circular dichroism (CD), Fourier transforms infrared (FTIR), three-dimensional (3D) fluorescence spectroscopy, and molecular docking techniques. The Stern-Volmer quenching constants K(SV) and the corresponding thermodynamic parameters ΔH, ΔG, and ΔS have been estimated by the fluorescence quenching method. The results indicated that parecoxib binds spontaneously with HSA through van der Waals forces and hydrogen bonds with binding constant of 3.45 × 10(4) M(-1) at 298 K. It can be seen from far-UV CD spectra that the α-helical network of HSA is disrupted and its content decreases from 60.5% to 49.6% at drug:protein = 10:1. Protein tertiary structural alterations induced by parecoxib were also confirmed by FTIR and 3D fluorescence spectroscopy. The molecular docking study indicated that parecoxib is embedded into the hydrophobic pocket of HSA. © 2014 Wiley Periodicals, Inc.

Study on the interaction of the epilepsy drug, zonisamide with human serum albumin (HSA) by spectroscopic and molecular docking techniques

NASA Astrophysics Data System (ADS)

Shahabadi, Nahid; Khorshidi, Aref; Moghadam, Neda Hossinpour

2013-10-01

In the present investigation, an attempt has been made to study the interaction of zonisamide (ZNS) with the transport protein, human serum albumin (HSA) employing UV-Vis, fluorometric, circular dichroism (CD) and molecular docking techniques. The results indicated that binding of ZNS to HSA caused strong fluorescence quenching of HSA through static quenching mechanism, hydrogen bonds and van der Waals contacts are the major forces in the stability of protein ZNS complex and the process of the binding of ZNS with HSA was driven by enthalpy (ΔH = -193.442 kJ mol-1). The results of CD and UV-Vis spectroscopy showed that the binding of this drug to HSA induced conformational changes in HSA. Furthermore, the study of molecular docking also indicated that zonisamide could strongly bind to the site I (subdomain IIA) of HSA mainly by hydrophobic interaction and there were hydrogen bond interactions between this drug and HSA, also known as the warfarin binding site.

Spin-orbit effects on reflectance anisotropy spectroscopy of aclean CdTe(001) surface

NASA Astrophysics Data System (ADS)

Vázquez-Nava, Raül A.

2005-03-01

The spectroscopical reflectance anisotropy (RA) response of a clean (001) surface of CdTe, which exhibits a c(2 x2) surface reconstruction, is studied using a microscopic formulation based on a semi-empirical tight binding approach (SETB) which includes the spin-orbit (SO) interaction. Following Ref. 1, we apply an unitary transformation to the usual SETB sp^3s^* basis to describe the electronic states in terms of a set of atomic states which are eigenstates of the total angular momentum (TAM). These states are better suited to treat the SO interaction in this model, and their use in the computation of the RA signal is straightforward [1]. We show how the RA changes when SO is taken into account and compare our theoretical results with experimental measurements of Ref. 2. [1] R.A. V'azquez-Nava, B.S. Mendoza and C. Castillo, Phys. Rev. B 70, 165306 (2004). [2] J. R. Molina and R. Espinosa-Luna, J. Phys. D: Appl. Phys. (2004), accepted.

Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface.

PubMed

Lian, Zichao; Sakamoto, Masanori; Matsunaga, Hironori; Vequizo, Junie Jhon M; Yamakata, Akira; Haruta, Mitsutaka; Kurata, Hiroki; Ota, Wataru; Sato, Tohru; Teranishi, Toshiharu

2018-06-13

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

New Butyrolactone Type Lignans from Arctii Fructus and Their Anti-inflammatory Activities.

PubMed

Yang, Ya-Nan; Huang, Xiao-Ying; Feng, Zi-Ming; Jiang, Jian-Shuang; Zhang, Pei-Cheng

2015-09-16

Arctiidilactone (1), a novel rare butyrolactone lignan with a 6-carboxyl-2-pyrone moiety, and 11 new butyrolactone lignans (2-12) were isolated from the fruits of Arctium lappa L., together with 5 known compounds (13-17). Their structures were elucidated by interpretation of their spectroscopic data (1D and 2D NMR, UV, IR, ORD, and HRESIMS) and comparison to literature data. The absolute configurations of compounds 1-12 were determined by a combination of rotating-frame nuclear Overhauser effect spectroscopy (ROESY), circular dichroism (CD) spectroscopy, and Rh2(OCOCF3)4-induced CD spectroscopy. All of the compounds were tested for their anti-inflammatory properties in terms of suppressing the production of NO in lipopolysaccharide-induced BV2 cells. Compounds 1, 6, 8, and 10 exhibited stronger anti-inflammatory effects than the positive control curcumin, particularly 1, which exhibited 75.51, 70.72, and 61.17% inhibition at 10, 1, and 0.1 μM, respectively.

Monitoring Nonenzymatic Glycation of Human Immunoglobulin G by methylglyoxal and glyoxal: A spectroscopic study

PubMed Central

Pampati, Praveen K; Suravajjala, Sreekanth; Dain, Joel A

2010-01-01

The accumulation of di-carbonyl compounds, methylglyoxal (MG) and glyoxal (G) has been observed in diabetic conditions. They are formed from non-oxidative mechanisms in anaerobic glycolysis and lipid peroxidation and act as advanced glycation endproduct (AGE) precursors. The objective of this study was to monitor and characterize the AGE formation of human immunoglobulin G (hIgG) by MG and G, utilizing UV-Fluorescence spectroscopy, circular dichroism (CD) and MALDI-Mass Spectrometry. Human IgG was incubated over time with MG and G at different concentrations. Formation of AGE was monitored by UV and fluorescence spectroscopy. The effect of AGE formation on secondary structure of hIgG has been studied by CD. Comparison of AGE profile for MG and G was performed by MALDI-Mass Spectrometry. Both MG and G formed AGE with MG being almost twice as reactive as G. The combination of these techniques is a convenient method for evaluating and characterizing the AGE proteins. PMID:20816660

Integrated photonics for infrared spectroscopic sensing

NASA Astrophysics Data System (ADS)

Lin, Hongtao; Kita, Derek; Han, Zhaohong; Su, Peter; Agarwal, Anu; Yadav, Anupama; Richardson, Kathleen; Gu, Tian; Hu, Juejun

2017-05-01

Infrared (IR) spectroscopy is widely recognized as a gold standard technique for chemical analysis. Traditional IR spectroscopy relies on fragile bench-top instruments located in dedicated laboratory settings, and is thus not suitable for emerging field-deployed applications such as in-line industrial process control, environmental monitoring, and point-ofcare diagnosis. Recent strides in photonic integration technologies provide a promising route towards enabling miniaturized, rugged platforms for IR spectroscopic analysis. Chalcogenide glasses, the amorphous compounds containing S, Se or Te, have stand out as a promising material for infrared photonic integration given their broadband infrared transparency and compatibility with silicon photonic integration. In this paper, we discuss our recent work exploring integrated chalcogenide glass based photonic devices for IR spectroscopic chemical analysis, including on-chip cavityenhanced chemical sensing and monolithic integration of mid-IR waveguides with photodetectors.

Caliste 64: detection unit of a spectro imager array for a hard x-ray space telescope

NASA Astrophysics Data System (ADS)

Limousin, O.; Meuris, A.; Lugiez, F.; Gevin, Olivier; Pinsard, F.; Blondel, C.; Le Mer, I.; Delagnes, E.; Vassal, M. C.; Soufflet, F.; Bocage, R.; Penquer, A.; Billot, M.

2017-11-01

In the frame of the hard X-ray Simbol-X observatory, a joint CNES-ASI space mission to be flown in 2014, a prototype of miniature Cd(Zn)Te camera equipped with 64 pixels has been designed. The device, called Caliste 64, is a spectro-imager with high resolution event timetagging capability. Caliste 64 integrates a Cd(Zn)Te semiconductor detector with segmented electrode and its front-end electronics made of 64 independent analog readout channels. This 1 × 1 × 2 cm3 camera, able to detect photons in the range from 2 keV up to 250 keV, is an elementary detection unit juxtaposable on its four sides. Consequently, large detector array can be made assembling a mosaic of Caliste 64 units. Electronics readout module is achieved by stacking four IDeF-X V1.1 ASICs, perpendicular to the detection plane. We achieved good noise performances, with a mean Equivalent Noise Charge of 65 electrons rms over the 64 channels. For the first prototypes, we chose Pt//CdTe//Al/Ti/Au Schottky detectors because of their very low dark current and excellent spectroscopic performances. Recently a Caliste 64 prototype has been also equipped with a 2 mm thick Au//CdZnTe//Au detector. This paper presents the performances of these four prototypes and demonstrates spectral performances better than 1 keV fwhm at 59.54 keV when the samples are moderately cooled down to -10°C.

Dissection of the binding of hydrogen peroxide to trypsin using spectroscopic methods and molecular modeling

NASA Astrophysics Data System (ADS)

Song, Wei; Yu, Zehua; Hu, Xinxin; Liu, Rutao

2015-02-01

Studies on the effects of environmental pollutants to protein in vitro has become a global attention. Hydrogen peroxide (H2O2) is used as an effective food preservative and bleacher in industrial production. The toxicity of H2O2 to trypsin was investigated by multiple spectroscopic techniques and the molecular docking method at the molecular level. The intrinsic fluorescence of trypsin was proved to be quenched in a static process based on the results of fluorescence lifetime experiment. Hydrogen bonds interaction and van der Waals forces were the main force to generate the trypsin-H2O2 complex on account of the negative ΔH0 and ΔS0. The binding of H2O2 changed the conformational structures and internal microenvironment of trypsin illustrated by UV-vis absorption, fluorescence, synchronous fluorescence, three-dimensional (3D) fluorescence and circular dichroism (CD) results. However, the binding site was far away from the active site of trypsin and the trypsin activity was only slightly affected by H2O2, which was further explained by molecular docking investigations.

Combined spectroscopic, molecular docking and quantum mechanics study of β-casein and p-coumaric acid interactions following thermal treatment.

PubMed

Kaur, Jasmeet; Katopo, Lita; Hung, Andrew; Ashton, John; Kasapis, Stefan

2018-06-30

The molecular nature of interactions between β-casein and p-coumaric acid was studied following exposure of their solutions to ultra-high temperature (UHT at 145 °C). Interactions were characterised by employing multi-spectroscopic methods, molecular docking and quantum mechanics calculations. FTIR demonstrates that the ligand lies in the vicinity of the protein, hence inverting the absorbance spectrum of the complex. This outcome changes the conformational characteristics of the protein leading to a flexible and open structure that accommodates the phenolic microconstituent. Results are supported by UV-vis, CD and fluorescence quenching showing considerable shifts in spectra with complexation. Molecular docking indicates that there is at least a hydrogen bond between p-coumaric acid and the peptide backbone of isoleucine (Ile27). Quantum mechanics calculations further argue that changes in experimental observations are also due to a covalent interaction in the protein-phenolic adduct, which according to the best predicted binding pose involves the side chain of lysine 47. Copyright © 2018. Published by Elsevier Ltd.

Acute leukemia coexpressing myeloid, B- and T-lineage associated markers: multiparameter analysis of criteria defining lineage commitment and maturational stage in a case of undifferentiated leukemia.

PubMed

Meckenstock, G; Heyll, A; Schneider, E M; Hildebrandt, B; Runde, V; Aul, C; Bartram, C R; Ludwig, W D; Schneider, W

1995-02-01

Coexpression of myeloid, B-, and T-lineage associated markers was found in a patient with morphologically and cytochemically undifferentiated acute leukemia. Surface marker analysis using two-color immunofluorescence staining characterized blast cells to express CD34, CD38, CD117, and class II antigens, coexpressing TdT, CD4, CD7, CD13, CD19, and CD33. Cytoplasmic expression of myeloperoxidase, CD3, and CD22 could not be demonstrated. Monosomy for chromosome 7 was found by cytogenetic analysis. The absence of clonal rearrangements of immunoglobulin or T-cell receptor genes was shown by Southern blot analysis. Using a 3H-thymidine incorporation assay, DNA synthesis of leukemic blasts could be stimulated by IL-3, IL-6 and G-CSF in vitro. The present case did not offer specific criteria of lineage commitment. Corresponding to an equivalent counterpart in normal hematopoiesis, the involved cell population may reflect an early, most immature developmental stage within a multipotent progenitor cell compartment.

Photophysical Properties of II-VI Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Gong, Ke

As it is well known, semiconductor nanocrystals (also called quantum dots, QDs) are being actively pursued for use in many different types of luminescent optical materials. These materials include the active media for luminescence downconversion in artificial lighting, lasers, luminescent solar concentrators and many other applications. Chapter 1 gives general introduction of QDs, which describe the basic physical properties and optical properties. Based on the experimental spectroscopic study, a semiquantitative method-effective mass model is employed to give theoretical prediction and guide. The following chapters will talks about several topics respectively. A predictive understanding of the radiative lifetimes is therefore a starting point for the understanding of the use of QDs for these applications. Absorption intensities and radiative lifetimes are fundamental properties of any luminescent material. Meantime, achievement of high efficiency with high working temperature and heterostructure fabrication with manipulation of lattice strain are not easy and need systematic investigation. To make accurate connections between extinction coefficients and radiative recombination rates, chapter 2 will consider three closely related aspects of the size dependent spectroscopy of II-VI QDs. First, it will consider the existing literature on cadmium selenide (CdSe) QD absorption spectra and extinction coefficients. From these results and fine structure considerations Boltzmann weighted radiative lifetimes are calculated. These lifetimes are compared to values measured on very high quality CdSe and CdSe coated with zinc selenide (ZnSe) shells. Second, analogous literature data are analyzed for cadmium telluride (CdTe) nanocrystals and compared to lifetimes measured for very high quality QDs. Furthermore, studies of the absorption and excitation spectra and measured radiative lifetimes for CdTe/CdSe Type-II core/shell QDs are reported. These results are also analyzed in terms of a Boltzmann population of exciton sublevels and calculated electron and hole wave functions. Much of the absorption data and fine structure calculations are already in the literature. These results are combined with new measurements of radiative lifetimes and electron-hole overlap calculations to produce an integrated picture of the II-VI QD spectroscopic fundamentals. Finally, we adopt recent synthetic advances to make very monodisperse zincblende CdSe/CdS quantum dots having near-unity photoluminescence quantum yields (PLQYs). Due the absence of nonradiative decay pathways, accurate values of the radiative lifetimes can be obtained from time resolved PL measurements. Radiative lifetimes can also be obtained from the Einstein relations, using the static absorption spectra and the relative thermal populations in the angular momentum sublevels. One of the inputs into these calculations is the shell thickness, and it is useful to be able to determine shell thickness from spectroscopic measurements. We use an empirically corrected effective mass model to produce a "map" of exciton wavelength as a function of core size and shell thickness. These calculations use an elastic continuum model and the known lattice and elastic constants to include the effect of lattice strain on the band gap energy. Radiative lifetimes calculated both experimentally and theoretically are checked and the size dependence is compared to previous studied Type-I, II and single component particles. However, it is not enough to just understanding these basic photophysics of absorption and emission. The emission intensities (related to QYs) also change with changes of the temperature. The temperature dependent PLs of II-VI QDs is extensively studied, but most of this work is at low temperatures. Temperatures well above ambient are of interest to lighting applications and in this regime both the reversible and irreversible loss of quantum yield (thermal quenching) are serious impediments to the implementation of QDs in commercial devices. Chapter 3 will elucidate the mechanism of static thermal quenching, in which the reduction of QYs does not affect the PL decay kinetics, on CdSe, CdTe and CdSe/ZnSe QDs as a function of particle sizes/shapes, surface composition and surface ligands. Through systematic experiments, this part of the dissertation discusses several possible mechanisms (e.g. structural, activated excited state, and electronic charging) and examines which the dominant cause for loss of QY at high temperature is. The more practical step is to develop the synthetic method of highly luminescent and stable core/shell QDs with minimum thermal quenching, which greatly enhance the energy efficiency of light emitting and photovoltaic devices. As the nonradiative Auger processed are induced by surface charging described in chapter 3, static and time-resolved fluorescence and high and low power transient absorption results on CdSe/CdS and CdSe/ZnSe core/shell particles are presented in chapter 4. Two CdS shell thicknesses were examined and all of the particles had either octadecylamine (ODA) and tributylphosphine (TBP) or just ODA ligands. The results can be understood in terms of a mechanism in which there is a thermal equilibrium between electrons being in the valence band or in chalcogenide localized surface states. Thermal promotion of a valence band electron to a surface state leaves the particle core positively charged. Photon absorption when the particle is in this state results in a positive trion, which undergoes a fast Auger recombination, making the particle nonluminescent. A lack of TBP ligands results in more empty surface orbitals and therefore shifts the equilibrium toward surface trapped electrons and hence trion formation. Low- and high-power transient absorption measurements give the trion and biexciton lifetimes and the ratio of the trion to biexciton Auger lifetimes are examined and compared to the degeneracies of Auger pathways. We also study the shell thickness and composition dependence of Auger times, which is compared to the scaling factors of effective volume and electron-hole overlap considerations. Core/shell QDs often exhibit much higher luminescence quantum yields (QYs), more stability, and are depicted as having a nearly spherical core and a shell of very nearly uniform thickness, which results in a very simple picture of surface passivation. The uniformity of the shell is crucial in obtaining QDs with well passivated surfaces. However, transmission electron microscope (TEM) images disprove the ideal situation. Defects and thickness inhomogeneity in shell materials are treated qualitatively as an analog to film thickness inhomogeneity in epitaxially grown thin films. More quantitatively, the extent to which the shell thickness of core/shell particles is constant can be determined by time-resolved PL studies that measure the dynamics of hole tunneling to acceptors that are adsorbed on the shell surface due that tunneling rates varies strongly with core-acceptor separation. Careful analysis of the hole transfer kinetics reveals the extent of shell thickness inhomogeneity, however, it may be complicated by the distribution of numbers of adsorbed acceptors. All the considerations can be incorporated into a model we establish in Chapter 5for the distribution of measured hole tunneling rates. From this analysis the distribution of shell thicknesses can be extracted from the luminescence kinetic results. This approach is therefore a sensitive measure of the distribution of tunneling distances. Thus, any defects or structural irregularities that allow the hole acceptors to adsorb closer to the particle core increases the hole tunneling rate and can be detected and quantified. A quantitative treatment of the lattice strain energy in determining the shell morphology of CdSe/CdS core/shell nanoparticles is presented in chapter 5. We use the inhomogeneity in hole tunneling rates through the shell to adsorbed hole acceptors to quantify the extent of shell thickness inhomogeneity. The results can be understood in terms of a model based on elastic continuum calculations, which indicate that the lattice strain energy depends on both core size and shell thickness. This model assumes thermodynamic equilibrium, i.e., that the shell morphology corresponds to a minimum total (lattice strain plus surface) energy. Comparison with the experimental results indicates that CdSe/CdS nanoparticles undergo an abrupt transition from smooth to rough shells when the total lattice strain energy exceeds about 27eV or the strain energy density exceeds 0.59 eV/nm2. The predictions of this model are not followed for CdSe/CdS nanoparticles when the shell is deposited at very low temperature and therefore equilibrium is not established. The effects of lattice strain on the spectroscopy and photoluminescence quantum yields of zincblende CdSe/CdS core/shell quantum dots are examined. The quantum yields are measured as a function of core size and shell thickness. High quantum yields are achieved as long as the lattice strain energy density is below ~0.85 eV/nm2, which is considerably greater than the limiting value of 0.59 eV/nm2 for thermodynamicstability of a smooth, defect free shell, as previously reported in chapter 5. Thus, core/shell quantum dots having strain energy densities between 0.59 and 0.85 eV/nm2 can have very high PL QYs, but are metastable with respect to surface defect formation. Such metastable core/shell QDs can be produced by shell deposition at comparatively low temperatures (< 140 °C). Annealing of these particles causes partial loss of core pressure, and a red shift of the spectrum.

Spectroscopic analysis of solar and cosmic X-ray spectra. 1: The nature of cosmic X-ray spectra and proposed analytical techniques

NASA Technical Reports Server (NTRS)

Walker, A. B. C., Jr.

1975-01-01

Techniques for the study of the solar corona are reviewed as an introduction to a discussion of modifications required for the study of cosmic sources. Spectroscopic analysis of individual sources and the interstellar medium is considered. The latter was studied via analysis of its effect on the spectra of selected individual sources. The effects of various characteristics of the ISM, including the presence of grains, molecules, and ionization, are first discussed, and the development of ISM models is described. The expected spectral structure of individual cosmic sources is then reviewed with emphasis on supernovae remnants and binary X-ray sources. The observational and analytical requirements imposed by the characteristics of these sources are identified, and prospects for the analysis of abundances and the study of physical parameters within them are assessed. Prospects for the spectroscopic study of other classes of X-ray sources are also discussed.

Use of different spectroscopic techniques in the analysis of Roman age wall paintings.

PubMed

Agnoli, Francesca; Calliari, Irene; Mazzocchin, Gian-Antonio

2007-01-01

In this paper the analysis of samples of Roman age wall paintings coming from: Pordenone, Vicenza and Verona is carried out by using three different techniques: energy dispersive x-rays spectroscopy (EDS), x-rays fluorescence (XRF) and proton induced x-rays emission (PIXE). The features of the three spectroscopic techniques in the analysis of samples of archaeological interest are discussed. The studied pigments were: cinnabar, yellow ochre, green earth, Egyptian blue and carbon black.

The use of isotypic control antibodies in the analysis of CD3+ and CD3+, CD4+ lymphocyte subsets by flow cytometry. Are they really necessary?

PubMed

Sreenan, J J; Tbakhi, A; Edinger, M G; Tubbs, R R

1997-02-01

Isotypic control reagents are defined as irrelevant antibodies of the same immunoglobulin class as the relevant reagent antibody in a flow cytometry panel. The use of the isotypic control antibody has been advocated as a necessary quality control measure in analysis of flow cytometry. The purpose of this study was to determine the necessity of an isotypic control antibody in the analysis of CD3+ and CD3+, CD4+ lymphocyte subsets. We performed a prospective study of 46 consecutive patient samples received for lymphocyte subset analysis to determine the need for the isotypic control. For each sample, a sham buffer (autocontrol) and isotypic control reagent were stained for three-color immunofluorescence, processed, and identically analyzed with Attractors software. The Attractors software allowed independent, multiparametric, simultaneous gating; was able to identically and reproducibly process each list mode file; and yielded population data in spreadsheet form. Statistical analysis (Fisher's z test) revealed no difference between the CD3+ autocontrol and CD3+ isotypic control (correlation = 1, P < .0001) or between the CD3+, CD4+ autocontrol and the CD3+, CD4+ isotypic control (correlation = 1, P < .0001). The elimination of the isotypic control reagent resulted in a total cost savings of $3.36 per test. Additionally, the subtraction of isotypic background can artifactually depress population enumeration. The use of an isotypic control antibody is not necessary to analyze flow cytometric data that result in discrete cell populations, such as CD3+ and CD3+, CD4+ lymphocyte subsets. The elimination of this unnecessary quality control measure results in substantial cost savings.

Spectroscopic elucidation of energy transfer in hybrid inorganic–biological organisms for solar-to-chemical production

DOE PAGES

Kornienko, Nikolay; Sakimoto, Kelsey K.; Herlihy, David M.; ...

2016-10-03

We present that the rise of inorganic–biological hybrid organisms for solar-to-chemical production has spurred mechanistic investigations into the dynamics of the biotic–abiotic interface to drive the development of next-generation systems. The model system, Moorella thermoacetica–cadmium sulfide (CdS), combines an inorganic semiconductor nanoparticle light harvester with an acetogenic bacterium to drive the photosynthetic reduction of CO 2 to acetic acid with high efficiency. In this work, we report insights into this unique electrotrophic behavior and propose a charge-transfer mechanism from CdS to M. thermoacetica. Transient absorption (TA) spectroscopy revealed that photoexcited electron transfer rates increase with increasing hydrogenase (H 2ase) enzymemore » activity. On the same time scale as the TA spectroscopy, time-resolved infrared (TRIR) spectroscopy showed spectral changes in the 1,700–1,900-cm -1 spectral region. The quantum efficiency of this system for photosynthetic acetic acid generation also increased with increasing H 2ase activity and shorter carrier lifetimes when averaged over the first 24 h of photosynthesis. However, within the initial 3 h of photosynthesis, the rate followed an opposite trend: The bacteria with the lowest H 2ase activity photosynthesized acetic acid the fastest. These results suggest a two-pathway mechanism: a high quantum efficiency charge-transfer pathway to H 2ase generating H 2 as a molecular intermediate that dominates at long time scales (24 h), and a direct energy-transducing enzymatic pathway responsible for acetic acid production at short time scales (3 h). Lastly, this work represents a promising platform to utilize conventional spectroscopic methodology to extract insights from more complex biotic–abiotic hybrid systems.« less

Spectroscopic elucidation of energy transfer in hybrid inorganic-biological organisms for solar-to-chemical production.

PubMed

Kornienko, Nikolay; Sakimoto, Kelsey K; Herlihy, David M; Nguyen, Son C; Alivisatos, A Paul; Harris, Charles B; Schwartzberg, Adam; Yang, Peidong

2016-10-18

The rise of inorganic-biological hybrid organisms for solar-to-chemical production has spurred mechanistic investigations into the dynamics of the biotic-abiotic interface to drive the development of next-generation systems. The model system, Moorella thermoacetica-cadmium sulfide (CdS), combines an inorganic semiconductor nanoparticle light harvester with an acetogenic bacterium to drive the photosynthetic reduction of CO 2 to acetic acid with high efficiency. In this work, we report insights into this unique electrotrophic behavior and propose a charge-transfer mechanism from CdS to M. thermoacetica Transient absorption (TA) spectroscopy revealed that photoexcited electron transfer rates increase with increasing hydrogenase (H 2 ase) enzyme activity. On the same time scale as the TA spectroscopy, time-resolved infrared (TRIR) spectroscopy showed spectral changes in the 1,700-1,900-cm -1 spectral region. The quantum efficiency of this system for photosynthetic acetic acid generation also increased with increasing H 2 ase activity and shorter carrier lifetimes when averaged over the first 24 h of photosynthesis. However, within the initial 3 h of photosynthesis, the rate followed an opposite trend: The bacteria with the lowest H 2 ase activity photosynthesized acetic acid the fastest. These results suggest a two-pathway mechanism: a high quantum efficiency charge-transfer pathway to H 2 ase generating H 2 as a molecular intermediate that dominates at long time scales (24 h), and a direct energy-transducing enzymatic pathway responsible for acetic acid production at short time scales (3 h). This work represents a promising platform to utilize conventional spectroscopic methodology to extract insights from more complex biotic-abiotic hybrid systems.

