A Methoxydiphenylamine-Substituted Carbazole Twin Derivative: An Efficient Hole-Transporting Material for Perovskite Solar Cells.

PubMed

Gratia, Paul; Magomedov, Artiom; Malinauskas, Tadas; Daskeviciene, Maryte; Abate, Antonio; Ahmad, Shahzada; Grätzel, Michael; Getautis, Vytautas; Nazeeruddin, Mohammad Khaja

2015-09-21

The small-molecule-based hole-transporting material methoxydiphenylamine-substituted carbazole was synthesized and incorporated into a CH3NH3PbI3 perovskite solar cell, which displayed a power conversion efficiency of 16.91%, the second highest conversion efficiency after that of Spiro-OMeTAD. The investigated hole-transporting material was synthesized in two steps from commercially available and relatively inexpensive starting reagents. Various electro-optical measurements (UV/Vis, IV, thin-film conductivity, hole mobility, DSC, TGA, ionization potential) have been carried out to characterize the new hole-transporting material. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Data-driven discovery of energy materials: efficient BaM2Si3O10 : Eu2+ (M = Sc, Lu) phosphors for application in solid state white lighting.

PubMed

Brgoch, Jakoah; Hasz, Kathryn; Denault, Kristin A; Borg, Christopher K H; Mikhailovsky, Alexander A; Seshadri, Ram

2014-01-01

In developing phosphors for application in solid state lighting, it is advantageous to target structures from databases with highly condensed polyhedral networks that produce rigid host compounds. Rigidity limits channels for non-radiative decay that will decrease the luminescence quantum yield. BaM(2)Si(3)O(10) (M = Sc, Lu) follows this design criterion and is studied here as an efficient Eu(2+)-based phosphor. M = Sc(3+) and Lu(3+) compounds with Eu(2+) substitution were prepared and characterized using synchrotron X-ray powder diffraction and photoluminescence spectroscopy. Substitution with Eu(2+) according to Ba(1-x)Eu(x)Sc(2)Si(3)O(10) and Ba(1-x)Eu(x)Lu(2)Si(3)O(10) results in UV-to-blue and UV-to-blue-green phosphors, respectively. Interestingly, substitution with Eu(2+) in the Lu(3+) containing material produces two emission peaks at low temperature and with 365 nm excitation, as allowed by the two substitution sites. The photoluminescence of the Sc(3+) compound is robust at high temperature, decreasing by only 25% of its room temperature intensity at 503 K, while the Lu-analogue suffers a large drop (75%) from its room temperature intensity. The decrease in emission intensity is explained as stemming from charge transfer quenching due to the short distances separating the luminescent centers on the Lu(3+) substitution site. The correlation between structure and optical response in these two compounds indicates that even though the structures are three-dimensionally connected, high symmetry is required to prevent structural distortions that could impact photoluminescence.

The Effect of Sulfur Substitution on the Excited-State Dynamics of DNA and RNA Base Derivatives

NASA Astrophysics Data System (ADS)

Pollum, Marvin; Crespo-Hernández, Carlos E.

2014-06-01

Substitution of oxygen by a sulfur atom in the natural DNA and RNA bases gives rise to a family of derivatives commonly known as the thiobases. Upon excitation with UV radiation, the natural bases are able to quickly and efficiently dissipate the imparted energy as heat to their surroundings. Thiobases, on the other hand, relax into a long-lived triplet excited state in quantum yields that approach unity. This finding has both fundamental and biological relevance because the triplet state plays a foremost role in the photochemistry of the thiobases, this is especially important in the current medicinal applications of thiobase derivatives. Using femtosecond transient absorption spectroscopy, we are able uncover the ultrafast dynamics leading to the population of this reactive triplet state. In particular, I will present our results on how the site of sulfur substitution and the degree of substitution impact these dynamics and I will compare these experimental results to some recent computational work. Pinning down the excited-state dynamics of the thiobases is important to furthering the understanding of dynamics in natural DNA/RNA bases, as well as to the discovery of thiobase derivatives with desirable therapeutic properties. The authors acknowledge the CAREER program of the National Science Foundation (Grant No. CHE-1255084) for financial support.

40 CFR 721.8775 - Substituted pyridines.

Code of Federal Regulations, 2011 CFR

2011-07-01

... tertiary waste treatment will occur, or treatment in a lined, self-contained solar evaporation pond where...-contained solar evaporation pond where UV light will degrade the substance, the number of kilograms per day... a lined, self-contained solar evaporation pond where UV light will degrade the substance, the number...

40 CFR 721.8775 - Substituted pyridines.

Code of Federal Regulations, 2010 CFR

2010-07-01

... tertiary waste treatment will occur, or treatment in a lined, self-contained solar evaporation pond where...-contained solar evaporation pond where UV light will degrade the substance, the number of kilograms per day... a lined, self-contained solar evaporation pond where UV light will degrade the substance, the number...

Characterisation of the ester-substituted products of the reaction of p-t-butyl calix[4]arene and ethyl bromoacetate using LC-UV-MS and LC-DAD.

PubMed

McMahon, Gillian; Wall, Rachel; Nolan, Kieran; Diamond, Dermot

2002-07-19

A series of derivatisation reactions between p-t-butyl calix[4]arene and ethyl bromoacetate were carried out in order to prepare 1,3 diester substituted calix[4]arene. Mass spectral data, obtained from direct injection of samples, indicated that the reactions were rich in the desired product. Since the ultra violet (UV) spectra of the desired product and possible impurities are very similar, liquid chromatography (LC) chromatographic data seemed to corroborate these results. However, when on-line LC-UV-MS was carried out and each LC peak subjected to MS analysis as it eluted, a very different picture emerged. It was found that many of these reactions actually contained high levels of the monoester product which, having less affinity for sodium in the MS, is therefore seriously underestimated in any direct injection assay. LC-diode array detection (DAD) methods were also used to help successfully identify and characterise the compounds being formed in these complex reactions. The overall results obtained in this paper allowed the optimal reaction conditions to be determined for this reaction. LC-MS analysis of the chromatographic peaks also identified the presence of two isomers of the diester substituted calix[4]arene (1,3 and 1,2 diesters). The combination of LC and UV/MS detection is required for accurate analysis of the products of such reactions.

Toluene nitration in irradiated nitric acid and nitrite solutions

NASA Astrophysics Data System (ADS)

Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.

2011-04-01

The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the rad NO2 radical.

Resonance Enhanced Multi-Photon Ionization and Uv-Uv Hole-Burning Spectroscopic Studies of Jet-Cooled Acetanilide Derivatives

NASA Astrophysics Data System (ADS)

Moon, Ceol Joo; Min, Ahreum; Ahn, Ahreum; Lee, Seung Jun; Choi, Myong Yong; Kim, Seong Keun

2013-06-01

Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.

Mechanisms of the Formation of Adenine, Guanine, and Their Analogues in UV-Irradiated Mixed NH3:H2O Molecular Ices Containing Purine

NASA Astrophysics Data System (ADS)

Bera, Partha P.; Stein, Tamar; Head-Gordon, Martin; Lee, Timothy J.

2017-08-01

We investigated the formation mechanisms of the nucleobases adenine and guanine and the nucleobase analogues hypoxanthine, xanthine, isoguanine, and 2,6-diaminopurine in a UV-irradiated mixed 10:1 H2O:NH3 ice seeded with precursor purine by using ab initio and density functional theory computations. Our quantum chemical investigations suggest that a multistep reaction mechanism involving purine cation, hydroxyl and amino radicals, together with water and ammonia, explains the experimentally obtained products in an independent study. The relative abundances of these products appear to largely follow from relative thermodynamic stabilities. The key role of the purine cation is likely to be the reason why purine is not functionalized in pure ammonia ice, where cations are promptly neutralized by free electrons from NH3 ionization. Amine group addition to purine is slightly favored over hydroxyl group attachment based on energetics, but hydroxyl is much more abundant due to higher abundance of H2O. The amino group is preferentially attached to the 6 position, giving 6-aminopurine, that is, adenine, while the hydroxyl group is preferentially attached to the 2 position, leading to 2-hydroxypurine. A second substitution by hydroxyl or amino group occurs at either the 6 or the 2 position depending on the first substitution. Given that H2O is far more abundant than NH3 in the experimentally studied ices (as well as based on interstellar abundances), xanthine and isoguanine are expected to be the most abundant bi-substituted photoproducts.

Nanoparticles of nickel oxide: growth and organization on zinc-substituted anionic clay matrix by one-pot route at room temperature

NASA Astrophysics Data System (ADS)

Carja, Gabriela; Nakajima, Akira; Dranca, Cristian; Okada, Kiyoshi

2010-10-01

A room temperature nanocarving strategy is developed for the fabrication of nanoparticles of nickel oxide on zinc-substituted anionic clay matrix (Ni/ZnLDH). It is based on the growth and organization of nanoparticles of nickel oxide which occur during the structural reconstruction of the layered structure of the anionic clay in NiSO4 aqueous solution. No organic compounds are used during the fabrication. The described material was characterized by X-ray diffraction (XRD), IR spectroscopy (FTIR), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that the nickel-clay nanoarchitecture consists of small nanoparticles of nickel oxide (average size 7 nm) deposited on the larger nanoparticles (average size 90 nm) of zinc-substituted clay. The optical properties of the new nickel-zinc formulation are studied by UV-Vis.

Competitive/co-operative interactions in acid base sandwich: role of cation vs. substituents.

PubMed

Kalpana, Ayyavoo; Akilandeswari, Lakshminarayanan

2017-11-15

The cation-π interaction can be envisaged as a lewis acid base interaction, and it is in line with Pearson's acid base concept. The critical examination of interactions between the π-acids (alkali metal cations - Li + , Na + and alkaline earth metal cations Mg 2+ , Ca 2+ ) on one face and tripodal Cr(CO) 3 moiety on the other π face of substituted arenes demonstrates the role of cation and substitutents in manipulating the interactions between them. The interaction of the two π acids on both faces of arene is not expectedly additive, rather it shows either depreciation of interaction energy revealing the competition of acids toward the base or enhancement of interaction energy denoting a cooperative effect. Among the metal cations under study, Mg 2+ shows a cooperative gesture. Although the substituents play a meek role, they unfailingly exert their electronic effects and are amply documented by excellent correlation of various parameters with the Hammett constant σ m . The elusive switching of λ max from the UV to IR region on binding Mg 2+ with substituted arene-Cr(CO) 3 complex is a characteristic clue that TDDFT can help design the ionic sensors for Mg 2+ cations.

Abnormal, Error-Prone Bypass of Photoproducts by Xeroderma Pigmentosum Variant Cell Extracts Results in Extreme Strand Bias for the Kinds of Mutations Induced by UV Light

PubMed Central

McGregor, W. Glenn; Wei, Dong; Maher, Veronica M.; McCormick, J. Justin

1999-01-01

Xeroderma pigmentosum (XP) is a rare genetic disease characterized by a greatly increased susceptibility to sunlight-induced skin cancer. Cells from the majority of patients are defective in nucleotide excision repair. However, cells from one set of patients, XP variants, exhibit normal repair but are abnormally slow in replicating DNA containing UV photoproducts. The frequency of UV radiation-induced mutations in the XP variant cells is significantly higher than that in normal human cells. Furthermore, the kinds of UV-induced mutations differ very significantly from normal. Instead of transitions, mainly C→T, 30% of the base substitutions consist of C→A transversions, all arising from photoproducts located in one strand. Mutations involving cytosine in the other strand are almost all C→T transitions. Forty-five percent of the substitutions involve thymine, and the majority are transversions. To test the hypothesis that the UV hypermutability and the abnormal spectrum of mutations result from abnormal bypass of photoproducts in DNA, we compared extracts from XP variant cells with those from HeLa cells and a fibroblast cell strain, MSU-1.2, for the ability to replicate a UV-irradiated form I M13 phage. The M13 template contains a simian virus 40 origin of replication located directly to the left or to the right of the target gene, lacZα, so that the template for the leading and lagging strands of DNA replication is defined. Reduction of replication to ∼37% of the control value required only 1 photoproduct per template for XP variant cell extracts, but ∼2.2 photoproducts for HeLa or MSU-1.2 cell extracts. The frequency of mutants induced was four times higher with XP variant cell extracts than with HeLa or MSU-1.2 cell extracts. With XP variant cell extracts, the proportion of C→A transversions reached as high as 43% with either M13 template and arose from photoproducts located in the template for leading-strand synthesis; with HeLa or MSU-1.2 cell extracts, this value was only 5%, and these arose from photoproducts in either strand. With the XP variant extracts, 26% of the substitutions involved thymine, and virtually all were T→A transversions. Sequence analysis of the coding region of the catalytic subunit of DNA polymerase delta in XP variant cell lines revealed two polymorphisms, but these do not account for the reduced bypass fidelity. Our data indicate that the UV hypermutability of XP variant cells results from reduced bypass fidelity and that unlike for normal cells, bypass of photoproducts involving cytosine in the template for the leading strand differs significantly from that of photoproducts in the lagging strand. PMID:9858539

Determining optimum wavelength of ultraviolet rays to pre-exposure of non-uniformity error correction in Gafchromic EBT2 films

NASA Astrophysics Data System (ADS)

Katsuda, Toshizo; Gotanda, Rumi; Gotanda, Tatsuhiro; Akagawa, Takuya; Tanki, Nobuyoshi; Kuwano, Tadao; Noguchi, Atsushi; Yabunaka, Kouichi

2018-03-01

Gafchromic films have been used to measure X-ray doses in diagnostic radiology such as computed tomography. The double-exposure technique is used to correct non-uniformity error of Gafchromic EBT2 films. Because of the heel effect of diagnostic x-rays, ultraviolet A (UV-A) is intended to be used as a substitute for x-rays. When using a UV-A light-emitting diode (LED), it is necessary to determine the effective optimal UV wavelength for the active layer of Gafchromic EBT2 films. This study evaluated the relation between the increase in color density of Gafchromic EBT2 films and the UV wavelengths. First, to correct non-uniformity, a Gafchromic EBT2 film was pre-irradiated using uniform UV-A radiation for 60 min from a 72-cm distance. Second, the film was irradiated using a UV-LED with a wavelength of 353-410 nm for 60 min from a 5.3-cm distance. The maximum, minimum, and mean ± standard deviation (SD) of pixel values of the subtraction images were evaluated using 0.5 inches of a circular region of interest (ROI). The highest mean ± SD (8915.25 ± 608.86) of the pixel value was obtained at a wavelength of 375 nm. The results indicated that 375 nm is the most effective and sensitive wavelength of UV-A for Gafchromic EBT2 films and that UV-A can be used as a substitute for x-rays in the double-exposure technique.

Synthesis and characterization of Heck-cross coupling 4-(4-nitrostyryl) aniline as potential precursor in Schiff-base synthesis

NASA Astrophysics Data System (ADS)

Hassan, Norhafiefa; Izwani, Fatin; Yusoff, H. M.

2017-09-01

This is a preliminary study of alkoxy substituted Heck-schiff base compound as recognition layer in electrochemical DNA sensor for liver cancer. 4-(4-nitrostyryl)aniline was synthesized by bis (triphenylphosphine) palladium (II) dichloride as catalyst and has been characterized by using Fourier transform-infrared spectrometer (FTIR), UV-Vis spectrophotometer and Nuclear Magnetic Resonance (NMR) spectra. The result obtained from FTIR show that there are formation of N=O (NO2) asymmetric stretching vibrations 1340 cm-1. In UV-vis, absorbance of NO2 can be observed at peak 410 nm. While in the 1H NMR and 13C NMR the peak of C-C coupling was found in the range of δH 6.84-7.09 ppm and δC 125.23 ppm.

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

2017-08-01

In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

[Synthesis, characterization and fluorescent properties of copper phthalocyanine derivates substituted by aliphatic alcohol].

PubMed

Zhang, Liang; Xu, Qing-Feng; Lu, Jian-Mei; Yao, She-Chun

2007-04-01

A series of copper phthalocyanine derivatives substituted by aliphatic chain were obtained by the reaction of tetra-formyl chloride copper phthalocyanine and aliphatic alcohol such as n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-caprylic alcohol and lauryl alcohol. IR, UV-Vis, elemental analysis and 1H NMR verified the structures and substituting degree. The solubility and the relationship between fluorescence and concentration and substituting group were studied in organic solution. It was confirmed that the solubility in organic solution was improved greatly, the fluorescence did not change in linear according to the concentration and the fluorescence of copper phthalocyanine derivatives substituted by the long alkyl was stronger than that substituted by the relatively short alkyl.

Abnormal ultraviolet mutagenic spectrum in plasmid DNA replicated in cultured fibroblasts from a patient with the skin cancer-prone disease, xeroderma pigmentosum

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

Seetharam, S.; Protic-Sabljic, M.; Seidman, M.M.

1987-12-01

A shuttle vector plasmid, pZ189, was utilized to assess the types of mutations that cells from a patient with xeroderma pigmentosum, complementation group D, introduce into ultraviolet (UV) damaged, replicating DNA. Patients with xeroderma pigmentosum have clinical and cellular UV hypersensitivity, increased frequency of sun-induced skin cancer, and deficient DNA repair. In comparison to UV-treated pZ189 replicated in DNA repair-proficient cells, there were fewer surviving plasmids, a higher frequency of plasmids with mutations, fewer plasmids with two or more mutations in the marker gene, and a new mutagenic hotspot. The major type of base substitution mutation was the G:C tomore » A:T transition with both cell lines. These results, together with similar findings published earlier with cells from a xeroderma pigmentosum patient in complementation group A, suggest that isolated G:C to A:T somatic mutations may be particularly important in generation of human skin cancer by UV radiation.« less

On the Interpretation of the Influence of Substituents on the UV-Spectroscopic Properties of Benzimidazole and Indazole Derivatives (In German)

NASA Astrophysics Data System (ADS)

Fabian, Walter

1983-12-01

On the interpretation of the influence of substituents on the UV-spectroscopic properties of benzimidazole and indazole derivatives. The UV spectra of a series of substituted benzimidazoles and indazoles were calculated by means of semiempirical quantum chemical methods (PPP, CNDO/S-CI). The results of the PPP calculations were subjected to a configuration analysis. Using this method, the influence of the nature and position of substituents on the absorption characteristics could be rationalized.