Spectroscopic studies of the interaction mechanisms between mono-caffeoylquinic acids and transferrin

NASA Astrophysics Data System (ADS)

Guan, Yanqing; Dong, Jing; Chen, Shizhong; Liu, Meixian; Wang, Daidong; Zhang, Xiaotian; Wang, Hong; Lin, Zongtao

2017-06-01

Transferrin (Tf) is an important protein responsible for circulating and transporting iron into cytoplasm. Tf can be taken into cells through endocytosis mediated by Tf receptor, which usually overexpresses in cancer cells. The Tf-Tf receptor pathway opens a possible avenue for novel targeted cancer therapy by utilizing Tf-binding active compounds. Among which, anti-cancer active caffeoylquinic acids (CQAs) were recently found to be promising Tf-binders by our group. For better understanding the anti-cancer activities of CQAs, it is important to unveil the binding mechanisms between CQAs and Tf. In this study, the fluorescence quenching, surface plasmon resonance (SPR), circular dichroism (CD) and molecular docking were used to investigate the interactions between CQA and Tf. The results showed that the calculated apparent association constants of interactions between 1-, 3-, 4- and 5-CQA and Tf at 298 K were 7.97 × 105 M- 1, 4.36 × 107 M- 1, 6.58 × 105 M- 1 and 4.42 × 106 M- 1, respectively. The thermodynamic parameters indicated that the interaction between 1-, 3-, 5-CQA and Tf is due to H-bonding, and electrostatic interactions were likely involved in the binding of 4-CQA and Tf. The CD results indicated that bindings of 1-CQA, 4-CQA and 5-CQA with Tf resulted in more stretched β-turn and random coil translated from β-sheet. In contrast, 3-CQA led to more stable a-helix conformation. Molecular docking studies of CQAs with Tf further displayed that CQAs were able to interact with residues near Fe3 + binding site. The spectroscopic studies revealed the action mechanisms, thermodynamics and interacting forces between CQAs and Tf, and thus are helpful for future design and discovery of Tf-binders for targeted cancer therapy applying Tf-Tf receptor pathway.

Analysis of stem cell apheresis products using intermediate-dose filgrastim plus large volume apheresis for allogeneic transplantation.

PubMed

Engelhardt, M; Bertz, H; Wäsch, R; Finke, J

2001-04-01

Previously, a dose-dependent influence of recombinant human granulocyte colony-stimulating factor (rhG-CSF) on CD34+ mobilization was demonstrated. In this single-center prospective analysis, 52 healthy donors were investigated to determine the efficacy of intermediate-dose rhG-CSF 2x8 microg/kg donor body weight (bw) and intermediate large volume apheresis (LVA, median 12 l) to mobilize peripheral blood progenitor cells (PBPC) for allogeneic transplantation. The median number of CD34+ cells in apheresis products was 0.45% and 2.2x10(6)/kg recipient bw per single apheresis. A total of 5.4x10(6)/kg CD34+ cells were collected with two (range: one to three) LVA. In the analysis of donor subgroups, higher peripheral blood (PB) and apheresis results were obtained in male vs female donors; however, donor weight significantly differed in both groups. Heavier donors displayed higher PB and apheresis CD34+ counts; however, when CD34+ cells/kg were adjusted to a constant bw, similar harvest results were calculated in males and females, demonstrating that gender per se does not, whereas bw does affect apheresis results. Younger donors had significantly higher PB CD34+ counts, higher CD34+ numbers per single apheresis, increased CFU, more T, B, and CD61+, comparable NK, and less CD14+ cells. A correlation analysis of donor age and apheresis results displayed an age-related decline of 0.46x10(6)/kg CD34 cells per decade of donor aging. Cell subsets in apheresis products were CD14 (49%), CD3 (22%), CD4 (13%), CD8 (7%), CD61 (20%), CD19 (5%), and CD16/56+ (3%) cells, with increasing CD14+ cells and decreasing CD3, CD4, CD8, CD61, CD19, and CD16/56+ cells on subsequent days of apheresis. Compared to our previous analysis using high- (2x12 microg) and low-dose (1x10 microg) rhG-CSF for allogeneic PBPC mobilization, the intermediate-dose showed a similar CD34+ mobilization potential to 1x10 microg rhG-CSF; however, with use of LVA, two instead of three (p<0.05) aphereses were sufficient to mobilize > or =4x10(6)/kg bw CD34+ cells in most donors. Taken together, our results demonstrate that intermediate-dose rhG-CSF sufficiently mobilizes > or =4x10(6)/kg x bw CD34+ cells with use of LVA and that especially younger donors display increased CD34+ cell numbers.

A 10-A spectroscopic ruler applied to short polyprolines.

PubMed

Sahoo, Harekrushna; Roccatano, Danilo; Hennig, Andreas; Nau, Werner M

2007-08-08

Fluorescence resonance energy transfer (FRET) from the amino acid tryptophan (Trp) as donor and a 2,3-diazabicyclo[2.2.2]oct-2-ene-labeled asparagine (Dbo) as acceptor in peptides of the general structure Trp-(Pro)n-Dbo-NH2 (n = 1-6) was investigated by steady-state and time-resolved fluorescence, CD, and NMR spectroscopy as well as by molecular dynamics (MD) simulations (GROMOS96 force field). The Trp/Dbo FRET pair is characterized by a very short Förster radius (R0 ca. 9 A), which allowed distance determinations in such short peptides. Water and propylene glycol were investigated as solvents. The peptides were designed to show an early nucleation of the poly(Pro)II (PPII) secondary helix structure for n > or = 2, which was confirmed by their CD spectra. The shortest peptide (n = 1) adopts preferentially the trans conformation about the Trp-Pro bond, as confirmed by NMR spectra. The FRET efficiencies ranged 2-72% and were found to depend sensitively on the peptide length, i.e., the number of intervening proline residues. The analysis of the FRET data at different levels of theory (assuming either a fixed distance or distance distributions according to a wormlike chain or Gaussian model) afforded donor-acceptor distances between ca. 8 A (n = 1) and ca. 16 A (n = 6) in water, which were found to be similar or slightly higher in propylene glycol. The distances afforded by the Trp/Dbo FRET pair were found to be reasonable in comparison to literature data, expectations from the PPII helix structure, and the results from MD simulations. The persistence lengths for the longer peptides were found to lie at 30-70 A in water and 220 +/- 40 A in propylene glycol, suggesting a more rigid PPII helical structure in propylene glycol. A detailed comparison with literature data on FRET in polyprolines demonstrates that the donor-acceptor distances extracted by FRET are correlated with the Förster radii of the employed FRET pairs. This demonstrates the limitations of using FRET as a spectroscopic ruler for short polyprolines, which is presumably due to the breakdown of the point dipole approximation in Förster theory, when the size of the chromophores becomes comparable or larger than the distances under investigation.

Role of flow-cytometric immunophenotyping in prediction of BCR/ABL1 gene rearrangement in adult B-cell acute lymphoblastic leukemia.

PubMed

Corrente, Francesco; Bellesi, Silvia; Metafuni, Elisabetta; Puggioni, Pier Luigi; Marietti, Sara; Ciminello, Angela Maria; Za, Tommaso; Sorà, Federica; Fianchi, Luana; Sica, Simona; De Stefano, Valerio; Chiusolo, Patrizia

2018-05-01

We performed a retrospective analysis of 88 adult patients with B-ALL diagnosed in our center by a flow-cytometric assessment. Immunophenotypic expression of leukemic cells was explored by simultaneous evaluation of positivity, percentage of expressing cells and median fluorescence intensity (MFI). BCR/ABL1 fusion transcripts were assessed by RT-PCR analysis and were identified in 36 patients (40.9%). CD10 and CD34 were positive in the totality of BCR/ABL1-positive cases. Patients with gene rearrangement had a greater frequency of CD66c, CD13 and CD33 positivity compared with BCR/ABL1-negative cases. Moreover, BCR/ABL1-positive cases exhibited a greater median percentage and MFI values of CD13, CD33, CD66c, CD10, CD34 and CD25 expressions, but a lower median percentage and MFI values of CD38 and CD22 expressions than patients without gene rearrangement. Multivariate logistic regression analysis showed that CD10, CD38 and CD13 expressions were independent predictors for the presence of BCR/ABL1 rearrangement. Predictive probabilities of molecular occurrence based on these markers are proposed. © 2017 International Clinical Cytometry Society. © 2017 International Clinical Cytometry Society.

High fidelity polycrystalline CdTe/CdS heterostructures via molecular dynamics

DOE PAGES

Aguirre, Rodolfo; Chavez, Jose Juan; Zhou, Xiaowang; ...

2017-06-20

Molecular dynamics simulations of polycrystalline growth of CdTe/CdS heterostructures have been performed. First, CdS was deposited on an amorphous CdS substrate, forming a polycrystalline film. Subsequently, CdTe was deposited on top of the polycrystalline CdS film. Cross-sectional images show grain formation at early stages of the CdS growth. During CdTe deposition, the CdS structure remains almost unchanged. Concurrently, CdTe grain boundary motion was detected after the first 24.4 nanoseconds of CdTe deposition. With the elapse of time, this grain boundary pins along the CdS/CdTe interface, leaving only a small region of epitaxial growth. CdTe grains are larger than CdS grainsmore » in agreement with experimental observations in the literature. Crystal phase analysis shows that zinc blende structure dominates over the wurtzite structure inside both CdS and CdTe grains. Composition analysis shows Te and S diffusion to the CdS and CdTe films, respectively. Lastly, these simulated results may stimulate new ideas for studying and improving CdTe solar cell efficiency.« less

Flow cytometric analysis of cell-surface and intracellular antigens in leukemia diagnosis.

PubMed

Knapp, W; Strobl, H; Majdic, O

1994-12-15

New technology allows highly sensitive flow cytometric detection and quantitative analysis of intracellular antigens in normal and malignant hemopoietic cells. With this technology, the earliest stages of myeloid and lymphoid differentiation can easily and reliably be identified using antibodies directed against (pro-)myeloperoxidase/MPO, CD22 and CD3 antigens, respectively. Particularly for the analysis of undifferentiated acute myeloblastic leukemia (AML) cells, the immunological demonstration of intracellular MPO or its enzymatically inactive proforms is highly relevant, since other myeloid marker molecules such as CD33, CD13, or CDw65 are either not restricted to the granulomonocytic lineage or appear later in differentiation. By combining MPO staining with staining for lactoferrin (LF), undifferentiated cells can be distinguished from the granulomonocytic maturation compartment in bone marrow, since LF is selectively expressed from the myelocyte stage of differentiation onward. The list of informative intracellular antigens to be used in leukemia cell analysis will certainly expand in the near future. One candidate, intracellular CD68, has already been tested by us, and results are presented. Also dealt within this article are surface marker molecules not (as yet) widely used in leukemia cell analysis but with the potential to provide important additional information. Among them are the surface structures CD15, CD15s, CDw65, CD79a (MB-1), CD79b (B29), CD87 (uPA-R), and CD117 (c-kit).

Energy dispersive CdTe and CdZnTe detectors for spectral clinical CT and NDT applications

NASA Astrophysics Data System (ADS)

Barber, W. C.; Wessel, J. C.; Nygard, E.; Iwanczyk, J. S.

2015-06-01

We are developing room temperature compound semiconductor detectors for applications in energy-resolved high-flux single x-ray photon-counting spectral computed tomography (CT), including functional imaging with nanoparticle contrast agents for medical applications and non-destructive testing (NDT) for security applications. Energy-resolved photon-counting can provide reduced patient dose through optimal energy weighting for a particular imaging task in CT, functional contrast enhancement through spectroscopic imaging of metal nanoparticles in CT, and compositional analysis through multiple basis function material decomposition in CT and NDT. These applications produce high input count rates from an x-ray generator delivered to the detector. Therefore, in order to achieve energy-resolved single photon counting in these applications, a high output count rate (OCR) for an energy-dispersive detector must be achieved at the required spatial resolution and across the required dynamic range for the application. The required performance in terms of the OCR, spatial resolution, and dynamic range must be obtained with sufficient field of view (FOV) for the application thus requiring the tiling of pixel arrays and scanning techniques. Room temperature cadmium telluride (CdTe) and cadmium zinc telluride (CdZnTe) compound semiconductors, operating as direct conversion x-ray sensors, can provide the required speed when connected to application specific integrated circuits (ASICs) operating at fast peaking times with multiple fixed thresholds per pixel provided the sensors are designed for rapid signal formation across the x-ray energy ranges of the application at the required energy and spatial resolutions, and at a sufficiently high detective quantum efficiency (DQE). We have developed high-flux energy-resolved photon-counting x-ray imaging array sensors using pixellated CdTe and CdZnTe semiconductors optimized for clinical CT and security NDT. We have also fabricated high-flux ASICs with a two dimensional (2D) array of inputs for readout from the sensors. The sensors are guard ring free and have a 2D array of pixels and can be tiled in 2D while preserving pixel pitch. The 2D ASICs have four energy bins with a linear energy response across sufficient dynamic range for clinical CT and some NDT applications. The ASICs can also be tiled in 2D and are designed to fit within the active area of the sensors. We have measured several important performance parameters including: the output count rate (OCR) in excess of 20 million counts per second per square mm with a minimum loss of counts due to pulse pile-up, an energy resolution of 7 keV full width at half-maximum (FWHM) across the entire dynamic range, and a noise floor about 20 keV. This is achieved by directly interconnecting the ASIC inputs to the pixels of the CdZnTe sensors incurring very little input capacitance to the ASICs. We present measurements of the performance of the CdTe and CdZnTe sensors including the OCR, FWHM energy resolution, noise floor, as well as the temporal stability and uniformity under the rapidly varying high flux expected in CT and NDT applications.

Energy dispersive CdTe and CdZnTe detectors for spectral clinical CT and NDT applications

PubMed Central

Barber, W. C.; Wessel, J. C.; Nygard, E.; Iwanczyk, J. S.

2014-01-01

We are developing room temperature compound semiconductor detectors for applications in energy-resolved high-flux single x-ray photon-counting spectral computed tomography (CT), including functional imaging with nanoparticle contrast agents for medical applications and non destructive testing (NDT) for security applications. Energy-resolved photon-counting can provide reduced patient dose through optimal energy weighting for a particular imaging task in CT, functional contrast enhancement through spectroscopic imaging of metal nanoparticles in CT, and compositional analysis through multiple basis function material decomposition in CT and NDT. These applications produce high input count rates from an x-ray generator delivered to the detector. Therefore, in order to achieve energy-resolved single photon counting in these applications, a high output count rate (OCR) for an energy-dispersive detector must be achieved at the required spatial resolution and across the required dynamic range for the application. The required performance in terms of the OCR, spatial resolution, and dynamic range must be obtained with sufficient field of view (FOV) for the application thus requiring the tiling of pixel arrays and scanning techniques. Room temperature cadmium telluride (CdTe) and cadmium zinc telluride (CdZnTe) compound semiconductors, operating as direct conversion x-ray sensors, can provide the required speed when connected to application specific integrated circuits (ASICs) operating at fast peaking times with multiple fixed thresholds per pixel provided the sensors are designed for rapid signal formation across the x-ray energy ranges of the application at the required energy and spatial resolutions, and at a sufficiently high detective quantum efficiency (DQE). We have developed high-flux energy-resolved photon-counting x-ray imaging array sensors using pixellated CdTe and CdZnTe semiconductors optimized for clinical CT and security NDT. We have also fabricated high-flux ASICs with a two dimensional (2D) array of inputs for readout from the sensors. The sensors are guard ring free and have a 2D array of pixels and can be tiled in 2D while preserving pixel pitch. The 2D ASICs have four energy bins with a linear energy response across sufficient dynamic range for clinical CT and some NDT applications. The ASICs can also be tiled in 2D and are designed to fit within the active area of the sensors. We have measured several important performance parameters including; the output count rate (OCR) in excess of 20 million counts per second per square mm with a minimum loss of counts due to pulse pile-up, an energy resolution of 7 keV full width at half maximum (FWHM) across the entire dynamic range, and a noise floor about 20keV. This is achieved by directly interconnecting the ASIC inputs to the pixels of the CdZnTe sensors incurring very little input capacitance to the ASICs. We present measurements of the performance of the CdTe and CdZnTe sensors including the OCR, FWHM energy resolution, noise floor, as well as the temporal stability and uniformity under the rapidly varying high flux expected in CT and NDT applications. PMID:25937684

Energy dispersive CdTe and CdZnTe detectors for spectral clinical CT and NDT applications.

PubMed

Barber, W C; Wessel, J C; Nygard, E; Iwanczyk, J S

2015-06-01

We are developing room temperature compound semiconductor detectors for applications in energy-resolved high-flux single x-ray photon-counting spectral computed tomography (CT), including functional imaging with nanoparticle contrast agents for medical applications and non destructive testing (NDT) for security applications. Energy-resolved photon-counting can provide reduced patient dose through optimal energy weighting for a particular imaging task in CT, functional contrast enhancement through spectroscopic imaging of metal nanoparticles in CT, and compositional analysis through multiple basis function material decomposition in CT and NDT. These applications produce high input count rates from an x-ray generator delivered to the detector. Therefore, in order to achieve energy-resolved single photon counting in these applications, a high output count rate (OCR) for an energy-dispersive detector must be achieved at the required spatial resolution and across the required dynamic range for the application. The required performance in terms of the OCR, spatial resolution, and dynamic range must be obtained with sufficient field of view (FOV) for the application thus requiring the tiling of pixel arrays and scanning techniques. Room temperature cadmium telluride (CdTe) and cadmium zinc telluride (CdZnTe) compound semiconductors, operating as direct conversion x-ray sensors, can provide the required speed when connected to application specific integrated circuits (ASICs) operating at fast peaking times with multiple fixed thresholds per pixel provided the sensors are designed for rapid signal formation across the x-ray energy ranges of the application at the required energy and spatial resolutions, and at a sufficiently high detective quantum efficiency (DQE). We have developed high-flux energy-resolved photon-counting x-ray imaging array sensors using pixellated CdTe and CdZnTe semiconductors optimized for clinical CT and security NDT. We have also fabricated high-flux ASICs with a two dimensional (2D) array of inputs for readout from the sensors. The sensors are guard ring free and have a 2D array of pixels and can be tiled in 2D while preserving pixel pitch. The 2D ASICs have four energy bins with a linear energy response across sufficient dynamic range for clinical CT and some NDT applications. The ASICs can also be tiled in 2D and are designed to fit within the active area of the sensors. We have measured several important performance parameters including; the output count rate (OCR) in excess of 20 million counts per second per square mm with a minimum loss of counts due to pulse pile-up, an energy resolution of 7 keV full width at half maximum (FWHM) across the entire dynamic range, and a noise floor about 20keV. This is achieved by directly interconnecting the ASIC inputs to the pixels of the CdZnTe sensors incurring very little input capacitance to the ASICs. We present measurements of the performance of the CdTe and CdZnTe sensors including the OCR, FWHM energy resolution, noise floor, as well as the temporal stability and uniformity under the rapidly varying high flux expected in CT and NDT applications.

Spectroscopic characterization of low dose rate brachytherapy sources

NASA Astrophysics Data System (ADS)

Beach, Stephen M.

The low dose rate (LDR) brachytherapy seeds employed in permanent radioactive-source implant treatments usually use one of two radionuclides, 125I or 103Pd. The theoretically expected source spectroscopic output from these sources can be obtained via Monte Carlo calculation based upon seed dimensions and materials as well as the bare-source photon emissions for that specific radionuclide. However the discrepancies resulting from inconsistent manufacturing of sources in comparison to each other within model groups and simplified Monte Carlo calculational geometries ultimately result in undesirably large uncertainties in the Monte Carlo calculated values. This dissertation describes experimentally attained spectroscopic outputs of the clinically used brachytherapy sources in air and in liquid water. Such knowledge can then be applied to characterize these sources by a more fundamental and metro logically-pure classification, that of energy-based dosimetry. The spectroscopic results contained within this dissertation can be utilized in the verification and benchmarking of Monte Carlo calculational models of these brachytherapy sources. This body of work was undertaken to establish a usable spectroscopy system and analysis methods for the meaningful study of LDR brachytherapy seeds. The development of a correction algorithm and the analysis of the resultant spectroscopic measurements are presented. The characterization of the spectrometer and the subsequent deconvolution of the measured spectrum to obtain the true spectrum free of any perturbations caused by the spectrometer itself is an important contribution of this work. The approach of spectroscopic deconvolution that was applied in this work is derived in detail and it is applied to the physical measurements. In addition, the spectroscopically based analogs to the LDR dosimetry parameters that are currently employed are detailed, as well as the development of the theory and measurement methods to arrive at these analogs. Several dosimetrically-relevant water-equivalent plastics were also investigated for their transmission properties within a liquid water environment, as well as in air. The framework for the accurate spectrometry of LDR sources is established as a result of this dissertation work. In addition to the measurement and analysis methods, this work presents the basic measured spectroscopic characteristics of each LDR seed currently in use in the clinic today.

Multicomponent quantitative spectroscopic analysis without reference substances based on ICA modelling.

PubMed

Monakhova, Yulia B; Mushtakova, Svetlana P

2017-05-01

A fast and reliable spectroscopic method for multicomponent quantitative analysis of targeted compounds with overlapping signals in complex mixtures has been established. The innovative analytical approach is based on the preliminary chemometric extraction of qualitative and quantitative information from UV-vis and IR spectral profiles of a calibration system using independent component analysis (ICA). Using this quantitative model and ICA resolution results of spectral profiling of "unknown" model mixtures, the absolute analyte concentrations in multicomponent mixtures and authentic samples were then calculated without reference solutions. Good recoveries generally between 95% and 105% were obtained. The method can be applied to any spectroscopic data that obey the Beer-Lambert-Bouguer law. The proposed method was tested on analysis of vitamins and caffeine in energy drinks and aromatic hydrocarbons in motor fuel with 10% error. The results demonstrated that the proposed method is a promising tool for rapid simultaneous multicomponent analysis in the case of spectral overlap and the absence/inaccessibility of reference materials.

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor)

2013-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Thermodynamic analysis of vapor-phase epitaxy of CdTe using a metallic Cd source

NASA Astrophysics Data System (ADS)

Iso, Kenji; Murakami, Hisashi; Koukitu, Akinori

2017-07-01

Thermodynamic analysis of CdTe growth using cost-effective metallic Cd and dialkyl telluride was performed. The major vapor species at source zone in equilibrium were gaseous Cd for the group-II precursor, and Te2 and H2Te for the group-VI precursors. The driving force for the CdTe deposition was still positive even at 650 °C. This indicates that CdTe formation from gaseous Cd can proceed thermodynamically. Furthermore, the calculations showed that CdTe decomposes at higher temperature and increasing the II/VI ratio increases the limit of the growth temperature, which coincides with the experimental results.

Higher Body Mass Index Is Associated With Greater Proportions of Effector CD8+ T Cells Expressing CD57 in Women Living With HIV.

PubMed

Reid, Michael J A; Baxi, Sanjiv M; Sheira, Lila A; Landay, Alan L; Frongillo, Edward A; Adedimeji, Adebola; Cohen, Mardge H; Wentz, Eryka; Gustafson, Deborah R; Merenstein, Daniel; Hunt, Peter W; Tien, Phyllis C; Weiser, Sheri D

2017-08-15

A low proportion of CD28CD8 T cells that express CD57 is associated with increased mortality in HIV infection. The effect of increasing body mass index (BMI) changes in the proportion of CD57CD28CD8 T cells among HIV-infected individuals on antiretroviral therapy is unknown. In a US cohort of HIV-infected women, we evaluated associations of BMI and waist circumference with 3 distinct CD8 T cell phenotypes: % CD28CD57CD8 T cells, % CD57 of CD28CD8 T cells, and % CD28 of all CD8 T cells. Multivariable linear regression analysis was used to estimate beta coefficients for each of 3 T-cell phenotypes. Covariates included HIV parameters (current and nadir CD4, current viral load), demographics (age, race, income, and study site), and lifestyle (tobacco and alcohol use) factors. Of 225 participants, the median age was 46 years and 50% were obese (BMI >30 m/kg). Greater BMI and waist circumference were both associated with higher % CD28CD57CD8 T cells and % CD57 of all CD28CD8 T cells in multivariable analysis, including adjustment for HIV viral load (all P < 0.05). The association between greater BMI and the overall proportion of CD28 CD8 cells in fully adjusted models (0.078, 95% confidence interval: -0.053 to 0.209) was not significant. In this analysis, greater BMI and waist circumference are associated with greater expression of CD57 on CD28CD8 T cells and a greater proportion of CD57CD28 CD8 T cells. These findings may indicate that increasing BMI is immunologically protective in HIV-infected women. Future research is needed to understand the prognostic importance of these associations on clinical outcomes.

[Spectroscopic characteristics of novel Psidium meroterpenoids isolated from guava leaves].

PubMed

Ouyang, Wen; Zhu, Xiao-ai; Liu, Xiao-juan; Yie, Shu-min; Zhao, Litchao; Su, Lei; Cao, Yong

2015-07-01

Recently, novel Psidium meroterpenoids were reported in the guava leaves. According to careful analysis of the spectral data of literatures, the spectroscopic characteristics and biosynthetic pathway of Psidium meroterpenoids were summarized in this paper. The results showed that Psidium meroterpenoids had distinct spectroscopic features and reasonable biosynthetic routines, however the number order of carbon atoms was not consistent in the reported literatures. It was concluded that Psidium meroterpenoids were the characteristic chemical constituents of Psidium guajava Linn.

Terminally differentiated CD8+ T cells and CD57−FOXP3+CD8+ T cells are highly associated with the efficacy of immunotherapy using activated autologous lymphocytes

PubMed Central

Akagi, Junji; Baba, Hideo; Sekine, Teruaki; Ogawa, Kenji

2018-01-01

Treatment with activated autologous lymphocytes (AALs) has demonstrated mixed results for cancer treatment. Preliminary results revealed that the proportion of cluster of differentiation (CD)8+CD57+ T cells is significantly increased in AALs, indicating that they are able to determine treatment outcome. Therefore, the role of CD8+CD57+ T cells in AAL efficacy was investigated. T lymphocytes were isolated from 35 patients with stage IV gastric carcinomas (17 men and 18 women; aged 41–84 years) receiving immunotherapy using AALs (IAAL). Using fluorescence activated cell sorting, CD8, CD27, CD57, and forkhead box protein 3 (FOXP3) expression was investigated on CD8+ T cell populations in CD8+ T cell differentiation prior to and following in vitro culture. The association between these populations and progression-free survival (PFS) was analyzed using Cox univariate, and multivariate analyses and Kaplan-Meier survival analysis. CD57 expression was negative in early-differentiated CD8+ T cells (CD27+CD8+CD57−), and positive in intermediate- (CD27+CD8+CD57+) and terminal- (CD27−CD8+CD57+) differentiated CD8+ T cells. Univariate analysis revealed a significant association between terminal-CD8+ T cells and longer PFS times (P=0.035), whereas CD57−FOXP3+CD8+ T cells were associated with shorter PFS times. Multivariate analysis revealed that CD57−FOXP3+CD8+ T cells was an independent poor prognostic factor, whereas CD57+FOXP3+CD8+ T cells were not associated with PFS. Although IAAL increased the proportion of terminal-CD8+ T cells relative to the pre-culture proportions, patients with a high CD57−FOXP3+CD8+ T cell percentage exhibited repressed terminal-CD8+ T cell induction, leading to poor patient prognosis. Terminally differentiated CD27−CD8+CD57+ T cells were responsible for the effectiveness of AALs; however, CD57−FOXP3+CD8+ T cells abrogated their efficacy, possibly by inhibiting their induction.

Enzymatic synthesis and characterizations of cyclic GDP-ribose. A procedure for distinguishing enzymes with ADP-ribosyl cyclase activity.

PubMed

Graeff, R M; Walseth, T F; Fryxell, K; Branton, W D; Lee, H C

1994-12-02

Cyclic nucleotides such as cAMP and cGMP are second messengers subserving various signaling pathways. Cyclic ADP-ribose (cADPR), a recently discovered member of the family, is derived from NAD+ and is a mediator of Ca2+ mobilization in various cellular systems. The synthesis and degradation of cADPR are, respectively, catalyzed by ADP-ribosyl cyclase and cADPR hydrolase. CD38, a differentiation antigen of B lymphocytes, has recently been shown to be a bifunctional enzyme catalyzing both the formation and hydrolysis of cADPR. The overall reaction catalyzed by CD38 is the formation of ADP-ribose and nicotinamide from NAD+, identical to that catalyzed by NADase. The difficulties in detecting the formation of cADPR have led to frequent identification of CD38 as a classical NADase. In this study, we show that both ADP-ribosyl cyclase and CD38, but not NADase, can cyclize nicotinamide guanine dinucleotide (NGD+) producing a new nucleotide. Analyses by high performance liquid chromatography and mass spectroscopy indicate the product is cyclic GDP-ribose (cGDPR) with a structure similar to cADPR except with guanine replacing adenine. Compared to cADPR, cGDPR is a more stable compound showing 2.8 times more resistance to heat-induced hydrolysis. These results are consistent with a catalytic scheme for CD38 where the cyclization of the substrate precedes the hydrolytic reaction. Spectroscopic analyses show that cGDPR is fluorescent and has an absorption spectrum different from both NGD+ and GDPR, providing a very convenient way for monitoring its enzymatic formation. The use of NGD+ as substrate for assaying the cyclization reaction was found to be applicable to pure enzymes as well as crude tissue extracts making it a useful diagnostic tool for distinguishing CD38-like enzymes from degradative NADases.

A Compact, Portable, Reduced-Cost, Gamma Ray Spectroscopic System for Nuclear Verification Final Report CRADA No. TSB-1551-98

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavietes, A.; Kalkhoran, N.

The overall goal of this project was to demonstrate a compact gamma-ray spectroscopic system with better energy resolution and lower costs than scintillator-based detector systems for uranium enrichment analysis applications.

Breath Analysis Using Laser Spectroscopic Techniques: Breath Biomarkers, Spectral Fingerprints, and Detection Limits

PubMed Central

Wang, Chuji; Sahay, Peeyush

2009-01-01

Breath analysis, a promising new field of medicine and medical instrumentation, potentially offers noninvasive, real-time, and point-of-care (POC) disease diagnostics and metabolic status monitoring. Numerous breath biomarkers have been detected and quantified so far by using the GC-MS technique. Recent advances in laser spectroscopic techniques and laser sources have driven breath analysis to new heights, moving from laboratory research to commercial reality. Laser spectroscopic detection techniques not only have high-sensitivity and high-selectivity, as equivalently offered by the MS-based techniques, but also have the advantageous features of near real-time response, low instrument costs, and POC function. Of the approximately 35 established breath biomarkers, such as acetone, ammonia, carbon dioxide, ethane, methane, and nitric oxide, 14 species in exhaled human breath have been analyzed by high-sensitivity laser spectroscopic techniques, namely, tunable diode laser absorption spectroscopy (TDLAS), cavity ringdown spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS), cavity enhanced absorption spectroscopy (CEAS), cavity leak-out spectroscopy (CALOS), photoacoustic spectroscopy (PAS), quartz-enhanced photoacoustic spectroscopy (QEPAS), and optical frequency comb cavity-enhanced absorption spectroscopy (OFC-CEAS). Spectral fingerprints of the measured biomarkers span from the UV to the mid-IR spectral regions and the detection limits achieved by the laser techniques range from parts per million to parts per billion levels. Sensors using the laser spectroscopic techniques for a few breath biomarkers, e.g., carbon dioxide, nitric oxide, etc. are commercially available. This review presents an update on the latest developments in laser-based breath analysis. PMID:22408503

Comparative Gene Expression Profiling of Primary and Metastatic Renal Cell Carcinoma Stem Cell-Like Cancer Cells

PubMed Central

Czarnecka, Anna M.; Lewicki, Sławomir; Helbrecht, Igor; Brodaczewska, Klaudia; Koch, Irena; Zdanowski, Robert; Król, Magdalena; Szczylik, Cezary

2016-01-01

Background Recent advancement in cancer research has shown that tumors are highly heterogeneous, and multiple phenotypically different cell populations are found in a single tumor. Cancer development and tumor growth are driven by specific types of cells—stem cell-like cancer cells (SCLCCs)—which are also responsible for metastatic spread and drug resistance. This research was designed to verify the presence of SCLCCs in renal cell cancer cell lines. Subsequently, we aimed to characterize phenotype and cell biology of CD105+ cells, defined previously as renal cell carcinoma tumor-initiating cells. The main goal of the project was to describe the gene-expression profile of stem cell-like cancer cells of primary tumor and metastatic origin. Materials and Methods Real-time PCR analysis of stemness genes (Oct-4, Nanog and Ncam) and soft agar colony formation assay were conducted to check the stemness properties of renal cell carcinoma (RCC) cell lines. FACS analysis of CD105+ and CD133+ cells was performed on RCC cells. Isolated CD105+ cells were verified for expression of mesenchymal markers—CD24, CD146, CD90, CD73, CD44, CD11b, CD19, CD34, CD45, HLA-DR and alkaline phosphatase. Hanging drop assay was used to investigate CD105+ cell-cell cohesion. Analysis of free-floating 3D spheres formed by isolated CD105+ was verified, as spheres have been hypothesized to contain undifferentiated multipotent progenitor cells. Finally, CD105+ cells were sorted from primary (Caki-2) and metastatic (ACHN) renal cell cancer cell lines. Gene-expression profiling of sorted CD105+ cells was performed with Agilent’s human GE 4x44K v2 microarrays. Differentially expressed genes were further categorized into canonical pathways. Network analysis and downstream analysis were performed with Ingenuity Pathway Analysis. Results Metastatic RCC cell lines (ACHN and Caki-1) demonstrated higher colony-forming ability in comparison to primary RCC cell lines. Metastatic RCC cell lines harbor numerous CD105+ cell subpopulations and have higher expression of stemness genes (Oct-4 and Nanog). CD105+ cells adopt 3D grape-like floating structures under handing drop conditions. Sorted CD105+ cells are positive for human mesenchymal stem cell (MSC) markers CD90, CD73, CD44, CD146, and alkaline phosphatase activity, but not for CD24 and hematopoietic lineage markers CD34, CD11b, CD19, CD45, and HLA-DR. 1411 genes are commonly differentially expressed in CD105+ cells (both from primary [Caki-2] and metastatic RCC [ACHN] cells) in comparison to a healthy kidney epithelial cell line (ASE-5063). TGF-β, Wnt/β-catenine, epithelial-mesenchymal transition (EMT), Rap1 signaling, PI3K-Akt signaling, and Hippo signaling pathway are deregulated in CD105+ cells. TGFB1, ERBB2, and TNF are the most significant transcriptional regulators activated in these cells. Conclusions All together, RCC-CD105+ cells present stemlike properties. These stem cell-like cancer cells may represent a novel target for therapy. A unique gene-expression profile of CD105+ cells could be used as initial data for subsequent functional studies and drug design. PMID:27812180

Transcriptome Analysis of Mycobacteria-Specific CD4+ T Cells Identified by Activation-Induced Expression of CD154.

PubMed

Kunnath-Velayudhan, Shajo; Goldberg, Michael F; Saini, Neeraj K; Johndrow, Christopher T; Ng, Tony W; Johnson, Alison J; Xu, Jiayong; Chan, John; Jacobs, William R; Porcelli, Steven A

2017-10-01

Analysis of Ag-specific CD4 + T cells in mycobacterial infections at the transcriptome level is informative but technically challenging. Although several methods exist for identifying Ag-specific T cells, including intracellular cytokine staining, cell surface cytokine-capture assays, and staining with peptide:MHC class II multimers, all of these have significant technical constraints that limit their usefulness. Measurement of activation-induced expression of CD154 has been reported to detect live Ag-specific CD4 + T cells, but this approach remains underexplored and, to our knowledge, has not previously been applied in mycobacteria-infected animals. In this article, we show that CD154 expression identifies adoptively transferred or endogenous Ag-specific CD4 + T cells induced by Mycobacterium bovis bacillus Calmette-Guérin vaccination. We confirmed that Ag-specific cytokine production was positively correlated with CD154 expression by CD4 + T cells from bacillus Calmette-Guérin-vaccinated mice and show that high-quality microarrays can be performed from RNA isolated from CD154 + cells purified by cell sorting. Analysis of microarray data demonstrated that the transcriptome of CD4 + CD154 + cells was distinct from that of CD154 - cells and showed major enrichment of transcripts encoding multiple cytokines and pathways of cellular activation. One notable finding was the identification of a previously unrecognized subset of mycobacteria-specific CD4 + T cells that is characterized by the production of IL-3. Our results support the use of CD154 expression as a practical and reliable method to isolate live Ag-specific CD4 + T cells for transcriptomic analysis and potentially for a range of other studies in infected or previously immunized hosts. Copyright © 2017 by The American Association of Immunologists, Inc.

T-cell immunity and cytokine production in cosmonauts after long-duration space flights

NASA Astrophysics Data System (ADS)

Morukov, B.; Rykova, M.; Antropova, E.; Berendeeva, T.; Ponomaryov, S.; Larina, I.

2011-04-01

Long-duration spaceflight effects on T-cell immunity and cytokine production were studied in 12 Russian cosmonauts flown onto the International Space Station. Specific assays were performed before launch and after landing and included analysis of peripheral leukocyte distribution, analysis of T-cell phenotype, expression of activation markers, apoptosis, proliferation of T cells in response to a mitogen, concentrations of cytokines in supernatants of cell cultures. Statistically significant increase was observed in leukocytes', lymphocytes', monocytes' and granulocytes' total number, increase in percentage and absolutely number of CD3 +CD4 +-cells, CD4 +CD45RA +-cells and CD4 +CD45RA +/CD4 +CD45RО + ratio, CD4 +CD25 +Bright regulatory cells ( p<0,05) in peripheral blood after landing. T-lymphocytes' capacity to present CD69 and CD25 on its own surfaces was increased for the majority of crewmembers. Analysis of T-cell response to PHA-stimulation in vitro revealed there were some trends toward reduced proliferation of stimulated T-lymphocytes. There was an apparent post flight decrease in secreted IFN-g for the majority of crewmembers and in most instances there was elevation in secreted IL-10. It revealed depression of IFN-g/IL-10 ratio after flight. Correlation analysis according to Spearman's rank correlation test established significant positive correlations ( p<0.05) between cytokine production and T-cell activation (CD25+, CD38+) and negative correlation ( p<0.05) between cytokine production and number of bulk memory CD4+T-cells (CD45RO+). Thus, these results suggest that T-cell dysfunction can be conditioned by cytokine dysbalance and could lead to development of disease after long-duration space flights.

New Metabolites and Bioactive Chlorinated Benzophenone Derivatives Produced by a Marine-Derived Fungus Pestalotiopsis heterocornis.

PubMed

Lei, Hui; Lin, Xiuping; Han, Li; Ma, Jian; Ma, Qingjuan; Zhong, Jialiang; Liu, Yonghong; Sun, Tiemin; Wang, Jinhui; Huang, Xueshi

2017-03-13

Four new compounds, including two isocoumarins, pestaloisocoumarins A and B ( 1 , 2 ), one sesquiterpenoid degradation, isopolisin B ( 4 ), and one furan derivative, pestalotiol A ( 5 ), together with one known isocoumarin, gamahorin ( 3 ), and three chlorinated benzophenone derivatives, pestalachloride B ( 6 ), pestalachloride E ( 7 ) and a mixture of pestalalactone atropisomers ( 8a/8b ), were isolated from a culture of the fungus Pestalotiopsis heterocornis associated with sponge Phakellia fusca . These new chemical structures were established using NMR and MS spectroscopic data, as well as single-crystal X-ray crystallographic analysis and CD Cotton effects. All of the isolated compounds were evaluated for their antimicrobial and cytotoxic activities. Isocoumarins 1 - 3 , showed antibacterial activities against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis with MIC values ranging from 25 to 100 μg/mL and weak antifungal activities. Chlorinated benzophenone derivatives 6 - 8 exhibited antibacterial activities against S. aureus and B. subtilis with MIC values ranging from 3.0 to 50 μg/mL and cytotoxicities against four human cancer cell lines with IC 50 values of 6.8-87.8 μM.

Evaluation of the binding interaction between bovine serum albumin and dimethyl fumarate, an anti-inflammatory drug by multispectroscopic methods

NASA Astrophysics Data System (ADS)

Jattinagoudar, Laxmi; Meti, Manjunath; Nandibewoor, Sharanappa; Chimatadar, Shivamurti

2016-03-01

The information of the quenching reaction of bovine serum albumin with dimethyl fumarate is obtained by multi-spectroscopic methods. The number of binding sites, n and binding constants, KA were determined at different temperatures. The effect of increasing temperature on Stern-Volmer quenching constants (KD) indicates that a dynamic quenching mechanism is involved in the interaction. The analysis of thermodynamic quantities namely, ∆H° and ∆S° suggested hydrophobic forces playing a major role in the interaction between dimethyl fumarate and bovine serum albumin. The binding site of dimethyl fumarate on bovine serum albumin was determined by displacement studies, using the site probes viz., warfarin, ibuprofen and digitoxin. The determination of magnitude of the distance of approach for molecular interactions between dimethyl fumarate and bovine serum albumin is calculated according to the theory of Förster energy transfer. The CD, 3D fluorescence spectra, synchronous fluorescence measurements and FT-IR spectral results were indicative of the change in secondary structure of the protein. The influence of some of the metal ions on the binding interaction was also studied.

A novel class of α-glucosidase and HMG-CoA reductase inhibitors from Ganoderma leucocontextum and the anti-diabetic properties of ganomycin I in KK-Ay mice.

PubMed

Wang, Kai; Bao, Li; Ma, Ke; Zhang, Jinjin; Chen, Baosong; Han, Junjie; Ren, Jinwei; Luo, Huajun; Liu, Hongwei

2017-02-15

Three new meroterpenoids, ganoleucin A-C (1-3), together with five known meroterpenoids (4-8), were isolated from the fruiting bodies of Ganoderma leucocontextum. The structures of the new compounds were elucidated by extensive spectroscopic analysis, circular dichroism (CD) spectroscopy, and chemical transformation. The inhibitory effects of 1-8 on HMG-CoA reductase and α-glucosidase were tested in vitro. Ganomycin I (4), 5, and 8 showed stronger inhibitory activity against HMG-CoA reductase than the positive control atorvastatin. Compounds 1, and 3-8 presented potent noncompetitive inhibitory activity against α-glucosidase from both yeast and rat small intestinal mucosa. Ganomycin I (4), the most potent inhibitor against both α-glucosidase and HMG-CoA reductase, was synthesized and evaluated for its in vivo bioactivity. Pharmacological results showed that ganomycin I (4) exerted potent and efficacious hypoglycemic, hypolipidemic, and insulin-sensitizing effects in KK-A y mice. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Antioxidant neolignan and phenolic glucosides from the fruit of Euterpe oleracea.

PubMed

Hu, Jian; Zhao, Jianping; Khan, Shabana I; Liu, Qiang; Liu, Yang; Ali, Zulfiqar; Li, Xing-Cong; Zhang, Shui-han; Cai, Xiong; Huang, Hui-yong; Wang, Wei; Khan, Ikhlas A

2014-12-01

Three new glucosides, namely, (-)-7R8S-7',8'-dihydroxy-dihydrodehydroconiferyl alcohol-9-O-β-D-glucopyranoside (1), (+)-7S8R-7',8'-dihydroxy-dihydrodehydroconiferyl alcohol-9-O-β-D-glucopyranoside (2) and 4-hydroxy-2-methoxyphenyl 1-O-[6-(hydrogen 3-hydroxy-3-methylpentanedioate)]-β-D-glucopyranoside (3), along with 6 known compounds were isolated from the fruit of Euterpe oleracea Mart. Their structures were elucidated based on spectroscopic analyses including NMR, HR-ESI-MS and CD. All the isolated compounds demonstrated significant antioxidant activity and 2 displayed moderate cytotoxicity against HL-60 cells. Copyright © 2014 Elsevier B.V. All rights reserved.

Three new biflavonoids from the branches and leaves of Cephalotaxus oliveri and their antioxidant activity.

PubMed

Xiao, Shu; Mu, Zhen-Qiang; Cheng, Chun-Ru; Ding, Jie

2018-03-15

Three new biflavonoids, named oliveriflavones A-C (1-3), together with two known flavonoids (quercetin (4) and rutin (5)), were isolated from the endangered plant Cephalotaxus oliveri. The chemical structures of these compounds were elucidated by comprehensive spectroscopic methods including NMR, HRESIMS, IR, UV, and CD spectra. Compounds 1-5 were first isolated from the genus Cephalotaxus. All the compounds were tested for their antioxidant activity. Compounds 4 and 5 showed excellent activity with IC 50 values of 0.03 ± 0.06 μM and 0.02 ± 0.10 μM, respectively.

A multi-spectroscopic and molecular docking approach to investigate the interaction of antiviral drug oseltamivir with ct-DNA.

PubMed

Moghadam, Neda Hosseinpour; Salehzadeh, Sadegh; Shahabadi, Nahid; Golbedaghi, Reza

2017-07-03

The possible interaction between the antiviral drug oseltamivir and calf thymus DNA at physiological pH was studied by spectrophotometry, competitive spectrofluorimetry, differential pulse voltammogram (DPV), circular dichroism spectroscopy (CD), viscosity measurements, salt effect, and computational studies. Intercalation of oseltamivir between the base pairs of DNA was shown by a sharp increase in specific viscosity of DNA and a decrease of the peak current and a positive shift in differential pulse voltammogram. Competitive fluorescence experiments were performed using neutral red (NR) as a probe for the intercalation binding mode. The studies showed that oseltamivir is able to release the NR.

A new flavonoid from Sophora flavescens Ait.

PubMed

Huang, Rong; Liu, Yi; Zhao, Lin-Lin; Chen, Xi-Xin; Wang, Feng; Cai, Wei; Chen, Lei

2017-10-01

A new flavonoid, 8-(3-hydroxymethyl-2-butenyl)-5,7,2',4'-tetrahydroxyflavanone (1), along with seven known compounds, (2R)-3α,7,4'-Trihydroxy -5-methoxy-8-prenylflavanone (2), (2R)-3β,7,4'- Trihydroxy-5-methoxy-8-prenylflavanone (3), 3,7-dihydroxycoumarin (4), Shandougenines B (5), Specionin (6), Kushenol N (7) and Kushenol I (8) were isolated from the roots of Sophora flavescens. Among them, Compound 5 was isolated from Leguminous plants, and compounds 4 and 6 were isolated from Sophora flavescens for the first time. Their structures were elucidated by the aid of NMR, HRMS, HMBC and CD spectroscopic methods.

CD90/THY1 is over-expressed in prostate cancer-associated fibroblasts and could serve as a cancer biomarker

PubMed Central

True, Lawrence D; Zhang, Hui; Ye, Mingliang; Huang, Chung-Ying; Nelson, Peter S; von Haller, Priska D; Tjoelker, Larry W; Kim, Jong-Seo; Qian, Wei-Jun; Smith, Richard D; Ellis, William J; Liebeskind, Emily S; Liu, Alvin Y

2010-01-01

A by-product in the processing of prostate tissue for cell sorting by collagenase digestion is the media supernatant that remains after the cells are harvested. These supernatants contain proteins made by the cells within the tissue. Quantitative proteomic analysis of N-glycosylated proteins detected an increased amount of CD90/THY1 in cancer supernatants compared to non-cancer supernatants. Immunohistochemistry showed that in all carcinomas, regardless of Gleason grade, a layer of CD90-positive stromal fibroblastic cells, approximately 5-to-10 cells deep, was localized to tumor glands. In contrast, a no more than 1-cell wide girth of CD90-positive stromal cells was found around benign glands. The increased number of CD90-positive stromal cells in cancer correlated with overexpression of CD90 mRNA detected by gene expression analysis of stromal cells obtained by laser-capture microdissection. There is increasing evidence that cancer-associated stroma plays a role in both tumor progression and carcinogenesis. Most experiments to identify cancer biomarkers have focused on the cancer cells. CD90, being a marker for prostate cancer-associated stroma, might be a potential biomarker for this cancer. A non-invasive test could be provided by a urine test. Proteomic analysis of urine from patients with prostate cancer identified CD90; conversely, CD90 was not detected in the urine of post-prostatectomy patients. Furthermore, this urinary CD90 protein was a variant CD90 protein not known to be expressed by such cells as lymphocytes that express CD90. These CD90 results were obtained from ∼90 cases consisting of proteomic analysis of tissue and urine, immunohistochemistry, Western blot analysis of tissue media, flow cytometry of cells from digested tissue, and reverse transcriptase polymerase chain reaction analysis of isolated stromal cells. PMID:20562849

LaPO4:Eu fluorescent nanorods, synthesis, characterization and spectroscopic studies on interaction with human serum albumin

NASA Astrophysics Data System (ADS)

Guo, Xingjia; Yao, Jie; Liu, Xuehui; Wang, Hongyan; Zhang, Lizhi; Xu, Liping; Hao, Aijun

2018-06-01

Eu3+ doped LaPO4 fluorescent nanorods (LaPO4:Eu) was successfully fabricated by a hydrothermal process. The obtained LaPO4:Eu nanorods under the optimal conditions were characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD) technique, Fourier transform infrared (FTIR), UV-vis absorption and fluorescence spectroscopy. The nanorods with a length of 50-100 nm and a diameter of about 10 nm, can emit strong red fluorescence upon excitation at 241 nm. The FTIR result confirmed that there are lots of phosphate groups on the surfaces of nanorods. In order to better understand the physiological behavior of nanorods in human body, multiple spectroscopic methods were used to study the interaction between the LaPO4:Eu nanorods and human serum albumin (HSA) in the simulated physiological conditions. The results indicated that the nanorods can effectively quench the intrinsic fluorescence of HSA through a dynamic quenching mode with the association constants of the order of 103 L mol-1. The values of the thermodynamic parameters suggested that the binding of the nanorods to HSA was a spontaneous process and van der Waals forces and hydrogen bonds played a predominant role. The displacement experiments verified that the binding site of nanorods on HSA was mainly located in the hydrophobic pocket of subdomain IIA (site I) of HSA. The binding distance between nanorods and HSA was calculated to be 4.2 nm according to the theory of Förster non-radiation energy transfer. The analysis of synchronous fluorescence, three-dimensional fluorescence (3D) and circular dichroism (CD) spectra indicated that there the addition of LaPO4:Eu nanorods did not caused significant alterations in conformation of HSA secondary structure and the polarity around the amino acid residues.

Sensing of hydrophobic cavity of serum albumin by an adenosine analogue: fluorescence correlation and ensemble spectroscopic studies.

PubMed

Nag, Moupriya; Bera, Kallol; Chakraborty, Sandipan; Basak, Soumen

2013-10-05

Adenosine is a naturally occurring purine nucleoside that plays important role in various biochemical processes. We have studied the binding of TNP-Ado (trinitrophenylated-adenosine), a fluorescent analogue of adenosine (which itself is a weak fluorophore), with a model transport protein, bovine serum albumin (BSA). The binding affinity was determined using Fluorescence correlation spectroscopy (FCS) and compared with its value obtained from macroscopic fluorescence spectroscopic studies. Fluorescence and circular dichroism (CD) spectroscopies were employed together with molecular docking study to locate the probable binding site of TNP-Ado on BSA and its effect on the conformation and stability of BSA. Fluorescence studies showed that TNP-Ado binds to BSA in 1:1 stoichiometry via an entropically favoured process. Induced CD spectra revealed that a chiro-optical switching of TNP-Ado occurs upon binding to BSA. Results on urea-induced denaturation of BSA and docking study suggested that the binding site for the ligand is in the hydrophobic subdomain IIA of BSA, consistent with the results of other measurements. This study establishes TNP-Ado as a sensor of hydrophobic regions in proteins like serum albumin, having the capability of detecting a minimum concentration of 140ng/ml protein. FCS measurement of binding interaction of rhodamine-labeled TNP-Ado (RTNP-Ado) with BSA yielded an association constant of KFCS=(1.03±0.06) × 10(4)M(-1). The association constants (Ka) obtained for binding of BSA with rhodamine-free (i.e. TNP-Ado) and rhodamine-labeled (RTNP-Ado) ligands, obtained using the ensemble spectroscopic technique, were (2.3±0.06) × 10(5)M(-1) and (3.4±0.03) × 10(4)M(-1), respectively. The difference between the values of Ka for the free and labeled ligands suggests that fluorescent labeling of small molecules perceptibly interferes with the binding process. On the other hand, the difference in Ka obtained by FCS and ensemble techniques is due to the fact that while the former measures the change in the diffusion constant (i.e. size) of RTNP-Ado upon binding to BSA, the latter focuses on the change of tryptophan emission properties of BSA due to the presence of bound RTNP-Ado. Copyright © 2013 Elsevier B.V. All rights reserved.