Synthesis and XRD, FT-IR vibrational, UV-vis, and nonlinear optical exploration of novel tetra substituted imidazole derivatives: A synergistic experimental-computational analysis

NASA Astrophysics Data System (ADS)

Ahmad, Muhammad Saeed; Khalid, Muhammad; Shaheen, Muhammad Ashraf; Tahir, Muhammad Nawaz; Khan, Muhammad Usman; Braga, Ataualpa Albert Carmo; Shad, Hazoor Ahmad

2018-04-01

Heterocyclic compounds have potential applications in many fields of life. We synthesized novel tetra substituted imidazoles by four-component condensation of benzil, substituted aldehydes, substituted anilines and ammonium acetate as a source of ammonia and acetic acid as the solvent. Their chemical structures were resolved through X-ray crystallographic and spectroscopic (Fourier transform IR and UV-vis) techniques. In addition to experimental analysis, density functional theory (DFT) calculations at the B3LYP/6-311 + G(d,p) level were performed on 4-bromo-2-(1-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazole-2-yl)phenol (1), 4-bromo-2-(1-(1-naphthalen-yl)-4,5-diphenyl-1H-imidazole-2-yl)phenol (2), and 2-(1-(2-chlorophenyl)-4,5-diphenyl-1-H-imidazole-2-yl)-6-methoxyphenol (3) to obtain the optimized geometry and spectroscopic (Fourier transform IR and UV-vis) and non-linear optical properties. Frontier molecular orbital analysis was performed at the Hartee-Fock/6-311+g(d,p) and DFT/B3LYP/6-311+G(d,p) levels of theory. Natural bond orbital (NBO) and UV-vis spectral analyses were performed at the M06-2X/6-31+G(d,p) and time-dependent DFT/B3LYP/6-311+G(d,p) levels, respectively. Overall, the DFT findings show good agreement with the experimental data. The hyper conjugative interaction network, which is responsible for the stability of compounds 1, 2 and 3 was explored by the NBO approach. The global reactivity parameters were explored with use of the energy of the frontier molecular orbitals. DFT calculations predict the first-order hyperpolarizabilities of compounds 1, 2 and 3 are 294.89 × 10-30, 219.45 × 10-30 and 146.77 × 10-30 esu, respectively. A two-state model was used to describe the non-linear optical properties of the compounds investigated.

Roles for the yeast RAD18 and RAD52 DNA repair genes in UV mutagenesis.

PubMed

Armstrong, J D; Chadee, D N; Kunz, B A

1994-11-01

Experimental evidence indicates that although the Saccharomyces cerevisiae RAD18 and RAD52 genes are not required for nucleotide excision repair, they function in the processing of UV-induced DNA damage in yeast. Conflicting statements regarding the UV mutability of strains deleted for RAD18 prompted us to re-examine the influence of RAD18, and RAD52, on UV mutagenesis. To do so, we characterized mutations induced by UV in SUP4-o, a yeast suppressor tRNA gene. SUP4-o was maintained on a plasmid in isogenic strains that either carried one of two different rad18 deletions (rad18 delta) or had RAD52 disrupted. Both rad18 deletions decreased the frequency of UV-induced SUP4-o mutations to levels close to those for spontaneous mutagenesis in the rad18 delta backgrounds, and prevented a net increase in mutant yield. A detailed analysis of mutations isolated after UV irradiation of one of the rad18 delta strains uncovered little evidence of the specificity features typical for UV mutagenesis in the isogenic repair-proficient (RAD) parent (e.g., predominance of G.C-->A.T transitions). Evidently, UV induction of SUP4-o mutations is highly dependent on the RAD18 gene. Compared to the RAD strain, disruption of RAD52 reduced the frequency and yield of UV mutagenesis by about two-thirds. Closer inspection revealed that 80% of this reduction was due to a decrease in the frequency of G.C-->A.T transitions. In addition, there were differences in the distributions and site specificities of single base-pair substitutions. Thus, RAD52 also participates in UV mutagenesis of a plasmid-borne gene in yeast, but to a lesser extent than RAD18.

Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

PubMed Central

Takeshita, Yuki; Takakura, Kazuya; Akitsu, Takashiro

2015-01-01

We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO2 in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions. PMID:25686033

Crystal structures and catalytic performance of three new methoxy substituted salen type nickel(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine

NASA Astrophysics Data System (ADS)

Ghaffari, Abolfazl; Behzad, Mahdi; Pooyan, Mahsa; Amiri Rudbari, Hadi; Bruno, Giuseppe

2014-04-01

Three new nickel(II) complexes of a series of methoxy substituted salen type Schiff base ligands were synthesized and characterized by IR, UV-Vis and 1H NMR spectroscopy and elemental analysis. The ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with n-methoxysalicylaldehyde (n = 3, 4 and 5). Crystal structures of these complexes were determined. Electrochemical behavior of the complexes was studied by means of cyclic voltammetry in DMSO solutions. Catalytic performance of the complexes was studied in the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant under various conditions to find the optimum operating parameters. Low catalytic activity with moderate epoxide selectivity was observed in in-solvent conditions but in the solvent-free conditions, enhanced catalytic activity with high epoxide selectivity was achieved.

Fluoride-responsive gelator and colorimetric sensor based on simple and easy-to-prepare cyano-substituted amide.

PubMed

Zhang, Yuping; Jiang, Shimei

2012-09-14

A new and easy-to-prepare gelator based on cyano-substituted amide (BPNIA) was designed and synthesized. BPNIA could form thermoreversible gel in DMSO-H(2)O (v/v, 9 : 1) and ultrasound-stimulated gel in DMSO. FT-IR, UV-vis and XRD spectra indicated that the gelator molecules self-assemble into a fibrous network resulting from the cooperation of intermolecular hydrogen bonding, π-π stacking and cyano interactions. BPNIA can act as a highly selective colorimetric sensor for fluoride in DMSO, overcoming the interference of H(2)PO(4)(-), AcO(-) and other halide anions. The deprotonation of the NH groups is responsible for the dramatic color change from colorless to yellow. Interestingly, the organogel of BPNIA could allow a two channel fluoride response by proton controlled reversible sol-gel transition and color changes.

[The effect of structure of benzimidazoles on the character of forming intramolecular cross-links in DNA and chromatin].

PubMed

Mil', E M; Zhil'tsova, V M; Biniukov, V I; Zhizhina, G P; Stoliarova, L G; Kuznetsov, Iu P

1994-01-01

An investigation of a number of benzimidazole class preparations, being distinguished by a position of aminomethyl substitutes, has been carried out. It has been shown, that the non-substituted preparation BIO-10 does not form UV-cross-links in DNA and chromatine; BIO-40, having one substitute in the position 2, causes the formation of inter-molecular cross-links DNA-DNA. The preparation BIO-50, having 2 aminomethyl groups in the imidazole nucleus positions 2 and 6, forms cross-links DNA-DNA and DNA-protein in chromatine. The generation of radicals by the preparations BIO-10 and BIO-50 has been studied by the EPR-method by use of spin trap. It has been demonstrated, that BIO-10, unlike BIO-50, actively generates superoxide. A supposition has been made, that an UV-formation of superoxide-radical in the presence of BIO-10 might be a reason of DNA-macromolecule destruction.

[The UV-Vis spectra and substituent effect of organoimido derivatives of polyoxometalates].

PubMed

Li, Qiang; Wei, Yong-ge; Wang, Yuan; Guo, Hong-you

2005-06-01

In the presence of a carbodiimine, i.e. DCC, a series of organoimido derivatives of polyoxometalates have been synthesized via the reaction of [alpha-Mo8O26]4- with aromatic amines and its hydrochloride salt. Elemental analysis, IR, 1H-NMR and UV-Vis spectra were used to characterize those hybrids, in particular their UV-Vis spectra have been studied. The results show that typical metal-ligand charge transfer (MLCT) transitions occur in the organic-inorganic hybrid molecules. There is a good linear relationship between the shift of UV-Vis absorptions (delta lamda max) and conjugation effect of the p-substituted group (sigmaR).

Maleate/vinyl ether UV-cured coatings: Effects of composition on curing and properties

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

Noren, G.K.

1996-10-01

The effect of the composition of the maleate polyester and the vinyl ether terminated compound on their UV-curing and properties has been investigated. Linear unsaturated polyester resins based on maleic anhydride and 1,5-pentane diol were synthesized. The molecular weight of the unsaturated polyesters was varied by changing the ratio of maleic anhydride to 1,5-pentane diol and the double bond equivalent weight was varied by replacing maleic anhydride with succinic anhydride. Coating formulations containing these unsaturated polyesters, triethylene glycol divinyl ether and a free radical photoinitiator were crosslinked in the presence of UV light. The coatings were very brittle, exhibiting tensilemore » strengths in the range of 1.5-4.0 MPa and elongations of only 3-7%. Diethyl maleate and isobutyl vinyl ether were effective diluents for reducing viscosity but reduced the cure speed. A vinyl ether urethane oligomer was synthesized and enhanced the flexibility and toughness of the coatings when substituted for triethylene glycol divinyl ether.« less

Fabrication and characterization of environmental-friendly Ni1-xRxTiO3 nanopigments with high NIR reflectance

NASA Astrophysics Data System (ADS)

Tong, Yu-Ping; Chen, Zheng; Wang, Hui-Xian; Zhang, Xu-Fang; Ma, Jun-Tao; Chen, Xi

2015-04-01

A series of novel high dispersed environmental-friendly nanopigments based on NiTiO3 doped with rare earth ion such as Y, La, Eu, Sm have been developed. The products were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), commission internationale de l'Eclairage (CIE) 1976 L*α*b* color scales and UV-Vis-near-infrared radiation (NIR) reflectance spectroscopy. The substitution of R3+ for Ni2+ in NiTiO3 can improve the yellowness of pigments, especially for Eu3+ substitution. The sample with the substitution of Eu3+ for Ni2+ processes the highest NIR reflectance and enhances the NIR reflectance to 89.0%. SEM results revealed that the obtained pigments were composed of well-dispersed spherical-like particles with the range of 40-60 nm. EDS results indicated that the distribution of Ni, Ti, R, O element was considerably uniform with no chemical segregation phenomenon.