Spectroscopic quantification of extremely rare molecular species in the presence of interfering optical absorption

DOEpatents

Ognibene, Ted; Bench, Graham; McCartt, Alan Daniel; Turteltaub, Kenneth; Rella, Chris W.; Tan, Sze; Hoffnagle, John A.; Crosson, Eric

2017-05-09

Optical spectrometer apparatus, systems, and methods for analysis of carbon-14 including a resonant optical cavity configured to accept a sample gas including carbon-14, an optical source configured to deliver optical radiation to the resonant optical cavity, an optical detector configured to detect optical radiation emitted from the resonant cavity and to provide a detector signal; and a processor configured to compute a carbon-14 concentration from the detector signal, wherein computing the carbon-14 concentration from the detector signal includes fitting a spectroscopic model to a measured spectrogram, wherein the spectroscopic model accounts for contributions from one or more interfering species that spectroscopically interfere with carbon-14.

Spectroscopic and theoretical studies of charge-transfer interaction of 1-(2-pyridylazo)-2-napthol with nitroaromatics

NASA Astrophysics Data System (ADS)

Karmakar, Animesh; Singh, Bula

2017-05-01

1-(2-Pyridylazo)-2-napthol (hereafter 1Q) is widely used as a chelating ligand applied in chelatometric, spectrophotometric analysis of metal ions. It appeared from the literature survey that no inclusion complex of 1Q was reported with nitroaromatics. The formation of charge-transfer complex gives an opportunity to improve the physico-chemical properties of different donors. So the complex of 1Q with 4-nitrophenol (4-NP), 2,4-dinitrophenol (2,4-DNP), picric acid (PA), and 3,5-dinitrosalicylic acid (3,5-DNSA) was described in this work in methanol medium. The ground and excited state binding constants and other spectroscopic data have been determined using UV-vis and fluorescence spectroscopic studies. All the complexes have been synthesized and characterized using FT-IR, 1H NMR, and elemental analysis. Spectroscopic data reveal that 1Q joins by a N+sbnd Hsbnd O- type hydrogen bond with nitroaromatics. Job's plot of the continuous variation of absorbance indicates that stoichiometry of CT-complex was 1:1. Thermal stability of the synthesized complex has determined by TGA-DTA analysis. Energy-minimization DFT calculation further supported the formation of the H-bonded charge-transfer adduct.

Hybrid pigments resulting from several guest dyes onto γ-alumina host: A spectroscopic analysis

NASA Astrophysics Data System (ADS)

Pérez, Erik; Ibarra, Ilich A.; Guzmán, Ariel; Lima, Enrique

2017-02-01

The synthesis of hybrid pigments was made from combination of γ-Al2O3 and some organic chromophores such as carminic acid, alizarin, purpurin, curcumin, fluorescein and betacyanins. The γ-Al2O3 was obtained through sol-gel synthesis with 2-propanol and aluminium tri-sec-butoxide (ATB). This article presents some spectroscopic evidences related to the formation of aluminium complexes between coordinative unsaturated sites (CUS) of aluminium and some organic groups (carboxylic acid, quaternary ammonium and β-keto enol) present in the chromophores structure. The physicochemical properties upcoming from a spectroscopic analysis point out that these materials can be applied in the design of new materials with potential uses in artworks and in the field of cultural heritage.

Synchrotron-based X-Ray Spectroscopy Studies for Redox-based Remediation of Lead, Zinc, and Cadmium in Mine Waste Materials.

PubMed

Karna, Ranju R; Hettiarachchi, Ganga M; Newville, Matthew; Sun, ChengJun; Ma, Qing

2016-11-01

Several studies have examined the effect of submergence on the mobility of metals present in mine waste materials. This study examines the effect of organic carbon (OC) and sulfur (S) additions and submergence time on redox-induced biogeochemical transformations of lead (Pb), zinc (Zn), and cadmium (Cd) present in mine waste materials collected from the Tri-State mining district located in southeastern Kansas, southwestern Missouri, and northeastern Oklahoma. A completely randomized design, with a two-way treatment structure, was used for conducting a series of column experiments. Two replicates were used for each treatment combination. Effluent samples were collected at several time points, and soil samples were collected at the end of each column experiment. Because these samples are highly heterogeneous, we used a variety of synchrotron-based techniques to identify Pb, Zn, and Cd speciation at both micro- and bulk-scale. Spectroscopic analysis results from the study revealed that the addition of OC, with and without S, promoted metal-sulfide formation, whereas metal carbonates dominated in the nonamended flooded materials and in mine waste materials only amended with S. Therefore, the synergistic effect of OC and S may be more promising for managing mine waste materials disposed of in flooded subsidence mine pits instead of individual S or OC treatments. The mechanistic understanding gained in this study is also relevant for remediation of waste materials using natural or constructed wetland systems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Synthesis, spectroscopic, thermal and molecular modeling studies of Zn2+, Cd2+ and UO22+ complexes of Schiff bases containing triazole moiety. Antimicrobial, anticancer, antioxidant and DNA binding studies.

PubMed

Gaber, Mohamed; El-Ghamry, Hoda A; Fathalla, Shaimaa K; Mansour, Mohammed A

2018-02-01

A novel series of Zn 2+ , Cd 2+ and UO 2 2+ complexes of ligands namely 1-[(5-mercapto-1H-1,2,4-triazole-3-ylimino) methyl]naphthalene-2-ol (HL 1 ) and [(1H-1,2,4-triazole-3-ylimino) methyl] naphthalene-2-ol (HL 2 ) have been prepared and characterized by different analytical and spectral techniques. The stoichiometry, stereochemistry, conductivity measurements and mode of bonding of the complexes have been elucidated. Accurate comparison of the IR spectra of the ligands with their metal chelates proved the involvement of nitrogen atoms of the azomethine group and/or triazole ring in chelation in addition to the deprotonated hydroxyl oxygen. The UV-Vis and molar conductance data supported the octahedral geometry for the metal complexes. TGA technique has been used to study the thermal decomposition way of the metal complexes and the thermo kinetic parameters were estimated. Valuable information is obtained from calculations of molecular parameters using the molecular modeling techniques. The interaction between the metal complexes and CT-DNA has been studied from which the binding constants (k b ) were calculated. The Schiff bases and their metal chelates have shown potent antimicrobial, antioxidant and antitumor activities. The antitumor activities of the compounds have been tested in vitro against HEPG2 cell line and in silico by the molecular docking analysis with the VEGFR-2 receptor responsible for angiogenesis. Copyright © 2017 Elsevier B.V. All rights reserved.

Bridging Theory and Experiment to Address Structural Properties of Truncated Haemoglobins: Insights from Thermobifida fusca HbO.

PubMed

Howes, Barry D; Boechi, Leonardo; Boffi, Alberto; Estrin, Dario E; Smulevich, Giulietta

2015-01-01

In this chapter, we will discuss the paradigmatic case of Thermobifida fusca (Tf-trHb) HbO in its ferrous and ferric states and its behaviour towards a battery of possible ligands. This choice was dictated by the fact that it has been one of the most extensively studied truncated haemoglobins, both in terms of spectroscopic and molecular dynamics studies. Tf-trHb typifies the structural properties of group II trHbs, as the active site is characterized by a highly polar distal environment in which TrpG8, TyrCD1, and TyrB10 provide three potential H-bond donors in the distal cavity capable of stabilizing the incoming ligands. The role of these residues in key topological positions, and their interplay with the iron-bound ligands, has been addressed in studies carried out on the CO, F(-), OH(-), CN(-), and HS(-) adducts formed with the wild-type protein and a combinatorial set of mutants, in which the distal polar residues, TrpG8, TyrCD1, and TyrB10, have been singly, doubly, or triply replaced by a Phe residue. In this context, such a complete analysis provides an excellent benchmark for the investigation of the relationship between protein structure and function, allowing one to translate physicochemical properties of the active site into the observed functional behaviour. Tf-trHb will be compared with other members of the group II trHbs and, more generally, with members of the other trHb subgroups. © 2015 Elsevier Ltd. All rights reserved.

Narrow Radiative Recombination Continua: A Signature of Ions Crossing the Contact Discontinuity of Astrophysical Shocks

NASA Technical Reports Server (NTRS)

Behar, Ehud; Nordon, Raanan; Soker, Noam; Kastner, Joel H.; Yu, Young Sam

2009-01-01

X-rays from planetary nebulae (PNs) are believed to originate from a shock driven into the fast stellar wind (v 1000 kilometers per second) as it collides with an earlier circumstellar slow wind (v 10 kilometers per second). In theory, the shocked fast wind (hot hubble) and the ambient cold nebula can remain separated by magnetic fields along a surface referred to as the contact discontinuity (CD) that inhibits diffusion and heat conduction. The CD region is extremely difficult to probe directly owing to its small size and faint emission. This has largely left the study of CDs, stellar-shocks, and the associated micro-physics in the realm of theory. This paper presents spectroscopic evidence for ions from the hot bubble (kT approximately equal to 100 eV) crossing the CD and penetrating the cold nebular gas (kT approximately equal to 1 eV). Specifically, a narrow radiative recombination continuum (RRC) emission feature is identified in the high resolution X-ray spectrum of the PN BD+30degree3639 indicating bare C VII ions are recombining with cool electrons at kT(sub e) = 1.7 plus or minus 1.3 eV. An upper limit to the flux of the narrow RRC of H-like C VI is obtained as well. The RRCs are interpreted as due to C ions from the hot bubble of BD+30degree3639 crossing the CD into the cold nebula, where they ultimately recombine with its cool electrons. The RRC flux ratio of C VII to C VI constrains the temperature jump across the CD to deltakT greater than 80 eV, providing for the first time direct evidence for the stark temperature disparity between the two sides of an astrophysical CD, and constraining the role of magnetic fields and heat conduction accordingly. Two colliding-wind binaries are noted to have similar RRCs suggesting a temperature jump and CD crossing by ions may be common feature of stellar wind shocks.

ACVP-03: Novel CD4+ T Cell Specific Immunohistochemistry Detection and Analysis Utilizing Masking of Not-T Cell CD4 in Fixed Tissues from Virally Infected and Uninfected Specimens | Frederick National Laboratory for Cancer Research

Cancer.gov

The Tissue Analysis Core (TAC) within the AIDS and Cancer Virus Program will process, embed, and perform microtomy on fixed tissue samples presented in ethanol. CD4 (DAB) and CD68/CD163 (FastRed) double immunohistochemistry will be performed, in whic

Pyrrole Alkaloids with Potential Cancer Chemopreventive Activity Isolated from a Goji Berry-Contaminated Commercial Sample of African Mango

PubMed Central

2015-01-01

Bioassay-guided fractionation of a commercial sample of African mango (Irvingia gabonensis) that was later shown to be contaminated with goji berry (Lycium sp.) led to the isolation of a new pyrrole alkaloid, methyl 2-[2-formyl-5-(hydroxymethyl)-1H-pyrrol-1-yl]propanoate, 1, along with seven known compounds, 2–8. The structures of the isolated compounds were established by analysis of their spectroscopic data. The new compound 1g showed hydroxyl radical-scavenging activity with an ED50 value of 16.7 μM, whereas 4-[formyl-5-(methoxymethyl)-1H-pyrrol-1-yl]butanoic acid (2) was active in both the hydroxyl radical-scavenging (ED50 11.9 μM) and quinone reductase-induction [CD (concentration required to double QR activity) 2.4 μM)] assays used. The isolated compounds were shown to be absent in a taxonomically authenticated African mango sample but present in three separate authentic samples of goji berry (Lycium barbarum) using LC-MS and 1H NMR fingerprinting analysis, including one sample that previously showed inhibitory activity in vivo in a rat esophageal cancer model induced with N-nitrosomethylbenzylamine. Additionally, microscopic features characteristic of goji berry were observed in the commercial African mango sample. PMID:24792835

The conjugates of ferrocene-1,1'-diamine and amino acids. A novel synthetic approach and conformational analysis.

PubMed

Kovačević, Monika; Kodrin, Ivan; Cetina, Mario; Kmetič, Ivana; Murati, Teuta; Semenčić, Mojca Čakić; Roca, Sunčica; Barišić, Lidija

2015-10-07

A novel synthetic approach toward a poorly explored bioorganometallic consisting of ferrocene-1,1'-diamine bearing structurally and chirally diverse amino acid sequences is reported. Until now, ferrocene-1,1'-diamine was suitable for accommodating only identical amino acid sequences at its N-termini, leading to the symmetrically disubstituted homochiral products stabilized through a 14-membered intramolecular hydrogen-bonded ring as is seen in antiparallel β-sheet peptides. The key step of the novel synthetic pathway is the transformation of Ac-Ala-NH-Fn-COOH (5) (Fn = 1,1'-ferrocenylene) to orthogonally protected Ac-Ala-NH-Fn-NHBoc (7). The spectroscopic analysis (IR, NMR, CD) of the novel compounds, corroborated with DFT studies, suggests the interesting feature of the ferrocene-1,1'-diamine scaffold. The same hydrogen-bonding pattern, i.e. a 14-membered hydrogen-bonded ring, was determined both in solution and in the solid state, thus making them promising, yet simple scaffolds capable of mimicking β-sheet peptides. In vitro screening of potential anticancer activity in Hep G2 human liver carcinoma cells and Hs 578 T human breast cancer cells revealed a cytotoxic pattern for novel compounds (150-500 μM) with significantly decreased cell proliferation.

The effect of pH and triethanolamine on sulfisoxazole complexation with hydroxypropyl-beta-cyclodextrin.

PubMed

Gladys, Granero; Claudia, Garnero; Marcela, Longhi

2003-11-01

A novel complexation of sulfisoxazole with hydroxypropyl-beta-cyclodextrin (HP-beta-CD) was studied. Two systems were used: binary complexes prepared with HP-beta-CD and multicomponent system (HP-beta-CD and the basic compound triethanolamine (TEA)). Inclusion complex formation in aqueous solutions and in solid state were investigated by the solubility method, thermal analysis (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)), Fourier-transform infrared spectroscopy (FT-IR) and dissolution studies. The solid complexes of sulfisoxazole were prepared by freeze-drying the homogeneous concentrated aqueous solutions in molar ratios of sulfisoxazole:HP-beta-CD 1:1 and 1:2, and sulfisoxazole:TEA:HP-beta-CD 1:1:2. FT-IR and thermal analysis showed differences among sulfisoxazole:HP-beta-CD and sulfisoxazole:TEA:HP-beta-CD and their corresponding physical mixtures and individual components. The HP-beta-CD solubilization of sulfisoxazole could be improved by ionization of the drug molecule through pH adjustments. However, larger improvements of the HP-beta-CD solubilization are obtained when multicomponent systems are used, allowing to reduce the amount of CD necessary to prepare the target formulation.

Pixel CdTe semiconductor module to implement a sub-MeV imaging detector for astrophysics

NASA Astrophysics Data System (ADS)

Gálvez, J.-L.; Hernanz, M.; Álvarez, L.; Artigues, B.; Álvarez, J.-M.; Ullán, M.; Pellegrini, G.; Lozano, M.; Cabruja, E.; Martínez, R.; Chmeissani, M.; Puigdengoles, C.

2017-03-01

Stellar explosions are relevant and interesting astrophysical phenomena. Since long ago we have been working on the characterization of nova and supernova explosions in X and gamma rays, with the use of space missions such as INTEGRAL, XMM-Newton and Swift. We have been also involved in feasibility studies of future instruments in the energy range from several keV up to a few MeV, in collaboration with other research institutes, such as GRI, DUAL and e-ASTROGAM. High sensitivities are essential to perform detailed studies of cosmic explosions and cosmic accelerators, e.g., Supernovae, Classical Novae, Supernova Remnants (SNRs), Gamma-Ray Bursts (GRBs). In order to fulfil the combined requirement of high detection efficiency with good spatial and energy resolution, an initial module prototype based on CdTe pixel detectors is being developed. The detector dimensions are 12.5mm x 12.5mm x 2mm, with a pixel pitch of 1mm x 1mm. Each pixel is bump bonded to a fanout board made of Sapphire substrate and routed to the corresponding input channel of the readout ASIC, to measure pixel position and pulse height for each incident gamma-ray photon. An ohmic CdTe pixel detector has been characterised by means of 57Co, 133Ba and 22Na sources. Based on this, its spectroscopic performance and the influence of charge sharing is reported here. The pixel study is complemented by the simulation of the CdTe module performance using the GEANT 4 and MEGALIB tools, which will help us to optimise the pixel size selection.

Syntheses, structural characterization and spectroscopic studies of cadmium(II)-metal(II) cyanide complexes with 4-(2-aminoethyl)pyridine

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Hökelek, Tuncer

2017-02-01

Three new cadmium(II)-metal(II) cyanide complexes, [Cd(4aepy)2(H2O)2][Ni(CN)4] (1), [Cd(4aepy)2(H2O)2][Pd(CN)4] (2) and [Cd(4aepy)2(H2O)2][Pt(CN)4] (3) [4aepy = 4-(2-aminoethyl)pyridine], have been synthesized and characterized by elemental, thermal, FT-IR and Raman spectral analyses. The crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction technique, in which they crystallize in the monoclinic system and C2/c space group. The M(II) [M(II) = Ni(II), Pd(II) and Pt(II)] ions are coordinated with the carbon atoms of the four cyanide groups in the square planar geometries and the [M(CN)4]2- ions act as counter ions. The Cd(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. 3D supramolecular structures of 1 and 2 were occurred by M⋯π and hydrogen bonding (Nsbnd H⋯N and Osbnd H⋯N) interactions. Vibrational assignments of all the observed bands were given and the spectral properties were also supported the crystal structures of the complexes. A possible decompositions of the complexes were investigated in the temperature range 30-800 °C in the static atmosphere.

Zinc and cadmium complexes of a plant metallothionein under radical stress: desulfurisation reactions associated with the formation of trans-lipids in model membranes.

PubMed

Torreggiani, Armida; Domènech, Jordi; Orihuela, Ruben; Ferreri, Carla; Atrian, Sílvia; Capdevila, Mercè; Chatgilialoglu, Chryssostomos

2009-06-08

Metallothioneins (MTs) are sulfur-rich proteins capable of binding metal ions to give metal clusters. The metal-MT aggregates used in this work were Zn- and Cd-QsMT, where QsMT is an MT from the plant Quercus suber. Reactions of reductive reactive species (H(*) atoms and e(aq)(-)), produced by gamma irradiation of water, with Zn- and Cd-QsMT were carried out in both aqueous solutions and vesicle suspensions, and were characterized by different approaches. By using a biomimetic model based on unsaturated lipid vesicle suspensions, the occurrence of tandem protein/lipid damage was shown. The reactions of reductive reactive species with methionine residues and/or sulfur-containing ligands afford diffusible sulfur-centred radicals, which migrate from the aqueous phase to the lipid bilayer and transform the cis double bond of the oleate moiety into the trans isomer. Tailored experiments allowed the reaction mechanism to be elucidated in some detail. The formation of sulfur-centred radicals is accompanied by the modification of the metal-QsMT complexes, which were monitored by various spectroscopic and spectrometric techniques (Raman, CD, and ESI-MS). Attack of the H(*) atom and e(aq)(-) on the metal-QsMT aggregates can induce significant structural changes such as partial deconstruction and/or rearrangement of the metal clusters and breaking of the protein backbone. Substantial differences were observed in the behaviour of the Zn- and Cd-QsMT aggregates towards the reactive species, depending on the different folding of the polypeptide in these two cases.

CD147/EMMPRIN overexpression and prognosis in cancer: A systematic review and meta-analysis

PubMed Central

Xin, Xiaoyan; Zeng, Xianqin; Gu, Huajian; Li, Min; Tan, Huaming; Jin, Zhishan; Hua, Teng; Shi, Rui; Wang, Hongbo

2016-01-01

CD147/EMMPRIN (extracellular matrix metalloproteinase inducer) plays an important role in tumor progression and a number of studies have suggested that it is an indicator of tumor prognosis. This current meta-analysis systematically reevaluated the predictive potential of CD147/EMMPRIN in various cancers. We searched PubMed and Embase databases to screen the literature. Fixed-effect and random-effect meta-analytical techniques were used to correlate CD147 expression with outcome measures. A total of 53 studies that included 68 datasets were eligible for inclusion in the final analysis. We found a significant association between CD147/EMMPRIN overexpression and adverse tumor outcomes, such as overall survival, disease-specific survival, progression-free survival, metastasis-free survival or recurrence-free survival, irrespective of the model analysis. In addition, CD147/EMMPRIN overexpression predicted a high risk for chemotherapy drugs resistance. CD147/EMMPRIN is a central player in tumor progression and predicts a poor prognosis, including in patients who have received chemo-radiotherapy. Our results provide the evidence that CD147/EMMPRIN could be a potential therapeutic target for cancers. PMID:27608940

Reading disc-based bioassays with standard computer drives.

PubMed

Yu, Hua-Zhong; Li, Yunchao; Ou, Lily M-L

2013-02-19

Traditional methods of disease diagnosis are both time-consuming and labor-intensive, and many tests require expensive instrumentation and trained professionals, which restricts their use to biomedical laboratories. Because patients can wait several days (even weeks) for the results, the consequences of delayed treatment could be disastrous. Therefore, affordable and simple point-of-care (POC) biosensor devices could fill a diagnostic niche in the clinic or even at home, as personal glucose meters do for diabetics. These devices would allow patients to check their own health conditions and enable physicians to make prompt treatment decisions, which could improve the chances for rapid recovery and cure. Compact discs (CDs) provide inexpensive substrate materials for the preparation of microarray biochips, and conventional computer drives/disc players can be adapted as precise optical reading devices for signal processing. Researchers can employ the polycarbonate (PC) base of a CD as an alternative substrate to glass slides or silicon wafers for the preparation of microanalytical devices. Using the characteristic optical phenomena occurring on the metal layer of a CD, researchers can develop biosensors based on advanced spectroscopic readout (interferometry or surface plasmon resonance). If researchers integrate microfluidic functions with CD mechanics, they can control fluid transfer through the spinning motion of the disc, leading to "lab-on-a-CD" devices. Over the last decade, our laboratory has focused on the construction of POC biosensor devices from off-the-shelf CDs or DVDs and standard computer drives. Besides the initial studies of the suitability of CDs for surface and materials chemistry research (fabrication of self-assembled monolayers and oxide nanostructures), we have demonstrated that an ordinary optical drive, without modification of either the hardware or the software driver, can function as the signal transducing element for reading disc-based bioassays quantitatively. In this Account, we first provide a brief introduction to CD-related materials chemistry and microfluidics research. Then we describe the mild chemistry developed in our laboratory for the preparation of computer-readable biomolecular screening assays: photochemical activation of the polycarbonate (PC) disc surface and immobilization and delivery of probe and target biomolecules. We thoroughly discuss the analysis of the molecular recognition events: researchers can "read" these devices quantitatively with an unmodified optical drive of any personal computer. Finally, and critically, we illustrate our digitized molecular diagnosis approach with three trial systems: DNA hybridization, antibody-antigen binding, and ultrasensitive lead detection with a DNAzyme assay. These examples demonstrate the broad potential of this new analytical/diagnostic tool for medical screening, on-site food/water safety testing, and remote environmental monitoring.

Aminoacid N-substituted 1,4,7-triazacyclononane and 1,4,7,10-tetraazacyclododecane Zn2+, Cd2+ and Cu2+ complexes. A preparative, potentiometric titration and NMR spectroscopic study.

PubMed

Plush, Sally E; Lincoln, Stephen F; Wainwright, Kevin P

2004-05-07

The pK(a)s and Zn2+, Cd2+ and Cu2+ complexation constants (K) for 1,4,7-tris[(2''S)-acetamido-2''-(methyl-3''-phenylpropionate)]-1,4,7-triazacyclononane, 1, 1,4,7-tris[(2''S)-acetamido-2''-(1''-carboxy-3''-phenylpropane)]-1,4,7-triazacyclononane, H(3)2, 1,4,7-tris[(2''S)-acetamido-2''-(methyl-3''-(1H-3-indolyl)propionate)]-1,4,7-triazacyclononane, 3, and 1,4,7,10-tetrakis[(2''S)-acetamido-2''-(methyl-3''-phenylpropionate)]-1,4,7,10-tetraazacyclododecane, 4, 1,4,7,10-tetrakis[(2''S)-acetamido-2''-(1''-carboxy-3''-phenylpropane)]-1,4,7,10-tetraazacyclododecane, H(4)5, in 20 : 80 v/v water-methanol solution are reported. The pK(a)s within the potentiometric detection range for H(3)1(3+) = 8.69 and 3.59, for H(6)2(3+) = 9.06, 6.13, 4.93 and 4.52, H(3)3(3+) = 8.79 and 3.67, H(4)4(4+) = 8.50, 5.62 and 3.77 and for H(8)5(4+) = 9.89, 7.06, 5.53, 5.46, 4.44 and 4.26 where each tertiary amine nitrogen is protonated. The complexes of 1: [Zn(1)]2+(9.00), [Cd(1)]2+ (6.49), [Cd(H1)]3+ (4.54) and [Cu(1)]2+ (10.01) are characterized by the log(K/dm3 mol(-1)) values shown in parentheses. Analogous complexes are formed by 3 and 4: [Zn(3)]2+ (10.19), [Cd(3)]2+ (8.54), [Cu(3)]2+ (10.77), [Zn(4)]2+ (11.41) [Cd(4)]2+ (9.16), [Cd(H4)]3+ (6.16) and [Cu(4)]2+ (11.71). The tricarboxylic acid H(3)2 generates a greater variety of complexes as exemplified by: [Zn(2)-] (10.68) [Zn(H2)] (6.60) [Zn(H(2)2)+] (5.15), [Cd(2)](-) (4.99), [Cd(H2)] (4.64), [Cd(H2(2))]+ (3.99), [Cd(H(3)2)]2+ (3.55), [Cu(2)](-) (12.55) [Cu(H2)] (7.66), [Cu(H(2)2)]+ (5.54) and [Cu(2)2](4-) (3.23). The complexes of H(4)5 were insufficiently soluble to study in this way. The 1H and 13C NMR spectra of the ligands are consistent with formation of a predominant Zn2+ and Cd2+ Delta or Lambda diastereomer. The preparations of the new pendant arm macrocycles H(3)2, 3, 4 and H(4)5 are reported.