Ultraviolet 320 nm laser excitation for flow cytometry.

PubMed

Telford, William; Stickland, Lynn; Koschorreck, Marco

2017-04-01

Although multiple lasers and high-dimensional analysis capability are now standard on advanced flow cytometers, ultraviolet (UV) lasers (usually 325-365 nm) remain an uncommon excitation source for cytometry. This is primarily due to their cost, and the small number of applications that require this wavelength. The development of the Brilliant Ultraviolet (BUV fluorochromes, however, has increased the importance of this formerly niche excitation wavelength. Historically, UV excitation was usually provided by water-cooled argon- and krypton-ion lasers. Modern flow cytometers primary rely on diode pumped solid state lasers emitting at 355 nm. While useful for all UV-excited applications, DPSS UV lasers are still large by modern solid state laser standards, and remain very expensive. Smaller and cheaper near UV laser diodes (NUVLDs) emitting at 375 nm make adequate substitutes for 355 nm sources in many situations, but do not work as well with very short wavelength probes like the fluorescent calcium chelator indo-1. In this study, we evaluate a newly available UV 320 nm laser for flow cytometry. While shorter in wavelength that conventional UV lasers, 320 is close to the 325 nm helium-cadmium wavelength used in the past on early benchtop cytometers. A UV 320 nm laser was found to excite almost all Brilliant Ultraviolet dyes to nearly the same level as 355 nm sources. Both 320 nm and 355 nm sources worked equally well for Hoechst and DyeCycle Violet side population analysis of stem cells in mouse hematopoetic tissue. The shorter wavelength UV source also showed excellent excitation of indo-1, a probe that is not compatible with NUVLD 375 nm sources. In summary, a 320 nm laser module made a suitable substitute for conventional 355 nm sources. This laser technology is available in a smaller form factor than current 355 nm units, making it useful for small cytometers with space constraints. © 2017 International Society for Advancement of Cytometry. © 2017 International Society for Advancement of Cytometry.

Phosphorylation of Nucleotide Excision Repair Factor Xeroderma Pigmentosum Group A by Ataxia Telangiectasia Mutated and Rad3-Related-Dependent Checkpoint Pathway Promotes Cell Survival in Response to UV Irradiation

PubMed Central

Wu, Xiaoming; Shell, Steven M.; Yang, Zhengguan; Zou, Yue

2006-01-01

DNA damage triggers complex cellular responses in eukaryotic cells, including initiation of DNA repair and activation of cell cycle checkpoints. In addition to inducing cell cycle arrest, checkpoint also has been suggested to modulate a variety of other cellular processes in response to DNA damage. In this study, we present evidence showing that the cellular function of xeroderma pigmentosum group A (XPA), a major nucleotide excision repair (NER) factor, could be modulated by checkpoint kinase ataxia-telangiectasia mutated and Rad3-related (ATR) in response to UV irradiation. We observed the apparent interaction and colocalization of XPA with ATR in response to UV irradiation. We showed that XPA was a substrate for in vitro phosphorylation by phosphatidylinositol-3-kinase-related kinase family kinases whereas in cells XPA was phosphorylated in an ATR-dependent manner and stimulated by UV irradiation. The Ser196 of XPA was identified as a biologically significant residue to be phosphorylated in vivo. The XPA-deficient cells complemented with XPA-S196A mutant, in which Ser196 was substituted with an alanine, displayed significantly higher UV sensitivity compared with the XPA cells complemented with wild-type XPA. Moreover, substitution of Ser196 with aspartic acid for mimicking the phosphorylation of XPA increased the cell survival to UV irradiation. Taken together, our results revealed a potential physical and functional link between NER and the ATR-dependent checkpoint pathway in human cells and suggested that the ATR checkpoint pathway could modulate the cellular activity of NER through phosphorylation of XPA at Ser196 on UV irradiation. PMID:16540648

Analysis of point mutations in an ultraviolet-irradiated shuttle vector plasmid propagated in cells from Japanese xeroderma pigmentosum patients in complementation groups A and F

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

Yagi, T.; Tatsumi-Miyajima, J.; Sato, M.

1991-06-15

To assess the contribution to mutagenesis by human DNA repair defects, a UV-treated shuttle vector plasmid, pZ189, was passed through fibroblasts derived from Japanese xeroderma pigmentosum (XP) patients in two different DNA repair complementation groups (A and F). Patients with XP have clinical and cellular UV hypersensitivity, increased frequency of skin cancer, and defects in DNA repair. The XP DNA repair defects represented by complementation groups A (XP-A) and F (XP-F) are more common in Japan than in Europe or the United States. In comparison to results with DNA repair-proficient human cells (W138-VA13), UV-treated pZ189 passed through the XP-A (XP2OS(SV))more » or XP-F (XP2YO(SV)) cells showed fewer surviving plasmids (XP-A less than XP-F) and a higher frequency of mutated plasmids (XP-A greater than XP-F). Base sequence analysis of more than 200 mutated plasmids showed the major type of base substitution mutation to be the G:C----A:T transition with all three cell lines. The XP-A and XP-F cells revealed a higher frequency of G:C----A:T transitions and a lower frequency of transversions among plasmids with single or tandem mutations and a lower frequency of plasmids with multiple point mutations compared to the normal line. The spectrum of mutations in pZ189 with the XP-A cells was similar to that with the XP-F cells. Seventy-six to 91% of the single base substitution mutations occurred at G:C base pairs in which the 5{prime}-neighboring base of the cytosine was thymine or cytosine. These studies indicate that the DNA repair defects in Japanese XP patients in complementation groups A and F result in different frequencies of plasmid survival and mutagenesis but in similar types of mutagenic abnormalities despite marked differences in clinical features.« less

The structural and spectroscopic investigation of 2-chloro-3-methylquinoline by DFT method and UV-Vis, NMR and vibrational spectral techniques combined with molecular docking analysis

NASA Astrophysics Data System (ADS)

Kose, Etem; Atac, Ahmet; Bardak, Fehmi

2018-07-01

This study comprises the structural and spectroscopic evaluation of a quinoline derivative, 2-chloro-3-methylquinoline (2Cl3MQ), via UV-Vis, 1H and 13C NMR, FT-IR and FT-Raman techniques experimentally, theoretically with DFT and TD-DFT quantum chemical calculations at B3LYP/6-311++G (d, p) level of theory, and investigation of the in silico pharmaceutical potent of 2Cl3MQ in comparison to 2ClnMQ (n = 3,4,7,8,9,10) substituted quinolines. The experimental measurements were recorded as follows; UV-vis spectra were obtained in the range of 200-400 nm in the water and ethanol solvents. 1H and 13C NMR spectra were recorded in CDCl3. Vibrational spectra were obtained in the region of 4000-400 cm-1 and 3500-10 cm-1 for FT-IR and FT-Raman spectra, respectively. Structural and spectroscopic features obtained through theoretical evaluations include: electrostatic features, atomic charges and molecular electrostatic potential surface, the frontier molecular orbital characteristics, the density of states and their overlapping nature, the electronic transition properties, thermodynamical and nonlinear optical characteristics, and predicted UV-Vis, 1H and 13C NMR, FT-IR and FT-Raman spectra. Ligand-enzyme interactions of 2ClnMQ (n = 3,4,7,8,9,10) substituted quinolines with Malate Synthase from Mycobacterium Tuberculosis (MtbMS) were investigated via molecular docking. The role of position of methyl substitution on the inhibitor character of the ligands was discussed on the basis of noncovalent interaction profiles.

G-quadruplex and calf thymus DNA interaction of quaternized tetra and octa pyridyloxy substituted indium (III) phthalocyanines.

PubMed

Bağda, Efkan; Bağda, Esra; Durmuş, Mahmut

2017-10-01

The interactions of small molecules with G-quadruplex and double stranded DNA are important due to their potential biological and medical usages. In the present paper, the interactions of indium (III) phthalocyanines (quaternized 2,3,9,10,16,17,23,24-octakis-[(3-pyridyloxy) phthalocyaninato] chloroindium(III): OInPc and quaternized 2(3),9(10),16(17),23(24)-tetrakis-[(3-pyridyloxy) phthalocyaninato] chloroindium(III): TInPc) with hybrid G-quadruplex (Tel 21) and parallel G-quadruplexes (nucleolin, KRAS, c-MYC, vegf) were studied. The interactions of these phthalocyanines with ctDNA were also investigated. These interactions were measured by different spectroscopic techniques such as UV-Vis, fluorescence and circular dichroism. The UV-Vis spectroscopic data treated with Benesi-Hildebrand equation and Benesi-Hildebrand constants (K BH ) were calculated. These constants were found higher for octa peripheral pyridyloxy substituted phthalocyanine, OInPc. Besides, UV-Vis analysis showed that the interaction of G-quadruplexes with tetra peripheral pyridyloxy substituted phthalocyanine derivative (TInPc) resulted in removal of central indium (III) atom from the cavity of phthalocyanine macrocycle. The UV-Vis melting studies as well as fluorescence replacement techniques were also employed for clarification of mechanism. The binding mode of molecules with ct DNA was also supported with viscosity measurements. From the results, the stabilization and destabilization of G-quadruplex depending on the concentration of the OInPc and TInPc showed that these two indium (III) phthalocyanines have the potential of both the elucidation role of G-quadruplexes in gene expression and the usage in cancer therapy. Copyright © 2017. Published by Elsevier B.V.

Polarity dependent photoisomerization of ether substituted azodyes: Synthesis and photoswitching behavior.

PubMed

Gan, Siew Mei; Pearl, Zynia Fernandes; Yuvaraj, A R; Lutfor, M R; Gurumurthy, Hegde

2015-10-05

Two new ether substituted azodyes were synthesized and characterized by different spectral analysis such as (1)H NMR, (13)C NMR, FTIR and UV/Vis. Synthesized compounds were used to study the photoisomerization phenomenon by using UV-Vis spectro-photometer. Interesting polarity dependent effect is observed for the first time on these materials. Trans-cis (E-Z) and cis-trans (Z-E) conversion occurred within 41 s and 445 min, respectively for both the compounds in solutions. Polarizing optical microscopy studies revealed that there is no liquid crystal phase for both the compounds. The dramatic variation in the optical property is speculated to be the polarity of the chemical species. These derivatives are useful to fabricate optical data storage devices. Copyright © 2015 Elsevier B.V. All rights reserved.

Solvent and structural effects on the spectral shifts of 5-(substituted phenylazo)-3-cyano-6-hydroxy-1-(2-hydroxyethyl)-4-methyl-2-pyridones

NASA Astrophysics Data System (ADS)

Mirković, Jelena M.; Božić, Bojan Đ.; Mutavdžić, Dragosav R.; Ušćumlić, Gordana S.; Mijin, Dušan Ž.

2014-11-01

Spectral properties, solvatochromism and azo-hydrazone tautomerism of ten 5-(substituted phenylazo)-3-cyano-6-hydroxy-1-(2-hydroxyethyl)-4-methyl-2-pyridones in twenty-two solvents are investigated. For quantitative evaluation of the solvent effects on the UV-vis absorption maxima, the principles of the linear solvation energy relationships are used, i.e. models proposed by Kamlet-Taft and Catalán. Linear free energy relationships are applied to the UV-vis absorption spectra and correlation of absorption frequencies with Hammett substituent constants are performed. Furthermore, the influence of the electronic nature of the substituents on 1H and 13C NMR shifts is investigated by simple and extended Hammett equations, as well as by Swain-Lupton equation.

Chiral monolithic absorbent constructed by optically active helical-substituted polyacetylene and graphene oxide: preparation and chiral absorption capacity.

PubMed

Li, Weifei; Wang, Bo; Yang, Wantai; Deng, Jianping

2015-02-01

Chiral monolithic absorbent is successfully constructed for the first time by using optically active helical-substituted polyacetylene and graphene oxide (GO). The preparative strategy is facile and straightforward, in which chiral-substituted acetylene monomer (Ma), cross-linker (Mb), and alkynylated GO (Mc) undergo copolymerization to form the desired monolithic absorbent in quantitative yield. The resulting monoliths are characterized by circular dichroism, UV-vis absorption, scanning electron microscopy (SEM), FT-IR, Raman, energy-dispersive spectrometer (EDS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), XPS, and thermogravimetric analysis (TGA) techniques. The polymer chains derived from Ma form chiral helical structures and thus provide optical activity to the monoliths, while GO sheets contribute to the formation of porous structures. The porous structure enables the monolithic absorbents to demonstrate a large swelling ratio in organic solvents, and more remarkably, the helical polymer chains provide optical activity and further enantio-differentiating absorption ability. The present study establishes an efficient and versatile methodology for preparing novel functional materials, in particular monolithic chiral materials based on substituted polyacetylene and GO. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation Sensitivity of Soluble Polysilane Derivatives: Science and Applications

DTIC Science & Technology

1988-08-01

sigma bonded, all substituted silane polymers absorb strongly in the UV-visible region. Their absorption spectra depend to some extent on the nature...of the substituents. In this regard alkyl substituted, atatic, amphorous materials absorb from 300-325 nm with sterically bulky groups producing a...cases, the polysilane is the primary absorber of the incident radiation. Interestingly, when 3, which absorbs at -400 inm, was incorporated into a film

C-shaped diastereomers containing cofacial thiophene-substituted quinoxaline rings: synthesis, photophysical properties, and X-ray crystallography.

PubMed

DeBlase, Catherine R; Finke, Ryan T; Porras, Jonathan A; Tanski, Joseph M; Nadeau, Jocelyn M

2014-05-16

Synthesis and characterization of two diastereomeric C-shaped molecules containing cofacial thiophene-substituted quinoxaline rings are described. A previously known bis-α-diketone was condensed with an excess of 4-bromo-1,2-diaminobenzene in the presence of zinc acetate to give a mixture of two C-shaped diastereomers with cofacial bromine-substituted quinoxaline rings. After chromatographic separation, thiophene rings were installed by a microwave-assisted Suzuki coupling reaction, resulting in highly emissive diastereomeric compounds that were studied by UV-vis, fluorescence, and NMR spectroscopy, as well as X-ray crystallography. The unique symmetry of each diastereomer was confirmed by NMR spectroscopy. NMR data indicated that the syn isomer has restricted rotation about the bond connecting the thiophene and quinoxaline rings, which was also observed in the solid state. The spectroscopic properties of the C-shaped diastereomers were compared to a model compound containing only a single thiophene-substituted quinoxaline ring. Ground state intramolecular π-π interactions in solution were detected by NMR and UV-vis spectroscopy. Red-shifted emission bands, band broadening, and large Stokes shifts were observed, which collectively suggest excited state π-π interactions that produce excimer-like emissions, as well as a remarkable positive emission solvatochromism, indicating charge-transfer character in the excited state.

Luminescence properties and energy transfer of site-sensitive Ca(6-x-y)Mg(x-z)(PO(4))(4):Eu(y)(2+),Mn(z)(2+) phosphors and their application to near-UV LED-based white LEDs.

PubMed

Kwon, Ki Hyuk; Im, Won Bin; Jang, Ho Seong; Yoo, Hyoung Sun; Jeon, Duk Young

2009-12-21

On the basis of the structural information that the host material has excellent charge stabilization, blue-emitting Ca(6-x-y)Mg(x)(PO(4))(4):Eu(y)(2+) (CMP:Eu(2+)) phosphors were synthesized and systematically optimized, and their photoluminescence (PL) properties were evaluated. Depending upon the amount of Mg added, the emission efficiency of the phosphors could be enhanced. The substitution of Eu(2+) affected their maximum wavelength (lambda(max)) and thermal stability because the substitution site of Eu(2+) could be varied. To obtain single-phase two-color-emitting phosphors, we incorporated Mn(2+) into CMP:Eu(2+) phosphors. Weak red emission resulting from the forbidden transition of Mn(2+) could be enhanced by the energy transfer from Eu(2+) to Mn(2+) that occurs because of the spectral overlap between the photoluminescence excitation (PLE) spectrum of Mn(2+) and the PL spectrum of Eu(2+). The energy transfer process was confirmed by the luminescence spectra, energy transfer efficiency, and decay curve of the phosphors. Finally, the optimized Ca(6-x-y)Mg(x-z)(PO(4))(4):Eu(y)(2+),Mn(z)(2+) (CMP:Eu(2+),Mn(2+)) phosphors were applied with green emitting Ca(2)MgSi(2)O(7):Eu(2+) (CMS:Eu(2+)) phosphors to ultraviolet (UV) light emitting diode (LED)-pumped white LEDs. The CMS:Eu(2+)-mixed CMP:Eu(2+), Mn(2+)-based white LEDs showed an excellent color rendering index (CRI) of 98 because of the broader emission band and more stable color coordinates than those of commercial Y(3)Al(5)O(12):Ce(3+) (YAG:Ce(3+))-based white LEDs under a forward bias current of 20 mA. The fabricated white LEDs showed very bright natural white light that had the color coordinate of (0.3288, 0.3401), and thus CMP:Eu(2+),Mn(2+) could be regarded as a good candidate for UV LED-based white LEDs.

Synthesis and properties of feruloyl corn bran arabinoxylan esters.

PubMed

Li, Y; Yang, C

2016-06-01

To enhance the antioxidant activity and UV absorption coefficient of corn bran arabinoxylan (CAX), ferulic acid (FA) with this physiological activity is used to modify CAX. Corn bran arabinoxylan was extracted from corn bran according to alkaline hydrogen peroxide (AHP) method. FA was covalently linked to CAX by esterification in a two-step feasible synthesis to generate ferulic acid arabinoxylan esters (FA-CAX). The structure and molecular weight of FA-CAX were characterized by NMR and HPSEC, the degrees of substitution (DS) was determined by HPLC, and the ultraviolet (UV) coefficient of FA-CAX was tested by UV spectroscopy. The antioxidant activity of FA-CAX was investigated on the basis of 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical assay, and protecting ability of FA-CAX to UV-induced oxidative damage was tested using linolenic acid dispersion as stratum corneum lipid model. The results demonstrated that FA was attached to CAX successfully, and the inherent structure of CAX would not be broken during the process of the synthesis. FA-CAX-1 and FA-CAX-2 contained different amount of FA, with DS at 0.33 and 1.25, respectively, can absorb UV both at UVA and UVB. Moreover, FA-CAX-2 exhibited better antioxidant activity than FA-CAX-1 based on the two test methods. Ferulic acid modified CAX had significant antioxidant ability and UV absorption coefficient. And higher amount of FA leads to higher antioxidant activity and stronger UV absorption and stability. With increasing amount of FA attached to CAX, the antioxidant activities were better and the UV absorption was stronger and more durable. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Enhanced ultraviolet photo-response in Dy doped ZnO thin film

NASA Astrophysics Data System (ADS)

Kumar, Pawan; Singh, Ranveer; Pandey, Praveen C.