Study of electrostatically self-assembled thin films of CdS and ZnS nanoparticle semiconductors

NASA Astrophysics Data System (ADS)

Suryajaya

In this work, CdS and ZnS semiconducting colloid nanoparticles coated with organic shell, containing either SO[3-] or NH[2+] groups, were deposited as thin films using the technique of electrostatic self-assembly. The films produced were characterized with UV-vis spectroscopy and spectroscopic ellipsometry - for optical properties; atomic force microscopy (AFM) - for morphology study; mercury probe - for electrical characterisation; and photon counter - for electroluminescence study. UV-vis spectra show a substantial blue shift of the main absorption band of both CdS and ZnS, either in the form of solutions or films, with respect to the bulk materials. The calculation of nanoparticles' radii yields the value of about 1.8 nm for both CdS and ZnS.The fitting of standard ellipsometry data gave the thicknesses (d) of nanoparticle layers of around 5 nm for both CdS and ZnS which corresponds well to the size of particles evaluated from UV-vis spectral data if an additional thickness of the organic shell is taken into account. The values of refractive index (n) and extinction coefficient (k) obtained were about 2.28 and 0.7 at 633 nm wavelength, for both CdS and ZnS.Using total internal reflection (TIRE), the process of alternative deposition of poly-allylamine hydrochloride (PAH) and CdS (or ZnS) layers could be monitored in-situ. The dynamic scan shows that the adsorption kinetic of the first layer of PAH or nanoparticles was slower than that of the next layer. The fitting of TIRE spectra gavethicknesses of about 7 nm and 12 nm for CdS and ZnS, respectively. It supports the suggestion of the formation of three-dimensional aggregates of semiconductor nanoparticles intercalated with polyelectrolyte.AFM images show the formation of large aggregates of nanoparticles, about 40-50 nm, for the films deposited from original colloid solutions, while smaller aggregates, about 12-20 nm, were obtained if the colloid solutions were diluted.Current-voltage (I-V) and capacitance-frequency (C-f) measurements of polyelectrolyte/nanoparticles (CdS or ZnS) films suggest the tunnelling behaviour in the films while capacitance- voltage (C-V) and conductance-voltage (G-V) measurements suggest that these nanoparticles are conductive. The electroluminescence was detected in sandwich structures of (PAH/CdS/PAH)[N] using a photon counting detector, but not in the case of ZnS films.

Assessing the role of peripheral CD8 T cells in neurocognitive impairment in HIV-infected men who have sex with men: data from the MSM Neurocog Study.

PubMed

Rawson, T M; Dubb, S; Pozniak, A; Kelleher, W P; Mandalia, S; Gazzard, B; Barber, T J

2015-02-01

Studies have suggested CD8 lymphocytes may be a possible marker for inflammation, which is believed to be a contributing factor to neurocognitive impairment. Individuals enrolled in the MSM Neurocog Study were analysed. Those with depression, anxiety or mood disorders were excluded. Individuals with neurocognitive impairment were identified using the Brief NeuroCognitive Screen and compared to those with normal scores. CD4 and CD8 T cell values and CD4:CD8 ratios were compared between groups. In all, 144 men, aged 18-50 years, were included in the analysis. Twenty were diagnosed with neurocognitive impairment. We were unable to identify any significant difference between current, nadir or peak CD4 and CD8 counts. CD4:CD8 ratios and CD4:CD8 ratio inversion (<1) were also found to be similar between both groups. However, neurocognitive impairment subjects were 8% more likely to have inversion of CD4:CD8 ratio and higher median peak CD8 cell counts reported compared to non-impaired subjects. Analysis of data from the MSM Neurocog Study, demonstrated trends in peripheral CD8 counts and CD4:CD8 ratios. However, we are unable to demonstrate any significant benefit. Plasma biomarkers of neurocognitive impairment in HIV-infected subjects would be of great benefit over current methods of invasive CSF analysis and technical neuroimaging used in the diagnosis of neurocognitive impairment. Future, prospective, longitudinal work with large numbers of neurocognitive impairment subjects is required to further investigate the role of peripheral CD8 T cells as markers of neurocognitive impairment. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Applications of infrared photo-acoustic spectroscopy for wood samples

Treesearch

Mon-Lin Kuo; John F. McClelland; Siquan Luo; Po-Liang Chien; R.D. Walker; Chung-Yun Hse

1988-01-01

Various infrared (IR) spectroscopic techniques for the analysis of wood samples are briefly discussed. Theories and instrumentation of the newly developed photoacoustic spectroscopic (PAS) technique for measuring absorbance spectra of solids are presented. Some important applications of the PAS technique in wood science research are discussed. The application of the...

Comparative transcriptome analysis of duckweed (Landoltia punctata) in response to cadmium provides insights into molecular mechanisms underlying hyperaccumulation.

PubMed

Xu, Hua; Yu, Changjiang; Xia, Xinli; Li, Mingliang; Li, Huiguang; Wang, Yu; Wang, Shumin; Wang, Congpeng; Ma, Yubin; Zhou, Gongke

2018-01-01

Cadmium (Cd) is a detrimental environmental pollutant. Duckweeds have been considered promising candidates for Cd phytoremediation. Although many physiological studies have been conducted, the molecular mechanisms underlying Cd hyperaccumulation in duckweeds are largely unknown. In this study, clone 6001 of Landoltia punctata, which showed high Cd tolerance, was obtained by large-scale screening of over 200 duckweed clones. Subsequently, its growth, Cd flux, Cd accumulation, and Cd distribution characteristics were investigated. To further explore the global molecular mechanism, a comprehensive transcriptome analysis was performed. For RNA-Seq, samples were treated with 20 μM CdCl 2 for 0, 1, 3, and 6 days. In total, 9,461, 9,847, and 9615 differentially expressed unigenes (DEGs) were discovered between Cd-treated and control (0 day) samples. DEG clustering and enrichment analysis identified several biological processes for coping with Cd stress. Genes involved in DNA repair acted as an early response to Cd, while RNA and protein metabolism would be likely to respond as well. Furthermore, the carbohydrate metabolic flux tended to be modulated in response to Cd stress, and upregulated genes involved in sulfur and ROS metabolism might cause high Cd tolerance. Vacuolar sequestration most likely played an important role in Cd detoxification in L. punctata 6001. These novel findings provided important clues for molecular assisted screening and breeding of Cd hyperaccumulating cultivars for phytoremediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Urea-temperature phase diagrams capture the thermodynamics of denatured state expansion that accompany protein unfolding

PubMed Central

Tischer, Alexander; Auton, Matthew

2013-01-01

We have analyzed the thermodynamic properties of the von Willebrand factor (VWF) A3 domain using urea-induced unfolding at variable temperature and thermal unfolding at variable urea concentrations to generate a phase diagram that quantitatively describes the equilibrium between native and denatured states. From this analysis, we were able to determine consistent thermodynamic parameters with various spectroscopic and calorimetric methods that define the urea–temperature parameter plane from cold denaturation to heat denaturation. Urea and thermal denaturation are experimentally reversible and independent of the thermal scan rate indicating that all transitions are at equilibrium and the van't Hoff and calorimetric enthalpies obtained from analysis of individual thermal transitions are equivalent demonstrating two-state character. Global analysis of the urea–temperature phase diagram results in a significantly higher enthalpy of unfolding than obtained from analysis of individual thermal transitions and significant cross correlations describing the urea dependence of and that define a complex temperature dependence of the m-value. Circular dichroism (CD) spectroscopy illustrates a large increase in secondary structure content of the urea-denatured state as temperature increases and a loss of secondary structure in the thermally denatured state upon addition of urea. These structural changes in the denatured ensemble make up ∼40% of the total ellipticity change indicating a highly compact thermally denatured state. The difference between the thermodynamic parameters obtained from phase diagram analysis and those obtained from analysis of individual thermal transitions illustrates that phase diagrams capture both contributions to unfolding and denatured state expansion and by comparison are able to decipher these contributions. PMID:23813497

Method and apparatus for scientific analysis under low temperature vacuum conditions

DOEpatents

Winefordner, James D.; Jones, Bradley T.

1990-01-01

A method and apparatus for scientific analysis of a sample under low temperature vacuum conditions uses a vacuum chamber with a conveyor belt disposed therein. One end of the conveyor belt is a cool end in thermal contact with the cold stage of a refrigerator, whereas the other end of the conveyor belt is a warm end spaced from the refrigerator. A septum allows injection of a sample into the vacuum chamber on top of the conveyor belt for spectroscopic or other analysis. The sample freezes on the conveyor belt at the cold end. One or more windows in the vacuum chamber housing allow spectroscopic analysis of the sample. Following the spectroscopic analysis, the conveyor belt may be moved such that the sample moves toward the warm end of the conveyor belt where upon it evaporates, thereby cleaning the conveyor belt. Instead of injecting the sample by way of a septum and use of a syringe and needle, the present device may be used in series with capillary-column gas chromatography or micro-bore high performance liquid chromatography.

Selenium supplementation prevents metabolic and transcriptomic responses to cadmium in mouse lung.

PubMed

Hu, Xin; Chandler, Joshua D; Fernandes, Jolyn; Orr, Michael L; Hao, Li; Uppal, Karan; Neujahr, David C; Jones, Dean P; Go, Young-Mi

2018-04-12

The protective effect of selenium (Se) on cadmium (Cd) toxicity is well documented, but underlying mechanisms are unclear. Male mice fed standard diet were given Cd (CdCl 2 , 18 μmol/L) in drinking water with or without Se (Na 2 SeO 4, 20 μmol/L) for 16 weeks. Lungs were analyzed for Cd concentration, transcriptomics and metabolomics. Data were analyzed with biostatistics, bioinformatics, pathway enrichment analysis, and combined transcriptome-metabolome-wide association study. Mice treated with Cd had higher lung Cd content (1.7 ± 0.4 pmol/mg protein) than control mice (0.8 ± 0.3 pmol/mg protein) or mice treated with Cd and Se (0.4 ± 0.1 pmol/mg protein). Gene set enrichment analysis of transcriptomics data showed that Se prevented Cd effects on inflammatory and myogenesis genes and diminished Cd effects on several other pathways. Similarly, Se prevented Cd-disrupted metabolic pathways in amino acid metabolism and urea cycle. Integrated transcriptome and metabolome network analysis showed that Cd treatment had a network structure with fewer gene-metabolite clusters compared to control. Centrality measurements showed that Se counteracted changes in a group of Cd-responsive genes including Zdhhc11, (protein-cysteine S-palmitoyltransferase), Ighg1 (immunoglobulin heavy constant gamma-1) and associated changes in metabolite concentrations. Co-administration of Se with Cd prevented Cd increase in lung and prevented Cd-associated pathway and network responses of the transcriptome and metabolome. Se protection against Cd toxicity in lung involves complex systems responses. Environmental Cd stimulates proinflammatory and profibrotic signaling. The present results indicate that dietary or supplemental Se could be useful to mitigate Cd toxicity. Published by Elsevier B.V.

A novel natural killer cell line (KHYG-1) from a patient with aggressive natural killer cell leukemia carrying a p53 point mutation.

PubMed

Yagita, M; Huang, C L; Umehara, H; Matsuo, Y; Tabata, R; Miyake, M; Konaka, Y; Takatsuki, K

2000-05-01

We present the establishment of a natural killer (NK) leukemia cell line, designated KHYG-1, from the blood of a patient with aggressive NK leukemia, which both possessed the same p53 point mutation. The immunophenotype of the primary leukemia cells was CD2+, surface CD3-, cytoplasmic CD3epsilon+, CD7+, CD8alphaalpha+, CD16+, CD56+, CD57+ and HLA-DR+. A new cell line (KHYG-1) was established by culturing peripheral leukemia cells with 100 units of recombinant interleukin (IL)-2. The KHYG-1 cells showed LGL morphology with a large nucleus, coarse chromatin, conspicuous nucleoli, and abundant basophilic cytoplasm with many azurophilic granules. The immunophenotype of KHYG-1 cells was CD1-, CD2+, surface CD3-, cytoplasmic CD3epsilon+, CD7+, CD8alphaalpha+, CD16-, CD25-, CD33+, CD34-, CD56+, CD57-, CD122+, CD132+, and TdT-. Southern blot analysis of these cells revealed a normal germline configuration for the beta, delta, and gamma chains of the T cell receptor and the immunoglobulin heavy-chain genes. Moreover, the KHYG-1 cells displayed NK cell activity and IL-2-dependent proliferation in vitro, suggesting that they are of NK cell origin. Epstein-Barr virus (EBV) DNA was not detected in KHYG-1 cells by Southern blot analysis with a terminal repeat probe from an EBV genome. A point mutation in exon 7 of the p53 gene was detected in the KHYG-1 cells by PCR/SSCP analysis, and direct sequencing revealed the conversion of C to T at nucleotide 877 in codon 248. The primary leukemia cells also carried the same point mutation. Although the precise role of the p53 point mutation in leukemogenesis remains to be clarified, the establishment of an NK leukemia cell line with a p53 point mutation could be valuable in the study of leukemogenesis.

Gas Analysis Using Auroral Spectroscopy.

NASA Astrophysics Data System (ADS)

Alozie, M.; Thomas, G.; Medillin, M.

2017-12-01

As part of the Undergraduate Student Instrumentation Project at the University of Houston, an Auroral spectroscope was designed and built. This visible light spectroscope was constructed out of carbon fiber, aluminum, and 3D printed parts. The spectroscope was designed to calculate the wavelengths of the spectral lines and analyze the emitted light spectrum of the gases. The spectroscope contains a primary parabolic 6" mirror and a smaller secondary 2.46" mirror. The light captured through these mirrors will be guided to an optical train that consist of five lenses (1" in diameter and focal length), a slit, and a visible transmission grating. The light will then be led to a Sony Alpha A6000 camera to take images of the spectral lines.

Neutron Spectroscopic Factors from Transfer Reactions

NASA Astrophysics Data System (ADS)

Lee, Jenny; Tsang, M. B.

2007-05-01

We have extracted the ground state to ground state neutron spectroscopic factors for 80 nuclei ranging in Z from 3 to 24 by analyzing the past measurements of the angular distributions from (d,p) and (p,d) reactions. We demonstrate an approach that provides systematic and consistent values with a minimum of assumptions. A three-body model with global optical potentials and standard geometry of n-potential is applied. For the 60 nuclei where modern shell model calculations are available, such analysis reproduces, to within 20%, the experimental spectroscopic factors for most nuclei. If we constraint the nucleon-target optical potential and the geometries of the bound neutron-wave function with the modern Hartree-Fock calculations, our deduced neutron spectroscopic factors are reduced by 30% on average.

T.D.S. spectroscopic databank for spherical tops: DOS version

NASA Astrophysics Data System (ADS)

Tyuterev, V. G.; Babikov, Yu. L.; Tashkun, S. A.; Perevalov, V. I.; Nikitin, A.; Champion, J.-P.; Wenger, C.; Pierre, C.; Pierre, G.; Hilico, J.-C.; Loete, M.

1994-10-01

T.D.S. (Traitement de Donnees Spectroscopiques or Tomsk-Dijon-Spectroscopy project) is a computer package concerned with high resolution spectroscopy of spherical top molecules like CH4, CF4, SiH4, SiF4, SnH4, GeH4, SF6, etc. T.D.S. contains information, fundamental spectroscopic data (energies, transition moments, spectroscopic constants) recovered from comprehensive modeling and simultaneous fitting of experimental spectra, and associated software written in C. The T.D.S. goal is to provide an access to all available information on vibration-rotation molecular states and transitions including various spectroscopic processes (Stark, Raman, etc.) under extended conditions based on extrapolations of laboratory measurements using validated theoretical models. Applications for T.D.S. may include: education/training in molecular physics, quantum chemistry, laser physics; spectroscopic applications (analysis, laser spectroscopy, atmospheric optics, optical standards, spectroscopic atlases); applications to environment studies and atmospheric physics (remote sensing); data supply for specific databases; and to photochemistry (laser excitation, multiphoton processes). The reported DOS-version is designed for IBM and compatible personal computers.

Spectroscopic and Photometric Survey of Northern Sky for the ESA PLATO space mission

NASA Astrophysics Data System (ADS)

Ženovienė, Renata; Bagdonas, Vilius; Drazdauskas, Arnas; Janulis, Rimvydas; Klebonas, Lukas; Mikolaitis, Šarūnas; Pakštienė, Erika; Tautvaišienė, Gražina

2018-04-01

The ESA-PLATO 2.0 mission will perform an in-depth analysis of the large part of the sky-sphere searching for extraterrestrial telluric-like planets. At the Molėtai Astronomical Observatory of Vilnius University, we started a spectroscopic and photometric survey of the northern sky fields that potentially will be targeted by the PLATO mission. We aim to contribute in developing the PLATO input catalogue by delivering a long-duration stellar variability information and a full spectroscopic characterization of brightest targets. First results of this survey are overviewed.

Intravascular Raman spectroscopic catheter for molecular diagnosis of atherosclerotic coronary disease

NASA Astrophysics Data System (ADS)

Komachi, Yuichi; Sato, Hidetoshi; Tashiro, Hideo

2006-10-01

An intravascular catheter for Raman spectroscopic detection and analysis of coronary atherosclerotic disease has been developed. The catheter, having an outer diameter of 2 mm, consisted of a side-view-type micro-Raman probe, an imaging fiber bundle, a working channel (injection drain), and a balloon. By inflating the balloon, the probe was brought close to the inner wall of a modeled blood flow system and detected a phantom target buried in the wall. Results obtained demonstrate the possibility of using the spectroscopic catheter for molecular diagnosis of coronary lesions.

Application of a new non-linear least squares velocity curve analysis technique for spectroscopic binary stars

NASA Astrophysics Data System (ADS)

Karami, K.; Mohebi, R.; Soltanzadeh, M. M.

2008-11-01

Using measured radial velocity data of nine double lined spectroscopic binary systems NSV 223, AB And, V2082 Cyg, HS Her, V918 Her, BV Dra, BW Dra, V2357 Oph, and YZ Cas, we find corresponding orbital and spectroscopic elements via the method introduced by Karami and Mohebi (Chin. J. Astron. Astrophys. 7:558, 2007a) and Karami and Teimoorinia (Astrophys. Space Sci. 311:435, 2007). Our numerical results are in good agreement with those obtained by others using more traditional methods.

Infrared spectroscopic imaging for noninvasive detection of latent fingerprints.

PubMed

Crane, Nicole J; Bartick, Edward G; Perlman, Rebecca Schwartz; Huffman, Scott

2007-01-01

The capability of Fourier transform infrared (FTIR) spectroscopic imaging to provide detailed images of unprocessed latent fingerprints while also preserving important trace evidence is demonstrated. Unprocessed fingerprints were developed on various porous and nonporous substrates. Data-processing methods used to extract the latent fingerprint ridge pattern from the background material included basic infrared spectroscopic band intensities, addition and subtraction of band intensity measurements, principal components analysis (PCA) and calculation of second derivative band intensities, as well as combinations of these various techniques. Additionally, trace evidence within the fingerprints was recovered and identified.

The origin, composition and history of cometary ices from spectroscopic studies

NASA Technical Reports Server (NTRS)

Allamandola, L. J.

1989-01-01

The spectroscopic analysis of pristine cometary material provides a very important probe of the chemical identity of the material as well as of the physical and chemical conditions which prevailed during the comet's history. Concerning classical spectroscopy, the spectral regions which will most likely prove most useful are the infrared, the visible and ultraviolet. Newer spectroscopic techniques which have the potential to provide equally important information include nuclear magnetic resonance (NMR) and electron spin resonance (ESR). Each technique is summarized with emphasis placed on the kind of information which can be obtained.

Characterization of interaction between esculin and human serum albumin in membrane mimetic environments

NASA Astrophysics Data System (ADS)

Zhang, Yaheng; Li, Jiazhong; Dong, Lijun; Li, Ying; Chen, Xingguo

2008-10-01

In this study the interaction between esculin and human serum albumin (HSA) in AOT/isooctane/water microemulsions was studied for the first time using fluorescence quenching technique in combination with UV absorption spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, circular dichroism (CD) spectroscopy and dynamic light scattering (DLS) technique. Fluorescence data in ω o 20 microemulsions revealed the presence of the binding site of esculin on HSA and its binding constants at four different temperatures were obtained. The affinities in microemulsions are similar to that in buffer solution. The alterations of protein secondary structure in the microemulsions in the absence and presence of esculin compared with the free form of HSA in buffer were qualitatively and quantitatively analyzed by the evidence from CD and FT-IR spectroscopes. The displacement experiments confirmed that esculin could bind to the site I of HSA, which was in agreement with the result of the molecular modeling study. Furthermore, the DLS data suggested that HSA may locate at the interface of the microemulsion and esculin could interact with them.

A flexible 1,8-naphthyridyl derivative and its Zn(II) complexes: synthesis, structures, spectroscopic properties and recognition of Cd(II).

PubMed

Zhang, Hui-Miao; Fu, Wen-Fu; Gan, Xin; Xu, Yan-Qing; Wang, Jun; Xu, Quan-Qing; Chi, Shao-Ming

2008-12-21

A flexible ligand bis(7-methyl-1,8-naphthyridine-2-ylamino)methane (), having kappa(4)-chelating and kappa(2)-bridging modes, and its intriguing structural complexes of Zn(II) with mu-OH, kappa(1)-OAc, mu-kappa(1)-OAc and mu-kappa(2)-OAc ligands, [Zn(2)()(2)(OH)](ClO(4))(3) (), [Zn(4)()(2)(OAc)(6)(OH)(2)].CH(2)Cl(2) (.CH(2)Cl(2)) and [Zn(5)()(2)(OAc)(10)](n).4nH(2)O (.4H(2)O) were synthesized and their structures were determined by X-ray crystallography. These compounds exhibited intense blue fluorescent emissions with a lambda(max) in the range of 380-410 nm in CH(2)Cl(2), CH(3)CN and CH(3)OH solutions, and solid-state emissions centered at 416, 463, 490 and 451 nm were observed for the compounds , , and at room temperature, respectively. The investigated fluorescence properties of associated with various metal ions showed that the fluorescence enhancement of with Cd(II) was more sensitive than with other interfering cations.

Probing the stereoselective interaction of ofloxacin enantiomers with corresponding monoclonal antibodies by multiple spectrometry

NASA Astrophysics Data System (ADS)

Mu, Hongtao; Xu, Zhenlin; Liu, Yingju; Sun, Yuanming; Wang, Baoling; Sun, Xiulan; Wang, Zhanhui; Eremin, Sergei; Zherdev, Anatoly V.; Dzantiev, Boris B.; Lei, Hongtao

2018-04-01

Although stereoselective antibody has immense potential in chiral compounds detection and separation, the interaction traits between stereoselective antibody and the corresponding antigenic enantiomers are not yet fully exploited. In this study, the stereospecific interactions between ofloxacin isomers and corresponding monoclonal antibodies (McAb-WR1 and McAb-MS1) were investigated using time-resolved fluorescence, steady-state fluorescence, and circular dichroism (CD) spectroscopic methods. The chiral recognition discrepancies of antibodies with ofloxacin isomers were reflected through binding constant, number of binding sites, driving forces and conformational changes. The major interacting forces of McAb-WR1 and McAb-MS1 chiral interaction systems were hydrophobic force and van der Waals forces joined up with hydrogen bonds, respectively. Synchronous fluorescence spectra and CD spectra results showed that the disturbing of tyrosine and tryptophan micro-environments were so slightly that no obvious secondary structure changes were found during the chiral hapten binding. Clarification of stereospecific interaction of antibody will facilitate the application of immunoassay to analyze chiral contaminants in food and other areas.

Direct Observation of Photoexcited Hole Localization in CdSe Nanorods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ye; Wu, Kaifeng; Shabaev, Andrew

Quantum-confined 1D semiconductor nanostructures are being investigated for hydrogen generation photocatalysts. In the photoreaction, after fast electron transfer, holes that remain in the nanostructure play an important role in the total quantum yield of hydrogen production. Unfortunately, knowledge of hole dynamics is limited due to lack of convenient spectroscopic signatures. Here, we directly probe hole localization dynamics within CdSe nanorods (NRs) by combining transient absorption (TA) and time-resolved terahertz (TRTS) spectroscopy. We show that when methylene blue is used as an electron acceptor, the resulting electron transfer occurs with a time constant of 3.5 +/- 0.1 ps and leaves behindmore » a delocalized hole. However, the hole quickly localizes in the Coulomb potential well generated by the reduced electron acceptor near the NR surface with time constant of 11.7 +/- 0.2 ps. Our theoretical investigation suggests that the hole becomes confined to a ~ +/-0.8 nm region near the reduced electron acceptor and the activation energy to detrap the hole from the potential well can be as large as 235 meV.« less

Spectroscopic studies on the interaction of chromium (VI) and chromium (III) with keyhole limpet hemocyanin.

PubMed

Fan, Yulan; Zeng, Guidi; Liu, Jingyi; Chen, Huifang; Xue, Jun; Wu, Yongquan; Li, Xun

2017-03-01

The interactions of keyhole limpet hemocyanin (KLH) with chromium nitrate, potassium dichromate, and chromate were investigated using fluorescence, UV-vis absorption and circular dichroism (CD) spectroscopy under simulated physiological conditions. The experimental results showed that the different forms of chromium could quench the intrinsic fluorescence of KLH following a static quenching mechanism rather than by dynamic collision, which indicated that a Cr-KLH complex was formed. The Stern-Volmer quenching constants for the interaction indicated that the binding reaction of KLH with Cr(VI) was stronger the binding of KLH with Cr(III). The thermodynamic values for binding of Cr(VI) to KLH are ΔH > 0 and ΔS > 0. By contrast, the values for the interaction of Cr(III) with KLH are ΔH < 0 and ΔS < 0. The results of synchronous fluorescence, UV-vis absorption and CD spectroscopy showed that the α-helical secondary structure and conformation of KLH were altered by different forms of chromium. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

White/blue-emitting, water-dispersible CdSe quantum dots prepared by counter ion-induced polymer collapse

NASA Astrophysics Data System (ADS)

Wang, Jing; Goh, Jane Betty; Goh, M. Cynthia; Giri, Neeraj Kumar; Paige, Matthew F.

2015-09-01

The synthesis and characterization of water-dispersible, luminescent CdSe/ZnS semiconductor quantum dots that exhibit nominal "white" fluorescence emission and have potential applications in solid-state lighting is described. The nanomaterials, prepared through counter ion-induced collapse and UV cross-linking of high-molecular weight polyacrylic acid in the presence of appropriate aqueous inorganic ions, were of ∼2-3 nm diameter and could be prepared in gram quantities. The quantum dots exhibited strong luminescence emission in two bands, the first in the blue-region (band edge) of the optical spectrum and the second, a broad emission in the red-region (attributed to deep trap states) of the optical spectrum. Because of the relative strength of emission of the band edge and deep trap state luminescence, it was possible to achieve visible white luminescence from the quantum dots in aqueous solution and in dried, solid films. The optical spectroscopic properties of the nanomaterials, including ensemble and single-molecule spectroscopy, was performed, with results compared to other white-emitting quantum dot systems described previously in the literature.