2018-02-01

In the present work, a Dy doped ZnO thin film deposited by the spin coating method has been studied for its potential application in a ZnO based UV detector. The investigations on the structural property and surface morphology of the thin film ensure that the prepared samples are crystalline and exhibit a hexagonal crystal structure of ZnO. A small change in crystallite size has been observed due to Dy doping in ZnO. AFM analysis ascertains the grain growth and smooth surface of the thin films. The Dy doped ZnO thin film exhibits a significant enhancement in UV region absorption as compared to the pure ZnO thin film, which suggests that Dy doped ZnO can be used as a UV detector. Under UV irradiation of wavelength 325 nm, the photocurrent value of Dy doped ZnO is 105.54 μA at 4.5 V, which is 31 times greater than that of the un-doped ZnO thin film (3.39 μA). The calculated value of responsivity is found to increase significantly due to the incorporation of Dy in the ZnO lattice. The observed higher value of photocurrent and responsivity could be attributed to the substitution of Dy in the ZnO lattice, which enhances the conductivity, electron mobility, and defects in ZnO and benefits the UV sensing property.

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV / H2O2 process

NASA Astrophysics Data System (ADS)

Abidin, Che Zulzikrami Azner; Fahmi, Muhammad Ridwan; Fazara, Md Ali Umi; Nadhirah, Siti Nurfatin

2014-10-01

In this study, the degradation characteristic of monoazo, diazo and anthraquinone dye by UV / H2O2 process was evaluated based on the trend of color, chemical oxygen demand (COD) and total organic carbon (TOC) removal. Three types of dyes consist of monoazo, diazo and anthraquinone dyes were used to compare the degradation mechanism of the dyes. The UV / H2O2 experiments were conducted in a laboratory scale cylindrical glass reactor operated in semi-batch mode. The UV/Vis characterization of monoazo, diazo and anthraquinone dye indicated that the rapid degradation of the dyes by UV / H2O2 process is meaningful with respect to decolourization, as a result of the azo bonds and substitute antraquinone chromophore degradation. However, this process is not efficient for aromatic amines removal. The monoazo MO was difficult to be decolorized than diazo RR120 dye, which imply that number of sulphonic groups in the dye molecules determines the reactivity with hydroxyl radical. The increased in COD removal is the evidence for oxidation and decreased in carbon content of dye molecules. TOC removal analysis shows that low TOC removal of monoazo MO and diazo RR120, as compared to anthraquinone RB19 may indicate an accumulation of by-products that are resistant to the H2O2 photolysis.

Phosphates based pigments for new anti-corrosion application: Synthesis and characterization

NASA Astrophysics Data System (ADS)

Tbib, B.; Eddya, M.; El-Hami, K.

2018-02-01

Our study focused on pyrophosphates SrZn1-xMxP2O7 using four series by substituting M with manganese (Mn), cobalt (Co), nickel (Ni), and copper (Cu). They were prepared by reaction in the solid state at 1000 °C for 24 hours and then characterized by X-ray diffraction, which showed that the obtained products are pure. The characterization by UV-visible spectroscopy was used to explain the color of the obtained materials and the optical properties showing the optical energy gap and disorder of these materials. Potential application could be done using the new anti-corrosion pigments based on phosphates.

Ultraviolet exposure of Gafchromic XR‐RV3 and XR‐SP2 films

PubMed Central

Gotanda, Rumi; Gotanda, Tatsuhiro; Akagawa, Takuya; Tanki, Nobuyoshi; Kuwano, Tadao; Yabunaka, Kouichi

2015-01-01

Gafchromic film has been used for X‐ray dose measurement in diagnostic examinations. Their use has been initiated for three‐dimensional X‐ray dose measurement by using the high‐resolution characteristics of Gafchromic films in computed tomography. However, it is necessary to solve the problem of nonuniform thickness in the active layers of Gafchromic films. A double exposure technique using X‐rays is performed in therapeutic radiology; it is difficult to use in a diagnostic examination because of the heel effect. Therefore, it is suggested that ultraviolet (UV) rays be substituted for X‐rays. However, the appropriate UV wavelength is unknown. In this study, we aimed to determine which UV wavelengths are effective to expose Gafchromic XR‐RV3 and XR‐SP2. UV lamps with peak wavelengths of 245 nm, 310 nm, and 365 nm were used. The three UV wavelengths were used to irradiate Gafchromic XR‐RV3 and XR‐SP2 films for 60 min, and irradiation was repeated every 60 min for 600 min thereafter. Films were scanned after each irradiation period on a flatbed scanner. The images were split into their red‐green‐blue components, and red images were stored using ImageJ version 1.44o image analysis software. Regions of interest (ROI), 0.5 inches in diameter, were placed at the centers of the subtracted Gafchromic film images, and graphs of UV irradiation duration and mean pixel values were plotted. There were reactions to UV‐A on both Gafchromic XR‐RV3 and XR‐SP2; those to UV‐B were moderate. However, UV‐C demonstrated few reactions with Gafchromic XR‐RV3 and XR‐SP2. From these results, irradiation with UV‐A may be able to correct nonuniformity errors. Uniform UV‐A irradiation of Gafchromic films with large areas is possible, and UV rays can be used as a substitute for X‐rays in the double exposure technique. PACS number: 87.53 Bn PMID:26699326

Photooxidation of 3-substituted pyrroles:  a postcolumn reaction detection system for singlet molecular oxygen in HPLC.

PubMed

Denham, K; Milofsky, R E

1998-10-01

A postcolumn photochemical reaction detection scheme, based on the reaction of 3-substituted pyrroles with singlet molecular oxygen ((1)O(2)), has been developed. The method is selective and sensitive for the determination of a class of organic compounds called (1)O(2)-sensitizers and is readily coupled to HPLC. Following separation by HPLC, analytes ((1)O(2)-sensitizers) are excited by a Hg pen-ray lamp. Analytes that are efficient (1)O(2)-sensitizers promote ground-state O(2) ((3)Σ(g)(-)) to an excited state ((1)Σ(g)(+) or (1)Δ(g)), which reacts rapidly with tert-butyl-3,4,5-trimethylpyrrolecarboxylate (BTMPC) or N-benzyl-3-methoxypyrrole-2-tert-carboxylate (BMPC), which is added to the mobile phase. Detection is based on the loss of pyrrole (BTMPC or BMPC). The reaction is catalytic in nature since one analyte molecule may absorb light many times, producing large amounts of (1)O(2). Detection limits for several (1)O(2)-sensitizers were improved by 1-2 orders of magnitude over optimized UV-absorbance detection. This paper discusses the optimization of the reaction conditions for this photochemical reaction detection scheme and its application to the detection of PCBs, nitrogen heterocycles, nitro and chloro aromatics, and other substituted aromatic compounds.

Transition metal-substituted lead halide perovskite absorbers

DOE PAGES

Sampson, M. D.; Park, J. S.; Schaller, R. D.; ...

2017-01-27

Here, lead halide perovskites have proven to be a versatile class of visible light absorbers that allow rapid access to the long minority carrier lifetimes and diffusion lengths desirable for traditional single-junction photovoltaics. We explore the extent to which the attractive features of these semiconductors may be extended to include an intermediate density of states for future application in multi-level solar energy conversion systems capable of exceeding the Shockley–Queisser limit. We computationally and experimentally explore the substitution of transition metals on the Pb site of MAPbX 3 (MA = methylammonium, X = Br or Cl) to achieve a tunable densitymore » of states within the parent gap. Computational screening identified both Fe- and Co-substituted MAPbBr 3 as promising absorbers with a mid-gap density of states, and the later films were synthesized via conventional solution-based processing techniques. First-principles density functional theory (DFT) calculations support the existence of mid-gap states upon Co incorporation and enhanced sub-gap absorption, which are consistent with UV-visible-NIR absorption spectroscopy. Strikingly, steady state and time-resolved PL studies reveal no sign of self-quenching for Co-substitution up to 25%, which suggest this class of materials to be a worthy candidate for future application in intermediate band photovoltaics.« less

Synthesis, structural characterization, antimicrobial activities and theoretical investigations of some 4-(4-aminophenylsulfonyl) phenylimino) methyl)-4-(aryldiazenyl) phenol

NASA Astrophysics Data System (ADS)

Ghasemian, Motaleb; Kakanejadifard, Ali; Karami, Tahereh

2016-11-01

The azo-azomethine dyes with a different substitution have been designed from the reaction of 4,4‧-diaminodiphenyl sulfone with 2-hydroxy-5-(aryldiazenyl)benzaldehyde. The compounds have been characterized by elemental analysis, Mass, IR, UV-Vis, TGA-DTA and NMR spectroscopy. The solvatochromism behaviors, effects of substitution and pH on the electronic absorption spectra of dyes were evaluated. The in vitro antimicrobial activities were also screened for their potential for antibiotic activities by broth micro dilution method. Also, the optimum molecular geometries, molecular electrostatic potential (MEP), nucleus-independent chemical shift (NICS) and frontier molecular orbitals (FMO), vibrational spectra (IR) and electronic absorption (UV-Vis) spectra of the title compounds have been investigated with the help of DFT and TDDFT methods with 6-311 ++G(d,p) basis sets and PCM calculations. The results of the calculations show excellent agreement with the experimental value.

Immobilization of styrene-substituted 1,3,4-oxadiazoles into thermoreversible luminescent organogels and their unexpected photocatalyzed rearrangement.

PubMed

Dumur, Frédéric; Contal, Emmanuel; Wantz, Guillaume; Phan, Trang N T; Bertin, Denis; Gigmes, Didier

2013-01-21

A series of styrene-substituted 1,3,4-oxadiazoles has been designed and investigated as new low-molecular-weight organogelators. The photophysical properties of the resulting thermoreversible organogels have been characterized by UV/Vis absorption and luminescence spectroscopies. Surprisingly, the gelation ability of the oxadiazoles depended on the presence of the styrene moiety as gelation of the investigated oxadiazoles did not take place in its absence. Gel formation was accompanied by a modification of the fluorescence of the organogelators in the supramolecular state. UV irradiation of the gels caused a rearrangement of the immobilized 1,3,4-oxadiazoles bearing a styrene moiety by a tandem [4+2] and [3+2] cascade reaction. Structure modification and color change of the gels were also evident upon irradiation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design, synthesis and biological evaluation of novel hydroxy-phenyl-1H-benzimidazoles as radical scavengers and UV-protective agents.

PubMed

Bino, Alessia; Baldisserotto, Anna; Scalambra, Emanuela; Dissette, Valeria; Vedaldi, Daniela Ester; Salvador, Alessia; Durini, Elisa; Manfredini, Stefano; Vertuani, Silvia

2017-12-01

An ever-increasing incidence of skin neoplastic diseases is registered. Therefore, it is important to protect the skin from the UV radiation that reaches the epidermis and dermis but also to block ROS generated by them. Our attention was attracted in developing new compounds provided with both UV filtering and antioxidant capacities. To this end, 2-phenyl-1H-benzimidazole-5-sulfonic acid (PBSA), a known UV filter, was selected as lead compound for its lack of antioxidant activity, high water solubility and good safety profile. PBSA was sequentially modified introducing hydroxyls on the phenyl ring and also substituting the functional group in position 5 of the benzimidazole ring. At the end of the synthetic study, a new, very potent class of antioxidants has been obtained. Surprisingly some of the developed molecules, while devoid of significant UV-filtering activity was endowed with potent UV-filtering booster capability if associated with known commercial UVB and UVA filters.

Self-powered vision electronic-skin basing on piezo-photodetecting Ppy/PVDF pixel-patterned matrix for mimicking vision.

PubMed

Han, Wuxiao; Zhang, Linlin; He, Haoxuan; Liu, Hongmin; Xing, Lili; Xue, Xinyu

2018-06-22

The development of multifunctional electronic-skin that establishes human-machine interfaces, enhances perception abilities or has other distinct biomedical applications is the key to the realization of artificial intelligence. In this paper, a new self-powered (battery-free) flexible vision electronic-skin has been realized from pixel-patterned matrix of piezo-photodetecting PVDF/Ppy film. The electronic-skin under applied deformation can actively output piezoelectric voltage, and the outputting signal can be significantly influenced by UV illumination. The piezoelectric output can act as both the photodetecting signal and electricity power. The reliability is demonstrated over 200 light on-off cycles. The sensing unit matrix of 6 × 6 pixels on the electronic-skin can realize image recognition through mapping multi-point UV stimuli. This self-powered vision electronic-skin that simply mimics human retina may have potential application in vision substitution.

Self-powered vision electronic-skin basing on piezo-photodetecting Ppy/PVDF pixel-patterned matrix for mimicking vision

NASA Astrophysics Data System (ADS)

Han, Wuxiao; Zhang, Linlin; He, Haoxuan; Liu, Hongmin; Xing, Lili; Xue, Xinyu

2018-06-01

The development of multifunctional electronic-skin that establishes human-machine interfaces, enhances perception abilities or has other distinct biomedical applications is the key to the realization of artificial intelligence. In this paper, a new self-powered (battery-free) flexible vision electronic-skin has been realized from pixel-patterned matrix of piezo-photodetecting PVDF/Ppy film. The electronic-skin under applied deformation can actively output piezoelectric voltage, and the outputting signal can be significantly influenced by UV illumination. The piezoelectric output can act as both the photodetecting signal and electricity power. The reliability is demonstrated over 200 light on–off cycles. The sensing unit matrix of 6 × 6 pixels on the electronic-skin can realize image recognition through mapping multi-point UV stimuli. This self-powered vision electronic-skin that simply mimics human retina may have potential application in vision substitution.

Modified polyhydroxystyrenes as matrix resins for dissolution inhibition type photoresists

NASA Astrophysics Data System (ADS)

Pawlowski, Georg; Sauer, Thomas P.; Dammel, Ralph R.; Gordon, Douglas J.; Hinsberg, William D.; McKean, Dennis R.; Lindley, Charlet R.; Merrem, Hans-Joachim; Roeschert, Heinz; Vicari, Richard; Willson, C. Grant

1990-06-01

It is generally accepted that the production of shrink versions of the 16 MB DRAM and the 64 MB DRAM generations will be patterned using deep UV radiation. This provides a new challenge to the photoresist suppliers, as the standard photoresist formulations are not suitable for this technology, mainly because the presently used novolak resins are highly opaque in the 200 - 300 nm region. This is especially true for the 248 nm wavelength of KrF eximer lasers. Poly 4- hydroxystyrene [PHS] has several advantages in transmission and thermal stability; however, its dissolution rate in commercial grade developers is unacceptably high. We report some recent results on modified, alkyl-substituted PHS derivatives. These polymers combine reduced alkaline solubiity with adequate optical and thermal properties, making them acceptable for future deep UV based production processes. Selected data of these new (co)polymers are discussed.

Studies of structure of calcium-iron phosphate glasses by infrared, Raman and UV-Vis spectroscopies

NASA Astrophysics Data System (ADS)

Li, H. J.; Liang, X. F.; Yu, H. J.; Yang, D. Q.; Yang, S. Y.

2016-06-01

Glasses in the ternary CaO-Fe2O3-P2O5 system were prepared and studied by means of density, differential scanning calorimetry, infrared, Raman and UV-Vis spectroscopies. The results showed that density and molar volume in the glass system decreased with increasing substitution of CaO for Fe2O3. The variation of glass transition temperature and thermal stability was strictly related to the nature of bonding in the vitreous network. Spectroscopic analysis showed that substitution of CaO for Fe2O3 induced an evolution of structural units from pyrophosphate to metaphosphate species indicating the polymerization of phosphate chains and the decrease of non-bridging oxygen concentrations. With increasing substitution of CaO for Fe2O3 The P-O-Ca linkage and (P-O- Ca2+ -O-P) chains participated in the glass network by replacing P-O-Fe bonds. The absorption band of the P-O-Ca stretching mode in the glasses with high CaO content (≥32 mol%) was assigned at around 1084 cm-1. The absorption edge would fall in the region between 332 and 420 nm which are the absorption bands of Fe3+ ions.

Ultraviolet-B radiation and water deficit interact to alter flavonol and anthocyanin profiles in grapevine berries through transcriptomic regulation.

PubMed

Martínez-Lüscher, Johann; Sánchez-Díaz, Manuel; Delrot, Serge; Aguirreolea, Jone; Pascual, Inmaculada; Gomès, Eric

2014-11-01

UV-B radiation and water deficit may trigger flavonol and anthocyanin biosynthesis in plant tissues. In addition, previous research has showed strong qualitative effects on grape berry skin flavonol and anthocyanin profiles in response to UV-B and water deficit. The aim of this study is to identify the mechanisms leading to quantitative and qualitative changes in flavonol and anthocyanin profiles, in response to separate and combined UV-B and water deficit. Grapevines (Vitis vinifera L. cv. Tempranillo) were exposed to three levels of UV-B radiation (0, 5.98 and 9.66 kJ m(-2) day(-1)) and subjected to two water regimes. A strong effect of UV-B on flavonol and anthocyanin biosynthesis was found, resulting in an increased anthocyanin concentration and a change in their profile. Concomitantly, two key biosynthetic genes (FLS1 and UFGT) were up-regulated by UV-B, leading to increased flavonol and anthocyanin skin concentration. Changes in flavonol and anthocyanin composition were explained to a large extend by transcript levels of F3'H, F3'5'H and OMT2. A significant interaction between UV-B and water deficit was found in the relative abundance of 3'4' and 3'4'5' substituted flavonols, but not in their anthocyanin homologues. The ratio between 3'4'5' and 3'4' substituted flavonols was linearly related to the ratios of F3'5'H and FLS1 transcription, two steps up-regulated independently by water deficit and UV-B radiation, respectively. Our results indicate that changes in flavonol profiles in response to environmental conditions are not only a consequence of changes in the expression of flavonoid hydroxylases; but also the result of the competition of FLS, F3'5'H and F3'H enzymes for the same flavonol substrates. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

A new era for homolytic aromatic substitution: replacing Bu3SnH with efficient light-induced chain reactions.