Uptake of bright fluorophore core-silica shell nanoparticles by biological systems

PubMed Central

Zane, Andrew; McCracken, Christie; Knight, Deborah A; Young, Tanya; Lutton, Anthony D; Olesik, John W; Waldman, W James; Dutta, Prabir K

2015-01-01

Nanoparticles are used in a variety of consumer applications. Silica nanoparticles in particular are common, including as a component of foods. There are concerns that ingested nano-silica particles can cross the intestinal epithelium, enter the circulation, and accumulate in tissues and organs. Thus, tracking these particles is of interest, and fluorescence spectroscopic methods are well-suited for this purpose. However, nanosilica is not fluorescent. In this article, we focus on core-silica shell nanoparticles, using fluorescent Rhodamine 6G, Rhodamine 800, or CdSe/CdS/ZnS quantum dots as the core. These stable fluorophore/silica nanoparticles had surface characteristics similar to those of commercial silica particles. Thus, they were used as model particles to examine internalization by cultured cells, including an epithelial cell line relevant to the gastrointestinal tract. Finally, these particles were administered to mice by gavage, and their presence in various organs, including stomach, small intestine, cecum, colon, kidney, lung, brain, and spleen, was examined. By combining confocal fluorescence microscopy with inductively coupled plasma mass spectrometry, the presence of nanoparticles, rather than their dissolved form, was established in liver tissues. PMID:25759579

Caliste 64, a new CdTe micro-camera for hard X-ray spectro-imaging

NASA Astrophysics Data System (ADS)

Meuris, A.; Limousin, O.; Lugiez, F.; Gevin, O.; Blondel, C.; Pinsard, F.; Vassal, M. C.; Soufflet, F.; Le Mer, I.

2009-10-01

In the frame of the Simbol-X mission of hard X-ray astrophysics, a prototype of micro-camera with 64 pixels called Caliste 64 has been designed and several samples have been tested. The device integrates ultra-low-noise IDeF-X V1.1 ASICs from CEA and a 1 cm 2 Al Schottky CdTe detector from Acrorad because of its high uniformity and spectroscopic performance. The process of hybridization, mastered by the 3D Plus company, respects space applications standards. The camera is a spectro-imager with time-tagging capability. Each photon interacting in the semiconductor is tagged with a time, a position and an energy. Time resolution is better than 100 ns rms for energy deposits greater than 20 keV, taking into account electronic noise and technological dispersal of the front-end electronics. The spectrum summed across the 64 pixels results in an energy resolution of 664 eV fwhm at 13.94 keV and 842 eV fwhm at 59.54 keV, when the detector is cooled down to -10 °C and biased at -500 V.

Monitoring nonenzymatic glycation of human immunoglobulin G by methylglyoxal and glyoxal: A spectroscopic study.

PubMed

Pampati, Praveen K; Suravajjala, Sreekanth; Dain, Joel A

2011-01-01

The accumulation of dicarbonyl compounds, methylglyoxal (MG) and glyoxal (G), has been observed in diabetic conditions. They are formed from nonoxidative mechanisms in anaerobic glycolysis and lipid peroxidation, and they act as advanced glycation endproduct (AGE) precursors. The objective of this study was to monitor and characterize the AGE formation of human immunoglobulin G (hIgG) by MG and G using ultraviolet (UV) and fluorescence spectroscopy, circular dichroism (CD), and matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS). hIgG was incubated over time with MG and G at different concentrations. Formation of AGE was monitored by UV and fluorescence spectroscopy. The effect of AGE formation on secondary structure of hIgG was studied by CD. Comparison of AGE profile for MG and G was performed by MALDI-MS. Both MG and G formed AGE, with MG being nearly twice as reactive as G. The combination of these techniques is a convenient method for evaluating and characterizing the AGE proteins. Copyright © 2010 Elsevier Inc. All rights reserved.

Development of CD3 cell quantitation algorithms for renal allograft biopsy rejection assessment utilizing open source image analysis software.

PubMed

Moon, Andres; Smith, Geoffrey H; Kong, Jun; Rogers, Thomas E; Ellis, Carla L; Farris, Alton B Brad

2018-02-01

Renal allograft rejection diagnosis depends on assessment of parameters such as interstitial inflammation; however, studies have shown interobserver variability regarding interstitial inflammation assessment. Since automated image analysis quantitation can be reproducible, we devised customized analysis methods for CD3+ T-cell staining density as a measure of rejection severity and compared them with established commercial methods along with visual assessment. Renal biopsy CD3 immunohistochemistry slides (n = 45), including renal allografts with various degrees of acute cellular rejection (ACR) were scanned for whole slide images (WSIs). Inflammation was quantitated in the WSIs using pathologist visual assessment, commercial algorithms (Aperio nuclear algorithm for CD3+ cells/mm 2 and Aperio positive pixel count algorithm), and customized open source algorithms developed in ImageJ with thresholding/positive pixel counting (custom CD3+%) and identification of pixels fulfilling "maxima" criteria for CD3 expression (custom CD3+ cells/mm 2 ). Based on visual inspections of "markup" images, CD3 quantitation algorithms produced adequate accuracy. Additionally, CD3 quantitation algorithms correlated between each other and also with visual assessment in a statistically significant manner (r = 0.44 to 0.94, p = 0.003 to < 0.0001). Methods for assessing inflammation suggested a progression through the tubulointerstitial ACR grades, with statistically different results in borderline versus other ACR types, in all but the custom methods. Assessment of CD3-stained slides using various open source image analysis algorithms presents salient correlations with established methods of CD3 quantitation. These analysis techniques are promising and highly customizable, providing a form of on-slide "flow cytometry" that can facilitate additional diagnostic accuracy in tissue-based assessments.

Spectroscopic investigations on the effect of N-Acetyl-L-cysteine-Capped CdTe Quantum Dots on catalase

NASA Astrophysics Data System (ADS)

Sun, Haoyu; Yang, Bingjun; Cui, Erqian; Liu, Rutao

2014-11-01

Quantum dots (QDs) are recognized as some of the most promising semiconductor nanocrystals in biomedical applications. However, the potential toxicity of QDs has aroused wide public concern. Catalase (CAT) is a common enzyme in animal and plant tissues. For the potential application of QDs in vivo, it is important to investigate the interaction of QDs with CAT. In this work, the effect of N-Acetyl-L-cysteine-Capped CdTe Quantum Dots with fluorescence emission peak at 612 nm (QDs-612) on CAT was investigated by fluorescence, synchronous fluorescence, fluorescence lifetime, ultraviolet-visible (UV-vis) absorption and circular dichroism (CD) techniques. Binding of QDs-612 to CAT caused static quenching of the fluorescence, the change of the secondary structure of CAT and the alteration of the microenvironment of tryptophan residues. The association constants K were determined to be K288K = 7.98 × 105 L mol-1 and K298K = 7.21 × 105 L mol-1. The interaction between QDs-612 and CAT was spontaneous with 1:1 stoichiometry approximately. The CAT activity was also inhibited for the bound QDs-612. This work provides direct evidence about enzyme toxicity of QDs-612 to CAT in vitro and establishes a new strategy to investigate the interaction between enzyme and QDs at a molecular level, which is helpful for clarifying the bioactivities of QDs in vivo.

Adsorption of biometals to monosodium titanate in biological environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

HOBBS, D.T.; MESSER, R. L. W.; LEWIS, J. B.

2005-06-06

Monosodium titanate (MST) is an inorganic sorbent/ion exchanger developed for the removal of radionuclides from nuclear wastes. We investigated the ability of MST to bind Cd(II), Hg(II), or Au(III) to establish the utility of MST for applications in environmental decontamination or medical therapy (drug delivery). Adsorption isotherms for MST were determined at pH 7-7.5 in water or phosphate-buffered saline. The extent of metal binding was determined spectroscopically by measuring the concentrations of the metals in solution before and after contact with the MST. Cytotoxic responses to MST were assessed using THP1 monocytes and succinate dehydrogenase activity. Monocytic activation by MSTmore » was assessed by TNF{alpha} secretion (ELISA) with or without lipopolysaccharide (LPS) activation. MST sorbed Cd(II), Hg(II), and Au(III) under conditions similar to that in physiological systems. MST exhibited the highest affinity for Cd(II) followed by Hg(II) and Au (III). MST (up to 100 mg/L) exhibited only minor (< 25% suppression of succinate dehydrogenase) cytotoxicity and did not trigger TNF{alpha} secretion nor modulate LPS-induced TNF{alpha} secretion from monocytes. MST exhibits high affinity for biometals with no significant biological liabilities in these introductory studies. MST deserves further scrutiny as a substance with the capacity to decontaminate biological environments or deliver metals in a controlled fashion.« less

Cyclodextrin-insulin complex encapsulated polymethacrylic acid based nanoparticles for oral insulin delivery.

PubMed

Sajeesh, S; Sharma, Chandra P

2006-11-15

Present investigation was aimed at developing an oral insulin delivery system based on hydroxypropyl beta cyclodextrin-insulin (HPbetaCD-I) complex encapsulated polymethacrylic acid-chitosan-polyether (polyethylene glycol-polypropylene glycol copolymer) (PMCP) nanoparticles. Nanoparticles were prepared by the free radical polymerization of methacrylic acid in presence of chitosan and polyether in a solvent/surfactant free medium. Dynamic light scattering (DLS) experiment was conducted with particles dispersed in phosphate buffer (pH 7.4) and size distribution curve was observed in the range of 500-800 nm. HPbetaCD was used to prepare non-covalent inclusion complex with insulin and complex was analyzed by Fourier transform infrared (FTIR) and fluorescence spectroscopic studies. HPbetaCD complexed insulin was encapsulated into PMCP nanoparticles by diffusion filling method and their in vitro release profile was evaluated at acidic/alkaline pH. PMCP nanoparticles displayed good insulin encapsulation efficiency and release profile was largely dependent on the pH of the medium. Enzyme linked immunosorbent assay (ELISA) study demonstrated that insulin encapsulated inside the particles was biologically active. Trypsin inhibitory effect of PMCP nanoparticles was evaluated using N-alpha-benzoyl-L-arginine ethyl ester (BAEE) and casein as substrates. Mucoadhesive studies of PMCP nanoparticles were conducted using freshly excised rat intestinal mucosa and the particles were found fairly adhesive. From the preliminary studies, cyclodextrin complexed insulin encapsulated mucoadhesive nanoparticles appear to be a good candidate for oral insulin delivery.

Recovery of Active and Efficient Photocatalytic H 2 Production for CdSe Quantum Dots

DOE PAGES

Burke, Rebeckah; Cogan, Nicole M. Briglio; Oi, Aidan; ...

2018-05-07

Recently, colloidal semiconductor quantum dots (QDs) have shown great promise as photocatalysts for the production of chemical fuels by sunlight. Here, the efficiency of photocatalytic hydrogen (H 2) production for integrated systems of large diameter (4.4 nm) CdSe QDs as light harvesting nanoparticles with varying concentrations of nickel-dihydrolipoic acid (Ni-DHLA) small molecule catalysts was measured. While exhibiting excellent robustness and longevity, the efficiency of H 2 production for equimolar catalyst and QDs was relatively poor. However, the efficiency was found to increase substantially with increasing Ni-DHLA:QD molar ratios Surprisingly, this high activity was only observed with the use of 3-mercaptopropionicmore » acid (MPA) ligands, while CdSe QDs capped with dihydrolipoic acid (DHLA) exhibited poor performance in comparison, indicating that the QD capping ligand has a substantial impact on the catalytic performance. Finally, ultrafast transient absorption spectroscopic measurements of the electron transfer (ET) dynamics show fast ET to the catalyst. Importantly, an increase in ET efficiency is observed as the catalyst concentration is increased. Together, these results suggest that for these large QDs, tailoring the QD surface environment for facile ET and increasing catalyst concentrations increases the probability of ET from QDs to Ni-DHLA, overcoming the relatively small driving force for ET and decreased surface electron density for large diameter QDs.« less

Recovery of Active and Efficient Photocatalytic H 2 Production for CdSe Quantum Dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burke, Rebeckah; Cogan, Nicole M. Briglio; Oi, Aidan

Recently, colloidal semiconductor quantum dots (QDs) have shown great promise as photocatalysts for the production of chemical fuels by sunlight. Here, the efficiency of photocatalytic hydrogen (H 2) production for integrated systems of large diameter (4.4 nm) CdSe QDs as light harvesting nanoparticles with varying concentrations of nickel-dihydrolipoic acid (Ni-DHLA) small molecule catalysts was measured. While exhibiting excellent robustness and longevity, the efficiency of H 2 production for equimolar catalyst and QDs was relatively poor. However, the efficiency was found to increase substantially with increasing Ni-DHLA:QD molar ratios Surprisingly, this high activity was only observed with the use of 3-mercaptopropionicmore » acid (MPA) ligands, while CdSe QDs capped with dihydrolipoic acid (DHLA) exhibited poor performance in comparison, indicating that the QD capping ligand has a substantial impact on the catalytic performance. Finally, ultrafast transient absorption spectroscopic measurements of the electron transfer (ET) dynamics show fast ET to the catalyst. Importantly, an increase in ET efficiency is observed as the catalyst concentration is increased. Together, these results suggest that for these large QDs, tailoring the QD surface environment for facile ET and increasing catalyst concentrations increases the probability of ET from QDs to Ni-DHLA, overcoming the relatively small driving force for ET and decreased surface electron density for large diameter QDs.« less

A survey for pulsations in A-type stars using SuperWASP

NASA Astrophysics Data System (ADS)

Holdsworth, Daniel L.

2015-12-01

"It is sound judgement to hope that in the not too distant future we shall be competent to understand so simple a thing as a star." - Sir Arthur Stanley Eddington, The Internal Constitution of Stars, 1926 A survey of A-type stars is conducted with the SuperWASP archive in the search for pulsationally variable stars. Over 1.5 million stars are selected based on their (J-H) colour. Periodograms are calculated for light curves which have been extracted from the archive and cleaned of spurious points. Peaks which have amplitudes greater than 0.5 millimagnitude are identified in the periodograms. In total, 202 656 stars are identified to show variability in the range 5-300 c/d. Spectroscopic follow-up was obtained for 38 stars which showed high-frequency pulsations between 60 and 235 c/d, and a further object with variability at 636 c/d. In this sample, 13 were identified to be normal A-type δ Sct stars, 14 to be pulsating metallic-lined Am stars, 11 to be rapidly oscillating Ap (roAp) stars, and one to be a subdwarf B variable star. The spectra were used not only to classify the stars, but to determine an effective temperature through Balmer line fitting. Hybrid stars have been identified in this study, which show pulsations in both the high- and low-overtone domains; an observation not predicted by theory. These stars are prime targets to perform follow-up observations, as a confirmed detection of this phenomenon will have significant impact on the theory of pulsations in A-type stars. The detected number of roAp stars has expanded the known number of this pulsator class by 22 per cent. Within these results both the hottest and coolest roAp star have been identified. Further to this, one object, KIC 7582608, was observed by the Kepler telescope for 4 yr, enabling a detailed frequency analysis. This analysis has identified significant frequency variations in this star, leading to the hypothesis that this is the first close binary star of its type. The observational results presented in this thesis are able to present new challenges to the theory of pulsations in A-type stars, with potentially having the effect of further delaying the full understanding of 'so simple a thing as a star'.

On the advancement of quantum dot solar cell performance through enhanced charge carrier dynamics

NASA Astrophysics Data System (ADS)

Baker, David R.

The quantum dot solar cell is one of the few solar technologies which promises to compete with fossil fuels, but work is still needed to increase its performance. Electron transfer kinetics at interfaces and limitations of the redox couple within the cell, are responsible for lowering power conversion efficiency. Several techniques which are able to increase electron transfer within the working electrode and at the counter electrode/electrolyte interface are discussed in this dissertation. Trap sites on the surface of CdSe quantum dots are created when mercaptopropionic acid (MPA) is added to the suspension. The trap sites are emissive creating a loss pathway for photogenerated charges which will manifest as reduced photocurrent. MPA displaces amines on the surface of CdSe creating Se vacancies. Emission properties are controlled by the concentration of MPA. Because trap sites are generated, a more successful method to sensitize TiO2 films is the SILAR technique which directly grows quantum dots on the desired surface. Anodically etched TiO2 nanotubes yield photocurrents 20% greater than TiO2 nanoparticles because of longer electron diffusion lengths. Peak incident photon to charge carrier efficiencies of TiO2 nanotube samples show a doubling of photocurrent in the visible region compared to nanoparticles. The TiO2 substrates are sensitized with CdS by the SILAR process which is found to utilize both the inside and outside surfaces of the TiO2 nanotubes. Etched TiO2 nanotubes are removed from the underlying titanium foil in order to use spectroscopic techniques. Ultrafast transient absorption shows the extremely fast nature of charge injection from SILAR CdS into TiO 2 nanotubes. Surface area analysis of TiO2 nanotube powder gives an area of 77m2/g, a value 1.5 times larger than traditional TiO2 nanoparticles. By isolating the counter electrode with a salt bridge the effect of the polysulfide electrolyte is found to act as an electron scavenger on the working electrode. Though activity at the platinum counter electrode increases with the presence of polysulfides, the activity is too low to counteract scavenging at the working electrode. Cu2S, CoS and PbS electrochemically show promise as alternatives to platinum. Cu2S and CoS produce higher photocurrents and fill factors, greatly improving cell performance.

Chelation, spectroscopic characterization, biological activity and crystal structure of 2,3-butanedione isonicotinylhydrazone: Determination of Zr4+ after flotation separation

NASA Astrophysics Data System (ADS)

Al-Fulaij, O. A.; Jeragh, B.; El-Sayed, A. E. M.; El-Defrawy, M. M.; El-Asmy, A. A.

2015-02-01

New metal complexes of Co(II), Ni(II) Cu(II), Zn(II), Cd(II), Pd(II) and Hg(II) with 2,3-butanedione isonicotinylhydrazone [BINH] have been prepared and investigated. Single crystal for BINH is grown and solved as orthorhombic with P 21 21 2 space group. The formula of the ligand was assigned based on the elemental analysis, mass spectra and conductivity measurements. The complexes assigned the formulae [M(BINH-H)Cl]ṡnH2O (Mdbnd Co(II), Ni(II), Cu(II), Zn(II); n = 0 or 1); [Hg(BINH-H)(H2O)2Cl]; [Cd(BINH)Cl2]ṡ2H2O and [Pd(BINH)Cl2]ṡH2O. All complexes are nonelectrolytes. BINH acts as a tridentate ligand in [M(BINH-H)Cl]ṡnH2O and [Hg(BINH-H)(H2O)2Cl] coordinating through Cdbnd Oketonic, Csbnd Oamedic and Cdbnd Nhy and as a neutral bidentate through Cdbnd Oketonic and Cdbnd Nhy in [Cd(BINH)Cl2]ṡ2H2O and [Pd(BINH)Cl2]ṡH2O; the pyridine nitrogen has no rule in coordination. The data are supported by NMR (1H and 13C) spectra. The magnetic moments and electronic spectra provide a tetrahedral structure for the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes; square-planar for the Pd(II) complex and octahedral for the Hg(II) complex. The TGA of the complexes depicted the outer and inner water molecules as well as the final residue. The cobalt and cadmium complexes ended with the metal while the Cu(II), Zn(II) and Pd(II) complexes ended with complex species. [Hg(BINH-H)(H2O)2Cl] has no residue. The ligand is inactive against all tested organisms except for Bacillus thuringiensis. The Hg(II) complex is found more active than the other complexes. The flotation technique is found applicable for the separation of micro amount (10 ppm) of Zr4+ using 10 ppm of BINH and 1 × 10-5 mol L-1 of oleic acid at pH 6 with efficiency of 98% with no interferences.

Deep sequencing and flow cytometric characterization of expanded effector memory CD8+CD57+ T cells frequently reveals T-cell receptor Vβ oligoclonality and CDR3 homology in acquired aplastic anemia.

PubMed

Giudice, Valentina; Feng, Xingmin; Lin, Zenghua; Hu, Wei; Zhang, Fanmao; Qiao, Wangmin; Ibanez, Maria Del Pilar Fernandez; Rios, Olga; Young, Neal S

2018-05-01

Oligoclonal expansion of CD8 + CD28 - lymphocytes has been considered indirect evidence for a pathogenic immune response in acquired aplastic anemia. A subset of CD8 + CD28 - cells with CD57 expression, termed effector memory cells, is expanded in several immune-mediated diseases and may have a role in immune surveillance. We hypothesized that effector memory CD8 + CD28 - CD57 + cells may drive aberrant oligoclonal expansion in aplastic anemia. We found CD8 + CD57 + cells frequently expanded in the blood of aplastic anemia patients, with oligoclonal characteristics by flow cytometric Vβ usage analysis: skewing in 1-5 Vβ families and frequencies of immunodominant clones ranging from 1.98% to 66.5%. Oligoclonal characteristics were also observed in total CD8 + cells from aplastic anemia patients with CD8 + CD57 + cell expansion by T-cell receptor deep sequencing, as well as the presence of 1-3 immunodominant clones. Oligoclonality was confirmed by T-cell receptor repertoire deep sequencing of enriched CD8 + CD57 + cells, which also showed decreased diversity compared to total CD4 + and CD8 + cell pools. From analysis of complementarity-determining region 3 sequences in the CD8 + cell pool, a total of 29 sequences were shared between patients and controls, but these sequences were highly expressed in aplastic anemia subjects and also present in their immunodominant clones. In summary, expansion of effector memory CD8 + T cells is frequent in aplastic anemia and mirrors Vβ oligoclonal expansion. Flow cytometric Vβ usage analysis combined with deep sequencing technologies allows high resolution characterization of the T-cell receptor repertoire, and might represent a useful tool in the diagnosis and periodic evaluation of aplastic anemia patients. (Registered at clinicaltrials.gov identifiers: 00001620, 01623167, 00001397, 00071045, 00081523, 00961064 ). Copyright © 2018 Ferrata Storti Foundation.

The polymorphisms K469E and G261R of intercellular adhesion molecule-1 and susceptibility to inflammatory bowel disease: a meta-analysis.

PubMed

Song, Gwan Gyu; Lee, Young Ho

2015-01-01

The aim of this study was to explore whether polymorphisms of intercellular adhesion molecule-1 (ICAM-1) are associated with susceptibility to Crohn's disease (CD) and ulcerative colitis (UC). The authors conducted a meta-analysis on the associations between the polymorphisms K469E and G241R of ICAM-1 and susceptibility to CD and UC. A total of 8 studies with 801 patients with CD, 672 patients with UC, and 1,828 controls were included in the meta-analysis. The meta-analysis revealed no association between CD and the ICAM-1 469E allele among the subjects (OR = 1.175, 95% CI = 0.901-1.533, p = 0.233). However, stratification by ethnicity indicated an association between the ICAM-1 469E allele and CD in Europeans (OR = 1.425, 95% CI = 1.013-2.002, p = 0.042). Meta-analysis using the homozygosity also showed an association with CD in Europeans (OR = 2.054, 95% CI = 1.036-4.073, p = 0.039). The meta-analysis revealed no association between UC and the ICAM-1 K469E polymorphism. No association between CD or UC and the ICAM-1 G241R polymorphism was observed. This meta-analysis demonstrates that the ICAM-1 K469E polymorphism may be associated with susceptibility to CD in Europeans, but no association was found between ICAM-1 K469E and UC. In contrast, the G241R polymorphism was not found to be associated with susceptibility to either CD or UC.

Transparent Ultra-High-Loading Quantum Dot/Polymer Nanocomposite Monolith for Gamma Scintillation.

PubMed

Liu, Chao; Li, Zhou; Hajagos, Tibor Jacob; Kishpaugh, David; Chen, Dustin Yuan; Pei, Qibing

2017-06-27

Spectroscopic gamma-photon detection has widespread applications for research, defense, and medical purposes. However, current commercial detectors are either prohibitively expensive for wide deployment or incapable of producing the characteristic gamma photopeak. Here we report the synthesis of transparent, ultra-high-loading (up to 60 wt %) Cd x Zn 1-x S/ZnS core/shell quantum dot/polymer nanocomposite monoliths for gamma scintillation by in situ copolymerization of the partially methacrylate-functionalized quantum dots in a monomer solution. The efficient Förster resonance energy transfer of the high-atomic-number quantum dots to lower-band-gap organic dyes enables the extraction of quantum-dot-borne excitons for photon production, resolving the problem of severe light yield deterioration found in previous nanoparticle-loaded scintillators. As a result, the nanocomposite scintillator exhibited simultaneous improvements in both light yield (visible photons produced per MeV of gamma-photon energy) and gamma attenuation. With these enhancements, a 662 keV Cs-137 gamma photopeak with 9.8% resolution has been detected using a 60 wt % quantum-dot nanocomposite scintillator, demonstrating the potential of such a nanocomposite system in the development of high-performance low-cost spectroscopic gamma detectors.

Sequential events in the irreversible thermal denaturation of human brain-type creatine kinase by spectroscopic methods.

PubMed

Gao, Yan-Song; Su, Jing-Tan; Yan, Yong-Bin

2010-06-25

The non-cooperative or sequential events which occur during protein thermal denaturation are closely correlated with protein folding, stability, and physiological functions. In this research, the sequential events of human brain-type creatine kinase (hBBCK) thermal denaturation were studied by differential scanning calorimetry (DSC), CD, and intrinsic fluorescence spectroscopy. DSC experiments revealed that the thermal denaturation of hBBCK was calorimetrically irreversible. The existence of several endothermic peaks suggested that the denaturation involved stepwise conformational changes, which were further verified by the discrepancy in the transition curves obtained from various spectroscopic probes. During heating, the disruption of the active site structure occurred prior to the secondary and tertiary structural changes. The thermal unfolding and aggregation of hBBCK was found to occur through sequential events. This is quite different from that of muscle-type CK (MMCK). The results herein suggest that BBCK and MMCK undergo quite dissimilar thermal unfolding pathways, although they are highly conserved in the primary and tertiary structures. A minor difference in structure might endow the isoenzymes dissimilar local stabilities in structure, which further contribute to isoenzyme-specific thermal stabilities.

Effect of Bi2O3 on spectroscopic and structural properties of Er3+ doped cadmium bismuth borate glasses.

PubMed

Sanghi, S; Pal, I; Agarwal, A; Aggarwal, M P

2011-12-01

Glasses with composition 20CdO·xBi(2)O(3)·(79.5-x)B(2)O(3) (15≤x≤35, x in mol%) containing 0.5 mol% of Er(3+) ions were prepared by melt-quench technique (1150°C in air). The amorphous nature of the glasses was confirmed by X-ray diffraction. The spectroscopic properties of the glasses were investigated using optical absorption spectra and fluorescence spectra. The phenomenological Judd-Ofelt intensity parameters Ω(λ) (λ=2, 4, 6) were determined from the spectral intensities of absorption bands in order to calculate the radiative transition probability (A(R)), radiative life time (τ(R)), branching ratios (β(R)) for various excited luminescent states. Using the near infrared emission spectra, full width at half maxima (FWHM), stimulated emission cross-section (σ(e)) and figure of merit (FOM) were evaluated and compared with other hosts. Especially, the numerical values of these parameters indicate that the emission transition (4)I(13/2)→(4)I(15/2) at 1.506 μm in Er(3+)-doped cadmium bismuth borate glasses may be useful in optical communication. Copyright © 2011 Elsevier B.V. All rights reserved.

Gaps analysis for CD metrology beyond the 22nm node

NASA Astrophysics Data System (ADS)

Bunday, Benjamin; Germer, Thomas A.; Vartanian, Victor; Cordes, Aaron; Cepler, Aron; Settens, Charles

2013-04-01

This paper will examine the future for critical dimension (CD) metrology. First, we will present the extensive list of applications for which CD metrology solutions are needed, showing commonalities and differences among the various applications. We will then report on the expected technical limits of the metrology solutions currently being investigated by SEMATECH and others in the industry to address the metrology challenges of future nodes, including conventional CD scanning electron microscopy (CD-SEM) and optical critical dimension (OCD) metrology and new potential solutions such as He-ion microscopy (HeIM, sometimes elsewhere referred to as HIM), CD atomic force microscopy (CD-AFM), CD small-angle x-ray scattering (CD-SAXS), high-voltage scanning electron microscopy (HV-SEM), and other types. A technical gap analysis matrix will then be demonstrated, showing the current state of understanding of the future of the CD metrology space.

Different fecal microbiotas and volatile organic compounds in treated and untreated children with celiac disease.

PubMed

Di Cagno, Raffaella; Rizzello, Carlo G; Gagliardi, Francesca; Ricciuti, Patrizia; Ndagijimana, Maurice; Francavilla, Ruggiero; Guerzoni, M Elisabetta; Crecchio, Carmine; Gobbetti, Marco; De Angelis, Maria

2009-06-01

This study aimed at investigating the fecal microbiotas of children with celiac disease (CD) before (U-CD) and after (T-CD) they were fed a gluten-free diet and of healthy children (HC). Brothers or sisters of T-CD were enrolled as HC. Each group consisted of seven children. PCR-denaturing gradient gel electrophoresis (DGGE) analysis with V3 universal primers revealed a unique profile for each fecal sample. PCR-DGGE analysis with group- or genus-specific 16S rRNA gene primers showed that the Lactobacillus community of U-CD changed significantly, while the diversity of the Lactobacillus community of T-CD was quite comparable to that of HC. Compared to HC, the ratio of cultivable lactic acid bacteria and Bifidobacterium to Bacteroides and enterobacteria was lower in T-CD and even lower in U-CD. The percentages of strains identified as lactobacilli differed as follows: HC (ca. 38%) > T-CD (ca. 17%) > U-CD (ca. 10%). Lactobacillus brevis, Lactobacillus rossiae, and Lactobacillus pentosus were identified only in fecal samples from T-CD and HC. Lactobacillus fermentum, Lactobacillus delbrueckii subsp. bulgaricus, and Lactobacillus gasseri were identified only in several fecal samples from HC. Compared to HC, the composition of Bifidobacterium species of T-CD varied, and it varied even more for U-CD. Forty-seven volatile organic compounds (VOCs) belonging to different chemical classes were identified using gas-chromatography mass spectrometry-solid-phase microextraction analysis. The median concentrations varied markedly for HC, T-CD, and U-CD. Overall, the r(2) values for VOC data for brothers and sisters were equal to or lower than those for unrelated HC and T-CD. This study shows the effect of CD pathology on the fecal microbiotas of children.

The Prognostic Role of Cancer Stem Cell Markers for Long-term Outcome After Resection of Colonic Liver Metastases.

PubMed

Spelt, Lidewij; Sasor, Agata; Ansari, Daniel; Hilmersson, Katarzyna Said; Andersson, Roland

2018-01-01

To assess the expression of cancer stem cell (CSC) markers CD44, CD133 and CD24 in colon cancer liver metastases and analyse their predictive value for overall survival (OS) and disease-free survival (DFS) after liver resection. Patients operated on for colon cancer liver metastases were included. CSC marker expression was determined through immunohistochemistry analysis. OS and DFS were compared between marker-positive and marker-negative patients. Multivariate analysis was performed to select predictive variables for OS and DFS. CD133-positive patients had a worse DFS than CD133-negative patients, with a median DFS of 12 and 25 months (p=0.051). Multivariate analysis selected CD133 expression as a significant predictor for DFS. CD44 and CD24 were not found to predict OS or DFS. CD133 expression in colonic liver metastases is a negative prognostic factor for DFS after liver resection. In the future, CD133 could be used as a biomarker for risk stratification, and possibly for developing novel targeted therapy. Copyright© 2018, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Association of trauma, Posttraumatic Stress Disorder and Conduct Disorder: A systematic review and meta-analysis.

PubMed

Bernhard, Anka; Martinelli, Anne; Ackermann, Katharina; Saure, Daniel; Freitag, Christine M

2018-08-01

To summarize findings of previous studies on the prevalence of trauma and Posttraumatic Stress Disorder (PTSD) in Conduct Disorder (CD). We conducted a systematic review and meta-analysis following the PRISMA guidelines. EBSCOhost, PubMed, CDSR and ARIF databases were searched in October 2016, employing relevant keywords. 19 studies met inclusion criteria. Meta-analysis resulted in a lifetime PTSD prevalence of 11% (95% CI: 7-17%) in children and adolescents with CD, 14% (95% CI: 12-15%) in adults with pre-existing CD and 32% (95% CI: 25-40%) in juvenile offenders with CD. Higher lifetime PTSD prevalence was observed in individuals with than without CD, and in females compared to males with CD. Studies focusing on the association of trauma, PTSD and CD are still relatively rare. Possible comorbidity models are discussed considering psychological and biological risk factors in a comprehensive model. The high rate of PTSD in CD may be due to shared risk factors; furthermore, CD might increase the risk for comorbid PTSD due to CD inherent risk taking behavior. To study pathways of risk, especially longitudinal studies are necessary. Copyright © 2017 Elsevier Ltd. All rights reserved.

In-Depth Analysis of Citrulline-Specific CD4 T Cells in Rheumatoid Arthritis

DTIC Science & Technology

2017-01-01

AWARD NUMBER: W81XWH-15-1-0003 TITLE: In-Depth Analysis of Citrulline-Specific CD4 T Cells in Rheumatoid Arthritis PRINCIPAL INVESTIGATOR...TITLE AND SUBTITLE In-Depth Analysis of Citrulline-Specific CD4 T Cells in Rheumatoid Arthritis 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-15-1-0003...NOTES 14. ABSTRACT The goal of this project is to test the hypothesis that cit-specific CD4 T cells present in rheumatoid arthritis (RA) patients

In-Depth Analysis of Citrulline Specific CD4 T-Cells in Rheumatoid Arthritis

DTIC Science & Technology

2017-01-01

AWARD NUMBER: W81XWH-15-1-0004 TITLE: In-Depth Analysis of Citrulline-Specific CD4 T-Cells in Rheumatoid Arthritis PRINCIPAL INVESTIGATOR...2016 4. TITLE AND SUBTITLE In-Depth Analysis of Citrulline-Specific CD4 T Cells in Rheumatoid Arthritis 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH...NOTES 14. ABSTRACT The goal of this project is to test the hypothesis that cit-specific CD4 T cells present in rheumatoid arthritis (RA) patients

Nonionic and zwitterionic forms of glycylglycylarginine as a part of spider silk protein: Spectroscopic and theoretical study

NASA Astrophysics Data System (ADS)

Arı, Hatice; Özpozan, Talat

2016-01-01

Glycylglycylarginine as a part of GGX motif of spider silk spidroin in nonionic (non-GGR) and zwitterionic (zwt-GGR) forms have been examined from theoretical and spectroscopic aspects. The most stable conformational isomers of non-GGR and zwt-GGR were obtained through relaxed scan using the DFT/B3LYP with 6-31G(d) basis set. Nonionic and zwitterionic forms of 310-helix structures of GGR have also been calculated and compared with the most stable conformers obtained as a result of conformer analysis of isolated three peptide structures. This comparison should give an idea about the stability contribution of intermolecular interactions between the 310-helix structured peptide chains. O3LYP and B3PW91 hybrid functionals beside B3LYP have also been used for further calculations of geometry optimization, vibrational analysis, Natural Bond Orbital (NBO) analysis, HOMO-LUMO analysis and hydrogen bonding analysis. Normal Mode Analysis was carried through Potential Energy Distribution (PED) calculations by means of VEDA4 program package. IR and Raman spectra of GGR have also been used to relate the spectroscopic data obtained to electronic and structural features.

Nonionic and zwitterionic forms of glycylglycylarginine as a part of spider silk protein: Spectroscopic and theoretical study.

PubMed

Arı, Hatice; Özpozan, Talat

2016-01-05

Glycylglycylarginine as a part of GGX motif of spider silk spidroin in nonionic (non-GGR) and zwitterionic (zwt-GGR) forms have been examined from theoretical and spectroscopic aspects. The most stable conformational isomers of non-GGR and zwt-GGR were obtained through relaxed scan using the DFT/B3LYP with 6-31G(d) basis set. Nonionic and zwitterionic forms of 310-helix structures of GGR have also been calculated and compared with the most stable conformers obtained as a result of conformer analysis of isolated three peptide structures. This comparison should give an idea about the stability contribution of intermolecular interactions between the 310-helix structured peptide chains. O3LYP and B3PW91 hybrid functionals beside B3LYP have also been used for further calculations of geometry optimization, vibrational analysis, Natural Bond Orbital (NBO) analysis, HOMO-LUMO analysis and hydrogen bonding analysis. Normal Mode Analysis was carried through Potential Energy Distribution (PED) calculations by means of VEDA4 program package. IR and Raman spectra of GGR have also been used to relate the spectroscopic data obtained to electronic and structural features. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of some transition metal complexes with new heterocyclic thiazolyl azo dye and their uses as sensitizers in photo reactions

NASA Astrophysics Data System (ADS)

AL-Adilee, Khalid J.; Abass, Ahmed K.; Taher, Ali M.

2016-03-01

A new heterocyclic thiazolylazo dye ligand, 2- [bar2-(4, 5- dimethyl thiazolyl) azo ] -4-Ethoxy Phenol (DMeTAEP), (LH) was synthesized by the diazotization of 4.5-dimethyl thiazolylazonium chloride and coupling with 4- Ethoxy phenol in alkaline alcoholic solution under suitable optimized experimental conditions to yield a new azo dye ligand. The structure of ligand and its complexes was prepared from Co(III), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Ag (I) and Au(III) ions. They confirmed by XRD, SEM, (TG-DTG) thermal analysis, 1H-NMR,UV-visb, mass and FT-IR spectroscopic methods, elemental analysis, atomic absorption, magnetic susceptibility and molar conductance. The mole ratio [M: L], it was also studied which was 1:1 for Ag (I) and Au (III) complexes and 1:2 The rest of the metal complexes. The isolated solid complexes are found to have the general formula [M (L)2 ] Cln.mH2O, where n = 1, m = 0 when M = Co (III) and n = 0, m = 1 when M = Ni (II), and Hg(II) while n = 0 and m = 0 when M = Cu (II), Zn (II), Cd (II) and ]ML (H2O)] of Ag(I) - complex but Au(III)-complex structural formula was [Au(L)Cl] Cl conductivity measurements for prepared complexes showed 1:1 electrolyte for Co(III(and Au(III) complexes and non - electrolyte the rest of complexes. The spectral and analytical data revealed that this ligand behaves as a tridentate chelating agent and coordination number of all metal ions were found to be six except for Ag (I) and Au (III) which was four. The activities of complexes were examined as sensitizers in the photocatalytic reaction of p-nitro aniline (PNA) which is used as a model of water pollutants.

Spectroscopic analysis of 8-hydroxyquinoline derivatives and investigation of its reactive properties by DFT and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sureshkumar, B.; Mary, Y. Sheena; Resmi, K. S.; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, C.; Narayana, B.; Suma, S.

2018-03-01

Two 8-hydroxyquinoline derivatives, 5,7-dichloro-8-hydroxyquinoline (57DC8HQ) and 5-chloro-7-iodo-8-hydroxy quinoline (5CL7I8HQ) have been investigated in details by means of spectroscopic characterization and computational molecular modelling techniques. FT-IR and FT-Raman experimental spectroscopic approaches have been utilized in order to obtain detailed spectroscopic signatures of title compounds, while DFT calculations have been used in order to visualize and assign vibrations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the title molecules exhibit NLO properties. The evaluated HOMO and LUMO energies demonstrate the chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyperconjugative interactions and charge delocalization. DFT calculations have been also used jointly with MD simulations in order to investigate in details global and local reactivity properties of title compounds. Also, molecular docking has been also used in order to investigate affinity of title compounds against decarboxylase inhibitor and quinoline derivatives can be a lead compounds for developing new antiparkinsonian drug.

EEL spectroscopic tomography: towards a new dimension in nanomaterials analysis.

PubMed

Yedra, Lluís; Eljarrat, Alberto; Arenal, Raúl; Pellicer, Eva; Cabo, Moisés; López-Ortega, Alberto; Estrader, Marta; Sort, Jordi; Baró, Maria Dolors; Estradé, Sònia; Peiró, Francesca

2012-11-01

Electron tomography is a widely spread technique for recovering the three dimensional (3D) shape of nanostructured materials. Using a spectroscopic signal to achieve a reconstruction adds a fourth chemical dimension to the 3D structure. Up to date, energy filtering of the images in the transmission electron microscope (EFTEM) is the usual spectroscopic method even if most of the information in the spectrum is lost. Unlike EFTEM tomography, the use of electron energy-loss spectroscopy (EELS) spectrum images (SI) for tomographic reconstruction retains all chemical information, and the possibilities of this new approach still remain to be fully exploited. In this article we prove the feasibility of EEL spectroscopic tomography at low voltages (80 kV) and short acquisition times from data acquired using an aberration corrected instrument and data treatment by Multivariate Analysis (MVA), applied to Fe(x)Co((3-x))O(4)@Co(3)O(4) mesoporous materials. This approach provides a new scope into materials; the recovery of full EELS signal in 3D. Copyright © 2012 Elsevier B.V. All rights reserved.

Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

2015-05-01

The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader's quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN (1Σ) and hydrideisocyanidezinc HZnNC (1Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]+ composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn+ (2Σ) and HCNZn+ (2Σ).

Cycle bases to the rescue

NASA Astrophysics Data System (ADS)

Tóbiás, Roland; Furtenbacher, Tibor; Császár, Attila G.

2017-12-01

Cycle bases of graph theory are introduced for the analysis of transition data deposited in line-by-line rovibronic spectroscopic databases. The principal advantage of using cycle bases is that outlier transitions -almost always present in spectroscopic databases built from experimental data originating from many different sources- can be detected and identified straightforwardly and automatically. The data available for six water isotopologues, H216O, H217O, H218O, HD16O, HD17O, and HD18O, in the HITRAN2012 and GEISA2015 databases are used to demonstrate the utility of cycle-basis-based outlier-detection approaches. The spectroscopic databases appear to be sufficiently complete so that the great majority of the entries of the minimum cycle basis have the minimum possible length of four. More than 2000 transition conflicts have been identified for the isotopologue H216O in the HITRAN2012 database, the seven common conflict types are discussed. It is recommended to employ cycle bases, and especially a minimum cycle basis, for the analysis of transitions deposited in high-resolution spectroscopic databases.

Principal component and spatial correlation analysis of spectroscopic-imaging data in scanning probe microscopy.

PubMed

Jesse, Stephen; Kalinin, Sergei V

2009-02-25

An approach for the analysis of multi-dimensional, spectroscopic-imaging data based on principal component analysis (PCA) is explored. PCA selects and ranks relevant response components based on variance within the data. It is shown that for examples with small relative variations between spectra, the first few PCA components closely coincide with results obtained using model fitting, and this is achieved at rates approximately four orders of magnitude faster. For cases with strong response variations, PCA allows an effective approach to rapidly process, de-noise, and compress data. The prospects for PCA combined with correlation function analysis of component maps as a universal tool for data analysis and representation in microscopy are discussed.

Immunophenotypic analysis of Waldenstrom's macroglobulinemia.

PubMed

San Miguel, J F; Vidriales, M B; Ocio, E; Mateo, G; Sánchez-Guijo, F; Sánchez, M L; Escribano, L; Bárez, A; Moro, M J; Hernández, J; Aguilera, C; Cuello, R; García-Frade, J; López, R; Portero, J; Orfao, A

2003-04-01

Immunophenotyping has become an essential tool for diagnosis of hematological malignancies. By contrast, for diagnosis of Waldenstrom's macroglobulinemia (WM) immunophenotyping is used only occasionally. From 150 patients with a IgM monoclonal gammopathy we have selected 60 cases with (1) morphological lymphoplasmocytoid bone marrow (BM) infiltration (>20%); (2) IgM paraprotein (>10g/L); and (3) absence of features of other lymphoma types. Immunophenotypic analysis was based on the use of the triple or quadruple monoclonal antibody (MoAb) combinations. To increase the sensitivity of the analysis of antigen expression, selected CD19(+)CD20(+) B cells were targeted. We have also explored the antigenic characteristics of both the plasma cell (PC) and mast cell (MC) compartments present in the BM from 15 WM patients. Clonal WM lymphocytes were characterized by the constant expression of pan-B markers (CD19, CD20, CD22, CD24) together with sIg, predominantly kappa (5:1, kappa:lambda ratio). A high proportion of cases (75%) were positive for FMC7 and CD25, but in contrast to hairy cell leukemia (HCL), these lymphocytes were always negative for CD103 and CD11c. CD10 antigen was also absent in all WM patients and less than one fifth of patients were positive for CD5 and CD23, while CD27, CD45RA, and BCL-2 were present in most malignant cells. In two cases, the coexistence of two different clones of B lymphocytes was identified, and in eight additional cases, intraclonal phenotypic heterogeneity was observed. As far as PCs are concerned, in most patients (85%) the number of PCs was within the normal range (median, 0.36%). The antigenic profile of these PCs differed from that observed in normal and myelomatous PC (CD38(++)CD19(++/-)CD56(-)CD45(++)CD20(+)). In three cases, PCs showed aberrant expression for CD5, CD22, or FMC7. Finally, the number of mast cells was significantly higher (0.058 +/- 0.13) as compared to normal BM (0.019 +/- 0.02) (P <.01), although they were immunophenotypically normal (CD117(+)CD2(-)CD25(-)). Copyright 2003 Elsevier Inc. All rights reserved.

Standoff spectroscopic interrogation of samples irradiated by high energy lasers

NASA Astrophysics Data System (ADS)

Daigle, Jean-François; Pudo, Dominik; Théberge, Francis

2017-10-01

We report on a novel method that shows the potential to provide real-time, standoff forensic analysis of samples being irradiated by a high energy laser (HEL). The interaction of the HEL beam with matter produces specific optical signatures that can be detected from the location of the HEL system. A spectroscopic analysis of these signals can then provide useful information to the operator including the impact the laser has on the sample as well as providing data about the its structure and composition.

Novel Multidimensional Cross-Correlation Data Comparison Techniques for Spectroscopic Discernment in a Volumetrically Sensitive, Moderating Type Neutron Spectrometer

NASA Astrophysics Data System (ADS)

Hoshor, Cory; Young, Stephan; Rogers, Brent; Currie, James; Oakes, Thomas; Scott, Paul; Miller, William; Caruso, Anthony

2014-03-01

A novel application of the Pearson Cross-Correlation to neutron spectral discernment in a moderating type neutron spectrometer is introduced. This cross-correlation analysis will be applied to spectral response data collected through both MCNP simulation and empirical measurement by the volumetrically sensitive spectrometer for comparison in 1, 2, and 3 spatial dimensions. The spectroscopic analysis methods discussed will be demonstrated to discern various common spectral and monoenergetic neutron sources.

Extinction measurement of dense media by an optical coherence tomography technique

NASA Astrophysics Data System (ADS)

Ago, Tomoki; Iwai, Toshiaki; Yokota, Ryoko

2016-10-01

The optical coherence tomography will make progress as the next stage toward a spectroscopic analysis technique. The spectroscopic analysis is based on the Beer-Lambert law. The absorption and scattering coefficients even for the dense medium can be measured by the Beer-Lambert law because the OCT can detect only the light keeping the coherency which propagated rectilinearly and retro-reflected from scatters. This study is concerned with the quantitative verification of Beer-Lambert law in the OCT imaging.

Predictive spectroscopy and chemical imaging based on novel optical systems

NASA Astrophysics Data System (ADS)

Nelson, Matthew Paul

1998-10-01

This thesis describes two futuristic optical systems designed to surpass contemporary spectroscopic methods for predictive spectroscopy and chemical imaging. These systems are advantageous to current techniques in a number of ways including lower cost, enhanced portability, shorter analysis time, and improved S/N. First, a novel optical approach to predicting chemical and physical properties based on principal component analysis (PCA) is proposed and evaluated. A regression vector produced by PCA is designed into the structure of a set of paired optical filters. Light passing through the paired filters produces an analog detector signal directly proportional to the chemical/physical property for which the regression vector was designed. Second, a novel optical system is described which takes a single-shot approach to chemical imaging with high spectroscopic resolution using a dimension-reduction fiber-optic array. Images are focused onto a two- dimensional matrix of optical fibers which are drawn into a linear distal array with specific ordering. The distal end is imaged with a spectrograph equipped with an ICCD camera for spectral analysis. Software is used to extract the spatial/spectral information contained in the ICCD images and deconvolute them into wave length-specific reconstructed images or position-specific spectra which span a multi-wavelength space. This thesis includes a description of the fabrication of two dimension-reduction arrays as well as an evaluation of the system for spatial and spectral resolution, throughput, image brightness, resolving power, depth of focus, and channel cross-talk. PCA is performed on the images by treating rows of the ICCD images as spectra and plotting the scores of each PC as a function of reconstruction position. In addition, iterative target transformation factor analysis (ITTFA) is performed on the spectroscopic images to generate ``true'' chemical maps of samples. Univariate zero-order images, univariate first-order spectroscopic images, bivariate first-order spectroscopic images, and multivariate first-order spectroscopic images of the temporal development of laser-induced plumes are presented and interpreted. Reconstructed chemical images generated using bivariate and trivariate wavelength techniques, bimodal and trimodal PCA methods, and bimodal and trimodal ITTFA approaches are also included.

Associations between CD24 gene polymorphisms and inflammatory bowel disease: A meta-analysis.

PubMed

Huang, Xiao-Li; Xu, Dong-Hua; Wang, Guo-Pin; Zhang, Shu; Yu, Cheng-Gong

2015-05-21

To evaluate the relationships between CD24 gene polymorphisms and the risk of inflammatory bowel disease (IBD), including ulcerative colitis (UC) and Crohn's disease (CD). The PubMed, Web of Science and Cochrane Library databases were searched (up to May 30, 2014). The search terms "CD24", "inflammatory bowel disease", "Crohn's disease", "Ulcerative colitis", "IBD", "CD" or "UC"; and "polymorphism", "mutation" or "variant" were used. Association studies were limited to the English language, but no limitations in terms of race, ethnicity or geographic area were employed. Stata SE12 software was used to calculate the pooled odds ratios (ORs) with 95% confidence intervals (CIs). P < 0.05 was considered statistically significant. The information was independently extracted from each eligible study by two investigators. Two common polymorphisms, C170T (rs8734) and TG1527del (rs3838646), in the CD24 gene were assessed. A total of three case-control studies including 2342 IBD patients and 1965 healthy controls were involved in this meta-analysis. The patients and controls were from Caucasian cohorts. The three articles included in this meta-analysis all conformed to Hardy-Weinberg equilibrium. This meta-analysis revealed that there were no significant associations between the two CD24 polymorphisms and the risk for IBD (all P > 0.05). However, in a disease subgroup analysis, we found that the CD24 C170T polymorphism was associated with an increased risk of UC in a dominant model (OR = 1.79, 95%CI: 1.15-2.77, P = 0.009) and an additive model (OR = 1.87, 95%CI: 1.19-2.93, P = 0.007), but this relationship was not present for CD. The CD24 TG1570del polymorphism was significantly associated with CD in the additive model (OR = 1.24, 95%CI: 1.01-1.52, P = 0.037). Our findings provide evidence that the CD24 C170T polymorphism might contribute to the susceptibility to UC, and the CD24 TG1527del polymorphism might be associated with the risk of CD.

How specific Raman spectroscopic models are: a comparative study between different cancers

NASA Astrophysics Data System (ADS)

Singh, S. P.; Kumar, K. Kalyan; Chowdary, M. V. P.; Maheedhar, K.; Krishna, C. Murali

2010-02-01

Optical spectroscopic methods are being contemplated as adjunct/ alternative to existing 'Gold standard' of cancer diagnosis, histopathological examination. Several groups are actively pursuing diagnostic applications of Ramanspectroscopy in cancers. We have developed Raman spectroscopic models for diagnosis of breast, oral, stomach, colon and larynx cancers. So far, specificity and applicability of spectral- models has been limited to particular tissue origin. In this study we have evaluated explicitly of spectroscopic-models by analyzing spectra from already developed spectralmodels representing normal and malignant tissues of breast (46), cervix (52), colon (25), larynx (53), and oral (47). Spectral data was analyzed by Principal Component Analysis (PCA) using scores of factor, Mahalanobis distance and Spectral residuals as discriminating parameters. Multiparametric limit test approach was also explored. The preliminary unsupervised PCA of pooled data indicates that normal tissue types were always exclusive from their malignant counterparts. But when we consider tissue of different origin, large overlap among clusters was found. Supervised analysis by Mahalanobis distance and spectral residuals gave similar results. The 'limit test' approach where classification is based on match / mis-match of the given spectrum against all the available spectra has revealed that spectral models are very exclusive and specific. For example breast normal spectral model show matches only with breast normal spectra and mismatch to rest of the spectra. Same pattern was seen for most of spectral models. Therefore, results of the study indicate the exclusiveness and efficacy of Raman spectroscopic-models. Prospectively, these findings might open new application of Raman spectroscopic models in identifying a tumor as primary or metastatic.

Measurement of the Spectroscopic Quadrupole Moment for the 2+1 State in 10Be:. Testing AB Initio Calculations

NASA Astrophysics Data System (ADS)

Orce, J. N.; Djongolov, M.; Navratil, P.; Ball, G.; Garnsworthy, A. B.; Hackman, G.; Lassen, J.; Meissner, J.; Pearson, C. J.; Li, R.; Milovanovic, L.; Sjue, S. K. L.; Teigelhoefer, A.; Triambak, S.; Williams, S. J.; Falou, H. Al; Drake, T. E.; Andreoiu, C.; Cross, D.; Kshetri, R.; Finlay, P.; Garrett, P. E.; Leach, K. G.; Rand, E. T.; Sumithrarachchi, C. S.; Svensson, C. E.; Tardiff, E. R.; Wong, J.; Forssen, C.; Hayes, A. B.; Sarazin, F.; Stoyer, M. A.; Wu, C. Y.

2013-03-01

The highly efficient and segmented TIGRESS HPGe γ-ray array at TRIUMF has been used to perform a reorientation effect Coulomb excitation study of the 2+1 state at 3.368 MeV in 10Be. This is the first Coulomb excitation measurement that provides information on diagonal matrix elements for such a high lying first excited state from μ-ray data. With the availability of accurate lifetime data, a restriction on the diagonal < 2+1|M({E}2)|2+1> matrix element is determined. This result is compared to a no core shell model calculation with the CD-Bonn 2000 two nucleon potential.

Protein thermal stabilization in aqueous solutions of osmolytes.

PubMed

Bruździak, Piotr; Panuszko, Aneta; Jourdan, Muriel; Stangret, Janusz

2016-01-01

Proteins' thermal stabilization is a significant problem in various biomedical, biotechnological, and technological applications. We investigated thermal stability of hen egg white lysozyme in aqueous solutions of the following stabilizing osmolytes: Glycine (GLY), N-methylglycine (NMG), N,N-dimethylglycine (DMG), N,N,N-trimethylglycine (TMG), and trimethyl-N-oxide (TMAO). Results of CD-UV spectroscopic investigation were compared with FTIR hydration studies' results. Selected osmolytes increased lysozyme's thermal stability in the following order: Gly>NMG>TMAO≈DMG>TMG. Theoretical calculations (DFT) showed clearly that osmolytes' amino group protons and water molecules interacting with them played a distinctive role in protein thermal stabilization. The results brought us a step closer to the exact mechanism of protein stabilization by osmolytes.

Four new triterpenoids from the leaves of Psidium guajava.

PubMed

Shao, Meng; Wang, Ying; Huang, Xiao-Jun; Fan, Chun-Lin; Zhang, Qing-Wen; Zhang, Xiao-Qi; Ye, Wen-Cai

2012-01-01

Four new triterpenoids, psiguanins A-D (1-4), along with 13 known ones (5-17), were isolated from the leaves of Psidium guajava. The structures of new compounds were determined as 2α,3β-dihydroxy-taraxer-20-en-28-oic acid (1), 2α,3β,12α,13β-tetrahydroxy-urs-28-oic acid (2), 2α,3β,12β,13β-tetrahydroxy-urs-28-oic acid (3), and 2α,3β,12β,13α-tetrahydroxy-urs-28-oic acid (4), respectively, on the basis of comprehensive spectroscopic methods and molecular modeling calculation. Among them, compound 4 was characterized as an unusual ursane-type triterpenoid with cis-fused C/D ring system.

Evaluating diffraction based overlay metrology for double patterning technologies

NASA Astrophysics Data System (ADS)

Saravanan, Chandra Saru; Liu, Yongdong; Dasari, Prasad; Kritsun, Oleg; Volkman, Catherine; Acheta, Alden; La Fontaine, Bruno

2008-03-01

Demanding sub-45 nm node lithographic methodologies such as double patterning (DPT) pose significant challenges for overlay metrology. In this paper, we investigate scatterometry methods as an alternative approach to meet these stringent new metrology requirements. We used a spectroscopic diffraction-based overlay (DBO) measurement technique in which registration errors are extracted from specially designed diffraction targets for double patterning. The results of overlay measurements are compared to traditional bar-in-bar targets. A comparison between DBO measurements and CD-SEM measurements is done to show the correlation between the two approaches. We discuss the total measurement uncertainty (TMU) requirements for sub-45 nm nodes and compare TMU from the different overlay approaches.

Semiconductor Grade, Solar Silicon Purification Project. [photovoltaic solar energy conversion

NASA Technical Reports Server (NTRS)

Ingle, W. M.; Rosler, R. S.; Thompson, S. W.; Chaney, R. E.

1979-01-01

A low cost by-product, SiF4, is reacted with mg silicon to form SiF2 gas which is polymerized. The (SiF2)x polymer is heated forming volatile SixFy homologues which disproportionate on a silicon particle bed forming silicon and SiF4. The silicon analysis procedure relied heavily on mass spectroscopic and emission spectroscopic analysis. These analyses demonstrated that major purification had occured and some samples were indistinguishable from semiconductor grade silicon (except possibly for phosphorus). However, electrical analysis via crystal growth reveal that the product contains compensated phosphorus and boron.

Single-cell analysis of lymphokine imbalance in asymptomatic HIV-1 infection: evidence for a major alteration within the CD8+ T cell subset

PubMed Central

Sousa, A E; Victorino, R M M

1998-01-01

In this study we investigated at single-cell level by flow cytometry the potential of T cell cytokine production in asymptomatic HIV-1-infected subjects with > 200 CD4 counts and possible correlation with T helper cell depletion and viral load. Mitogen-stimulated peripheral blood mononuclear cells from 32 HIV-1+ patients and 16 healthy subjects were intracytoplasmically stained for IL-2, interferon-gamma (IFN-γ), IL-4 or IL-10, and the frequency of cytokine-producing cells was assessed in total T cells, CD4, CD8 and CD45RO subsets as well as in CD69+CD3+ gated lymphocytes. HIV-1+ patients, irrespective of their degree of CD4 depletion, exhibited a major increase in IFN-γ+ CD8 T cells, largely due to CD28− cells, as well as a decrease in the capacity of CD8 T cells to produce IL-2. Patients with > 500 CD4 counts showed a diminished frequency of IL-4 expression in CD4 T cells and a negative correlation was found between this parameter and the ex vivo CD4 counts in the 32 patients. Analysis of patients stratified according to viral load revealed a significantly higher proportion of IL-2-producing CD4 cells in the group with < 5000 RNA copies/ml. In short, using single-cell analysis and an antigen-presenting cell-independent stimulus, we have not been able to find any significant cytokine imbalances in the CD4 subset, suggesting that the well described T helper defects are not due to intrinsic alterations in the potential of CD4 T cells to produce cytokines. On the other hand, the major disturbances in the CD8 T lymphocytes agree with the marked activation and possible replicative senescence of CD8 T cells and emphasize the role of this subset in HIV immunopathogenesis. PMID:9649194

Characterization of a spectroscopic detector for application in x-ray computed tomography

NASA Astrophysics Data System (ADS)

Dooraghi, Alex A.; Fix, Brian J.; Smith, Jerel A.; Brown, William D.; Azevedo, Stephen G.; Martz, Harry E.

2017-09-01

Recent advances in cadmium telluride (CdTe) energy-discriminating pixelated detectors have enabled the possibility of Multi-Spectral X-ray Computed Tomography (MSXCT) to incorporate spectroscopic information into CT. MultiX ME 100 V2 is a CdTe-based spectroscopic x-ray detector array capable of recording energies from 20 to 160 keV in 1.1 keV energy bin increments. Hardware and software have been designed to perform radiographic and computed tomography tasks with this spectroscopic detector. Energy calibration is examined using the end-point energy of a bremsstrahlung spectrum and radioisotope spectral lines. When measuring the spectrum from Am-241 across 500 detector elements, the standard deviation of the peak-location and FWHM measurements are +/- 0.4 and +/- 0.6 keV, respectively. As these values are within the energy bin size (1.1 keV), detector elements are consistent with each other. The count rate is characterized, using a nonparalyzable model with a dead time of 64 +/- 5 ns. This is consistent with the manufacturer's quoted per detector-element linear-deviation at 2 Mpps (million photons per sec) of 8.9 % (typical) and 12 % (max). When comparing measured and simulated spectra, a low-energy tail is visible in the measured data due to the spectral response of the detector. If no valid photon detections are expected in the low-energy tail, then a background subtraction may be applied to allow for a possible first-order correction. If photons are expected in the low-energy tail, a detailed model must be implemented. A radiograph of an aluminum step wedge with a maximum height of 20 mm shows an underestimation of attenuation by about 10 % at 60 keV. This error is due to partial energy deposition from higher energy (>60 keV) photons into a lower-energy ( 60 keV) bin, reducing the apparent attenuation. A radiograph of a polytetrafluoroethylene (PTFE) cylinder taken using a bremsstrahlung spectrum from an x-ray voltage of 100 kV filtered by 1.3 mm Cu is reconstructed using Abel inversion. As no counts are expected in the low energy tail, a first order background correction is applied to the spectrum. The measured linear attenuation coefficient (LAC) is within 10% of the expected value in the 60 to 100 keV range. Below 60 keV, low counts in the corrected spectrum and partial energy deposition from incident photons of energy greater than 60 keV into energy bins below 60 keV impact the LAC measurements. This report ends with a demonstration of the tomographic capability of the system. The quantitative understanding of the detector developed in this report will enable further study in evaluating the system for characterization of an object's chemical make-up for industrial and security purposes.

Characterization of a spectroscopic detector for application in x-ray computed tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dooraghi, A. A.; Fix, B. J.; Smith, J. A.

Recent advances in cadmium telluride (CdTe) energy-discriminating pixelated detectors have enabled the possibility of Multi-Spectral X-ray Computed Tomography (MSXCT) to incorporate spectroscopic information into CT. MultiX ME 100 V2 is a CdTe-based spectroscopic x-ray detector array capable of recording energies from 20 to 160 keV in 1.1 keV energy bin increments. Hardware and software have been designed to perform radiographic and computed tomography tasks with this spectroscopic detector. Energy calibration is examined using the end-point energy of a bremsstrahlung spectrum and radioisotope spectral lines. When measuring the spectrum from Am-241 across 500 detector elements, the standard deviation of the peak-locationmore » and FWHM measurements are ±0.4 and ±0.6 keV, respectively. As these values are within the energy bin size (1.1 keV), detector elements are consistent with each other. The count rate is characterized, using a nonparalyzable model with a dead time of 64 ± 5 ns. This is consistent with the manufacturer’s quoted per detector-element linear-deviation at 2 Mpps (million photons per sec) of 8.9% (typical) and 12% (max). When comparing measured and simulated spectra, a low-energy tail is visible in the measured data due to the spectral response of the detector. If no valid photon detections are expected in the low-energy tail, then a background subtraction may be applied to allow for a possible first-order correction. If photons are expected in the low-energy tail, a detailed model must be implemented. A radiograph of an aluminum step wedge with a maximum height of about 20 mm shows an underestimation of attenuation by about 10% at 60 keV. This error is due to partial energy deposition from higher-energy (> 60 keV) photons into a lower-energy (~60 keV) bin, reducing the apparent attenuation. A radiograph of a PTFE cylinder taken using a bremsstrahlung spectrum from an x-ray voltage of 100 kV filtered by 1.3 mm Cu is reconstructed using Abel inversion. As no counts are expected in the low energy tail, a first order background correction is applied to the spectrum. The measured linear attenuation coefficient (LAC) is within 10% of the expected value in the 60 to 100 keV range. Below 60 keV, low counts in the corrected spectrum and partial energy deposition from incident photons of energy greater than 60 keV into energy bins below 60 keV impact the LAC measurements. This report ends with a demonstration of the tomographic capability of the system. The quantitative understanding of the detector developed in this report will enable further study in evaluating the system for characterization of an object’s chemical make-up for industrial and security purposes.« less

Association Between Cd Exposure and Risk of Prostate Cancer: A PRISMA-Compliant Systematic Review and Meta-Analysis.

PubMed

Ju-Kun, Song; Yuan, Dong-Bo; Rao, Hao-Fu; Chen, Tian-Fei; Luan, Bo-Shi; Xu, Xiao-Ming; Jiang, Fu-Neng; Zhong, Wei-De; Zhu, Jian-Guo

2016-02-01

Several observational studies on the association between Cd exposure and risk of prostate cancer have yielded inconsistent results. To address this issue, we conducted a meta-analysis to evaluate the correlation between Cd exposure and risk of prostate cancer.Relevant studies in PubMed and Embase databases were retrieved until October 2015. We compared the highest and lowest meta-analyses to quantitatively evaluate the relationship between Cd exposure and risk of prostate cancer. Summary estimates were obtained using a random-effects model.In the general population, high Cd exposure was not associated with increased prostate cancer (OR 1.21; 95% CI 0.91-1.64), whereas the combined standardized mortality ratio of the association between Cd exposure and risk of prostate cancer was 1.66 (95% CI 1.10-2.50) in populations exposed to occupational Cd. In addition, high D-Cd intake (OR 1.07; 95% CI 0.96-1.20) and U-Cd concentration (OR 0.86; 95% CI 0.48-1.55) among the general population was not related to the increased risk of prostate cancer. In the dose analysis, the summary relative risk was 1.07 (95% CI 0.73-1.57) for each 0.5 μg/g creatinine increase in U-Cd and 1.02 (95% CI 0.99-1.06) for each 10 μg/day increase of dietary Cd intake. However, compared with nonoccupational exposure, high occupational Cd exposure may be associated with the increased risk of prostate cancer.This meta-analysis suggests high Cd exposure as a risk factor for prostate cancer in occupational rather than nonoccupational populations. However, these results should be carefully interpreted because of the significant heterogeneity among studies. Additional large-scale and high-quality prospective studies are needed to confirm the association between Cd exposure and risk of prostate cancer.

Post-Spaceflight (STS-135) Mouse Splenocytes Demonstrate Altered Activation Properties and Surface Molecule Expression

PubMed Central

Crucian, Brian; Sams, Clarence

2015-01-01

Alterations in immune function have been documented during or post-spaceflight and in ground based models of microgravity. Identification of immune parameters that are dysregulated during spaceflight is an important step in mitigating crew health risks during deep space missions. The in vitro analysis of leukocyte activity post-spaceflight in both human and animal species is primarily focused on lymphocytic function. This report completes a broader spectrum analysis of mouse lymphocyte and monocyte changes post 13 days orbital flight (mission STS-135). Analysis includes an examination in surface markers for cell activation, and antigen presentation and co-stimulatory molecules. Cytokine production was measured after stimulation with T-cell mitogen or TLR-2, TLR-4, or TLR-5 agonists. Splenocyte surface marker analysis immediate post-spaceflight and after in vitro culture demonstrated unique changes in phenotypic populations between the flight mice and matched treatment ground controls. Post-spaceflight splenocytes (flight splenocytes) had lower expression intensity of CD4+CD25+ and CD8+CD25+ cells, lower percentage of CD11c+MHC II+ cells, and higher percentage of CD11c+MHC I+ populations compared to ground controls. The flight splenocytes demonstrated an increase in phagocytic activity. Stimulation with ConA led to decrease in CD4+ population but increased CD4+CD25+ cells compared to ground controls. Culturing with TLR agonists led to a decrease in CD11c+ population in splenocytes isolated from flight mice compared to ground controls. Consequently, flight splenocytes with or without TLR-agonist stimulation showed a decrease in CD11c+MHC I+, CD11c+MHC II+, and CD11c+CD86+ cells compared to ground controls. Production of IFN-γ was decreased and IL-2 was increased from ConA stimulated flight splenocytes. This study demonstrated that expression of surface molecules can be affected by conditions of spaceflight and impaired responsiveness persists under culture conditions in vitro. PMID:25970640

Molecular cloning, sequence characterization and expression analysis of a CD63 homologue from the coleopteran beetle, Tenebrio molitor.

PubMed

Patnaik, Bharat Bhusan; Kang, Seong Min; Seo, Gi Won; Lee, Hyo Jeong; Patnaik, Hongray Howrelia; Jo, Yong Hun; Tindwa, Hamisi; Lee, Yong Seok; Lee, Bok Luel; Kim, Nam Jung; Bang, In Seok; Han, Yeon Soo

2013-10-15

CD63, a member of the tetraspanin membrane protein family, plays a pivotal role in cell growth, motility, signal transduction, host-pathogen interactions and cancer. In this work, the cDNA encoding CD63 homologue (TmCD63) was cloned from larvae of a coleopteran beetle, Tenebrio molitor. The cDNA is comprised of an open reading frame of 705 bp, encoding putative protein of 235 amino acid residues. In silico analysis shows that the protein has four putative transmembrane domains and one large extracellular loop. The characteristic "Cys-Cys-Gly" motif and "Cys188" residues are highly conserved in the large extracellular loop. Phylogenetic analysis of TmCD63 revealed that they belong to the insect cluster with 50%-56% identity. Analysis of spatial expression patterns demonstrated that TmCD63 mRNA is mainly expressed in gut and Malphigian tubules of larvae and the testis of the adult. Developmental expression patterns of CD63 mRNA showed that TmCD63 transcripts are detected in late larval, pupal and adult stages. Interestingly, TmCD63 transcripts are upregulated to the maximum level of 4.5 fold, in response to DAP-type peptidoglycan during the first 6 h, although other immune elicitors also caused significant increase to the transcript level at later time-points. These results suggest that CD63 might contribute to T. molitor immune response against various microbial pathogens.

Molecular Cloning, Sequence Characterization and Expression Analysis of a CD63 Homologue from the Coleopteran Beetle, Tenebrio molitor

PubMed Central

Patnaik, Bharat Bhusan; Kang, Seong Min; Seo, Gi Won; Lee, Hyo Jeong; Patnaik, Hongray Howrelia; Jo, Yong Hun; Tindwa, Hamisi; Lee, Yong Seok; Lee, Bok Luel; Kim, Nam Jung; Bang, In Seok; Han, Yeon Soo

2013-01-01

CD63, a member of the tetraspanin membrane protein family, plays a pivotal role in cell growth, motility, signal transduction, host-pathogen interactions and cancer. In this work, the cDNA encoding CD63 homologue (TmCD63) was cloned from larvae of a coleopteran beetle, Tenebrio molitor. The cDNA is comprised of an open reading frame of 705 bp, encoding putative protein of 235 amino acid residues. In silico analysis shows that the protein has four putative transmembrane domains and one large extracellular loop. The characteristic “Cys-Cys-Gly” motif and “Cys188” residues are highly conserved in the large extracellular loop. Phylogenetic analysis of TmCD63 revealed that they belong to the insect cluster with 50%–56% identity. Analysis of spatial expression patterns demonstrated that TmCD63 mRNA is mainly expressed in gut and Malphigian tubules of larvae and the testis of the adult. Developmental expression patterns of CD63 mRNA showed that TmCD63 transcripts are detected in late larval, pupal and adult stages. Interestingly, TmCD63 transcripts are upregulated to the maximum level of 4.5 fold, in response to DAP-type peptidoglycan during the first 6 h, although other immune elicitors also caused significant increase to the transcript level at later time-points. These results suggest that CD63 might contribute to T. molitor immune response against various microbial pathogens. PMID:24132157

Diagnostic Chemical Analysis of Exhaled Human Breath Using a Novel Sub-Millimeter Spectroscopic Approach

NASA Astrophysics Data System (ADS)

Fosnight, Alyssa M.; Moran, Benjamin L.; Branco, Daniela R.; Thomas, Jessica R.; Medvedev, Ivan R.

2013-06-01

As many as 3000 chemicals are reported to be found in exhaled human breath. Many of these chemicals are linked to certain health conditions and environmental exposures. Present state of the art techniques used for analysis of exhaled human breath include mass spectrometry based methods, infrared spectroscopic sensors, electro chemical sensors and semiconductor oxide based testers. Some of these techniques are commercially available but are somewhat limited in their specificity and exhibit fairly high probability of false alarm. Here, we present the results of our most recent study which demonstrated a novel application of a terahertz high resolutions spectroscopic technique to the analysis of exhaled human breath, focused on detection of ethanol in the exhaled breath of a person which consumed an alcoholic drink. This technique possesses nearly ``absolute'' specificity and we demonstrated its ability to uniquely identify ethanol, methanol, and acetone in human breath. This project is now complete and we are looking to extend this method of chemical analysis of exhaled human breath to a broader range of chemicals in an attempt to demonstrate its potential for biomedical diagnostic purposes.

The interpretation of simultaneous soft X-ray spectroscopic and imaging observations of an active region. [in solar corona

NASA Technical Reports Server (NTRS)

Davis, J. M.; Gerassimenko, M.; Krieger, A. S.; Vaiana, G. S.

1975-01-01

Simultaneous soft X-ray spectroscopic and broad-band imaging observations of an active region have been analyzed together to determine the parameters which describe the coronal plasma. From the spectroscopic data, models of temperature-emission measure-elemental abundance have been constructed which provide acceptable statistical fits. By folding these possible models through the imaging analysis, models which are not self-consistent can be rejected. In this way, only the oxygen, neon, and iron abundances of Pottasch (1967), combined with either an isothermal or exponential temperature-emission-measure model, are consistent with both sets of data. Contour maps of electron temperature and density for the active region have been constructed from the imaging data. The implications of the analysis for the determination of coronal abundances and for future satellite experiments are discussed.

Synthesis, spectroscopic characterization (FT-IR, FT-Raman, and NMR), quantum chemical studies and molecular docking of 3-(1-(phenylamino)ethylidene)-chroman-2,4-dione

NASA Astrophysics Data System (ADS)

Avdović, Edina H.; Milenković, Dejan; Dimitrić Marković, Jasmina M.; Đorović, Jelena; Vuković, Nenad; Vukić, Milena D.; Jevtić, Verica V.; Trifunović, Srećko R.; Potočňák, Ivan; Marković, Zoran

2018-04-01

The experimental and theoretical investigations of structure of the 3-(1-(phenylamino)ethylidene)-chroman-2,4-dione were performed. X-ray structure analysis and spectroscopic methods (FTIR and FT-Raman, 1H and 13C NMR), along with the density functional theory calculations (B3LYP functional with empirical dispersion corrections D3BJ in combination with the 6-311 + G(d,p) basis set), were used in order to characterize the molecular structure and spectroscopic behavior of the investigated coumarin derivative. Molecular docking analysis was carried out to identify the potency of inhibition of the title molecule against human's Ubiquinol-Cytochrome C Reductase Binding Protein (UQCRB) and Methylenetetrahydrofolate reductase (MTHFR). The inhibition activity was obtained for ten conformations of ligand inside the proteins.

First principles calculations of point defect diffusion in CdS buffer layers: Implications for Cu(In,Ga)(Se,S){sub 2} and Cu{sub 2}ZnSn(Se,S){sub 4}-based thin-film photovoltaics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varley, J. B.; Lordi, V.; He, X.

2016-01-14

We investigate point defects in CdS buffer layers that may arise from intermixing with Cu(In,Ga)Se{sub 2} (CIGSe) or Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe) absorber layers in thin-film photovoltaics (PV). Using hybrid functional calculations, we characterize the migration barriers of Cu, In, Ga, Se, Sn, Zn, Na, and K impurities and assess the activation energies necessary for their diffusion into the bulk of the buffer. We find that Cu, In, and Ga are the most mobile defects in CIGS-derived impurities, with diffusion expected to proceed into the buffer via interstitial-hopping and cadmium vacancy-assisted mechanisms at temperatures ∼400 °C. Cu is predicted to stronglymore » favor migration paths within the basal plane of the wurtzite CdS lattice, which may facilitate defect clustering and ultimately the formation of Cu-rich interfacial phases as observed by energy dispersive x-ray spectroscopic elemental maps in real PV devices. Se, Zn, and Sn defects are found to exhibit much larger activation energies and are not expected to diffuse within the CdS bulk at temperatures compatible with typical PV processing temperatures. Lastly, we find that Na interstitials are expected to exhibit slightly lower activation energies than K interstitials despite having a larger migration barrier. Still, we find both alkali species are expected to diffuse via an interstitially mediated mechanism at slightly higher temperatures than enable In, Ga, and Cu diffusion in the bulk. Our results indicate that processing temperatures in excess of ∼400 °C will lead to more interfacial intermixing with CdS buffer layers in CIGSe devices, and less so for CZTSSe absorbers where only Cu is expected to significantly diffuse into the buffer.« less

Phenomenological and Spectroscopic Analysis on the Effects of Sediment Ageing and Organic Carbon on the Fate of a PCB Congener Spiked to Sediment

EPA Science Inventory

This study assesses the full cycle transport and fate of a polychlorinated biphenyl (PCB) congener spiked to sediment to empirically and spectroscopically investigate the effects of sediment ageing and organic carbon on the adsorption, desorption, and reaction of the PCB. Caesar ...

Spectroscopic determination of anthraquinone in kraft pulping liquors using a membrane interface

Treesearch

X.S. Chai; X.T. Yang; Q.X. Hou; J.Y. Zhu; L.-G. Danielsson

2003-01-01

A spectroscopic technique for determining AQ in pulping liquor was developed to effectively separate AQ from dissolved lignin. This technique is based on a flow analysis system with a Nafion membrane interface. The AQ passed through the membrane is converted into its reduced form, AHQ, using sodium hydrosulfite. AHQ has distinguished absorption characteristics in the...

Increasing the quantitative credibility of open-path FT-IR spectroscopic data with focus on several properties of the background spectrum

USDA-ARS?s Scientific Manuscript database

The choice of the type of background spectrum affects the credibility of open-path Fourier transform infrared (OP/FT-IR) spectroscopic data, and consequently the quality of data analysis. We systematically investigated several properties of the background spectrum. The results show that a short-pa...

In vitro FTIR microspectroscopy analysis of primary oral squamous carcinoma cells treated with cisplatin and 5-fluorouracil: a new spectroscopic approach for studying the drug-cell interaction.

PubMed

Giorgini, Elisabetta; Sabbatini, Simona; Rocchetti, Romina; Notarstefano, Valentina; Rubini, Corrado; Conti, Carla; Orilisi, Giulia; Mitri, Elisa; Bedolla, Diana E; Vaccari, Lisa

2018-06-22

In the present study, human primary oral squamous carcinoma cells treated with cisplatin and 5-fluorouracil were analyzed, for the first time, by in vitro FTIR Microspectroscopy (FTIRM), to improve the knowledge on the biochemical pathways activated by these two chemotherapy drugs. To date, most of the studies regarding FTIRM cellular analysis have been executed on fixed cells from immortalized cell lines. FTIRM analysis performed on primary tumor cells under controlled hydrated conditions provides more reliable information on the biochemical processes occurring in in vivo tumor cells. This spectroscopic analysis allows to get on the same sample and at the same time an overview of the composition and structure of the most remarkable cellular components. In vitro FTIRM analysis of primary oral squamous carcinoma cells evidenced a time-dependent drug-specific cellular response, also including apoptosis triggering. Furthermore, the univariate and multivariate analyses of IR data evidenced meaningful spectroscopic differences ascribable to alterations affecting cellular proteins, lipids and nucleic acids. These findings suggest for the two drugs different pathways and extents of cellular damage, not provided by conventional cell-based assays (MTT assay and image-based cytometry).