PubMed

Gurry, Michael; Aldabbagh, Fawaz

2016-04-28

Herein is a pertinent review of recent photochemical homolytic aromatic substitution (HAS) literature. Issues with using the reductant Bu3SnH in an oxidative process where the net loss of a hydrogen atom occurs is discussed. Nowadays more efficient light-induced chain reactions are used resulting in HAS becoming a synthetic mechanism of choice rivaling organometallic, transition-metal and electrophilic aromatic substitution protocols. The review includes aromatic substitution as part of a tandem or cascade reaction, Pschorr reaction, as well as HAS facilitated by ipso-substitution, and Smiles rearrangement. Recently visible-light photoredox catalysis, which is carried out at room temperature has become one of the most important means of aromatic substitution. The main photoredox catalysts used are polypyridine complexes of Ru(ii) and Ir(iii), although eosin Y is an alternative allowing metal-free HAS. Other radical initiator-free aromatic substitutions have used 9-mesityl-10-methylacridinium ion and N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide) as the photoredox catalyst, UV-light, photoinduced electron-transfer, zwitterionic semiquinone radical anions, and Barton ester intermediates.

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process

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

Abidin, Che Zulzikrami Azner, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com; Fahmi, Muhammad Ridwan, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com; Fazara, Md Ali Umi, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com

2014-10-24

In this study, the degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process was evaluated based on the trend of color, chemical oxygen demand (COD) and total organic carbon (TOC) removal. Three types of dyes consist of monoazo, diazo and anthraquinone dyes were used to compare the degradation mechanism of the dyes. The UV/H{sub 2}O{sub 2} experiments were conducted in a laboratory scale cylindrical glass reactor operated in semi-batch mode. The UV/Vis characterization of monoazo, diazo and anthraquinone dye indicated that the rapid degradation of the dyes by UV/H{sub 2}O{sub 2} process is meaningful with respectmore » to decolourization, as a result of the azo bonds and substitute antraquinone chromophore degradation. However, this process is not efficient for aromatic amines removal. The monoazo MO was difficult to be decolorized than diazo RR120 dye, which imply that number of sulphonic groups in the dye molecules determines the reactivity with hydroxyl radical. The increased in COD removal is the evidence for oxidation and decreased in carbon content of dye molecules. TOC removal analysis shows that low TOC removal of monoazo MO and diazo RR120, as compared to anthraquinone RB19 may indicate an accumulation of by-products that are resistant to the H{sub 2}O{sub 2} photolysis.« less

Synthesis, characterization and nonlinear optical properties of symmetrically substituted dibenzylideneacetone derivatives

NASA Astrophysics Data System (ADS)

Sunil Kumar Reddy, N.; Badam, Rajashekar; Sattibabu, Romala; Molli, Muralikrishna; Sai Muthukumar, V.; Siva Sankara Sai, S.; Rao, G. Nageswara

2014-11-01

We report here the nonlinear optical (NLO) properties of eight bis-chalcones of D-π-A-π-D type. These dibenzylideneacetone (DBA) derivatives are synthesized by Claisen-Schmidt reaction. The compounds are characterized by UV-vis, FTIR, 1H NMR, 13C NMR, mass spectroscopy and powder XRD. By substituting different groups (electron withdrawing and electron donating) at 'para' and 'meta' positions of the aromatic ring, we observed an enhancement in second harmonic generation with substitution at 'para' position. These compounds have also showed higher two-photon absorption compared to other chalcones reported in literature. These compounds, exhibiting both second and third order NLO effects, are plausible candidate materials in photonic devices.

UV treatments on the physicochemical properties of tilapia skin and pig skin gelatin.

PubMed

Wu, C K; Tsai, J S; Chen, Z Y; Sung, W C

2015-06-01

Tilapia skin gelatin, pig skin gelatin, and their mousse premixes were exposed to UV irradiation for 103, 206, and 309 kJ/cm(2). All samples after 309 kJ/cm(2) exposure exhibited a significant increase in gel strength, gel forming ability as well as viscosity of solutions. It was shown that UV treatment could also improve the pig skin gelatin foam stability and foam formation ability compared to those of tilapia skin gelatin. Nevertheless, the panelists gave the lowest scores to mousse made with 309 kJ/cm(2) UV-irradiated premix mousse pig skin gelatin. Tilapia skin gelatin could be used as a substitute ingredient for premix mousse made from pig skin gelatin. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Complete inhibition of anisomycin and UV radiation but not cytokine induced JNK and p38 activation by an aryl-substituted dihydropyrrolopyrazole quinoline and mixed lineage kinase 7 small interfering RNA.

PubMed

Wang, Xushan; Mader, Mary M; Toth, John E; Yu, Xiaohong; Jin, Najia; Campbell, Robert M; Smallwood, Jeffrey K; Christe, Michael E; Chatterjee, Arindam; Goodson, Theodore; Vlahos, Chris J; Matter, William F; Bloem, Laura J

2005-05-13

Mixed lineage kinase 7 (MLK7) is a mitogen-activated protein kinase kinase kinase (MAPKKK) that activates the pro-apoptotic signaling pathways p38 and JNK. A library of potential kinase inhibitors was screened, and a series of dihydropyrrolopyrazole quinolines was identified as highly potent inhibitors of MLK7 in vitro catalytic activity. Of this series, an aryl-substituted dihydropyrrolopyrazole quinoline (DHP-2) demonstrated an IC50 of 70 nM for inhibition of pJNK formation in COS-7 cell MLK7/JNK co-transfection assays. In stimulated cells, DHP-2 at 200 nM or MLK7 small interfering RNA completely blocked anisomycin and UV induced but had no effect on interleukin-1beta or tumor necrosis factor-alpha-induced p38 and JNK activation. Additionally, the compound blocked anisomycin and UV-induced apoptosis in COS-7 cells. Heart tissue homogenates from MLK7 transgenic mice treated with DHP-2 at 30 mg/kg had reduced JNK and p38 activation with no apparent effect on ERK activation, demonstrating that this compound can be used to block MLK7-driven MAPK pathway activation in vivo. Taken together, these data demonstrate that MLK7 is the MAPKKK required for modulation of the stress-activated MAPKs downstream of anisomycin and UV stimulation and that DHP-2 can be used to block MLK7 pathway activation in cells as well as in vivo.

Unfolding thermodynamics of intramolecular G-quadruplexes: base sequence contributions of the loops.

PubMed

Olsen, Chris M; Lee, Hui-Ting; Marky, Luis A

2009-03-05

G-quadruplexes are a highly studied DNA motif with a potential role in a variety of cellular processes and more recently are considered novel targets for drug therapy in aging and anticancer research. In this work, we have investigated the thermodynamic contributions of the loops on the stable formation of G-quadruplexes. Specifically, we use a combination of UV, circular dichroism (CD) and fluorescence spectroscopies, and differential scanning calorimetry (DSC) to determine thermodynamic profiles, including the differential binding of ions and water, for the unfolding of the thrombin aptamer: d(GGT2GGTGTGGT2GG) that is referred to as G2. The sequences in italics, TGT and T2, are known to form loops. Other sequences examined contained base substitutions in the TGT loop (TAT, TCT, TTT, TAPT, and UUU), in the T2 loops (T4, U2), or in both loops (UGU and U2, UUU and U2). The CD spectra of all molecules show a positive band centered at 292 nm, which corresponds to the "chair" conformation. The UV and DSC melting curves of each G-quadruplex show monophasic transitions with transition temperatures (T(M)s) that remained constant with increasing strand concentration, confirming their intramolecular formation. These G-quadruplexes unfold with T(M)s in the range from 43.2 to 56.5 degrees C and endothermic enthalpies from 22.9 to 37.2 kcal/mol. Subtracting the contribution of a G-quartet stack from each experimental profile indicated that the presence of the loops stabilize each G-quadruplex by favorable enthalpy contributions, larger differential binding of K+ ions (0.1-0.6 mol K+/ mol), and a variable uptake/release of water molecules (-6 to 8 mol H2O/mol). The thermodynamic contributions for these specific base substitutions are discussed in terms of loop stacking (base-base stacking within the loops) and their hydration effects.

Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes.

PubMed

Asadi, Zahra; Shorkaei, Mohammad Ranjkesh

2013-03-15

Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible. Copyright © 2012 Elsevier B.V. All rights reserved.

Evaluation of disinfection by-product formation during chlor(am)ination from algal organic matter after UV irradiation.

PubMed

Chen, Shi; Deng, Jing; Li, Lei; Gao, Naiyun

2018-02-01

This study evaluated the effect of low-pressure ultraviolet (UV) irradiation on the formation of disinfection by-products (DBPs) from algal organic matter of Microcystis aeruginosa during subsequent chlorination and chloramination. The algal organic matter includes extracellular organic matter (EOM) and intracellular organic matter (IOM). The fluorescence excitation-emission matrix spectra indicated that the humic/fulvic acid-like organics of EOM and the protein-like organics of IOM may be preferentially degraded by UV treatment. UV irradiation with low specific UV absorbance values was effective in reducing the formation of trihalomethanes and dichloroacetic acid from EOM and IOM during the subsequent chlorination. During the UV-chloramine process, higher UV dose (1000 mJ/cm 2 ) led to the decrease of the formation of dichloroacetic acid, trichloroacetic acid, and haloketones from IOM by an average of 24%. Furthermore, UV irradiation can slightly increase the bromine substitution factors (BSFs) of haloacetic acids from EOM during chlorination, including dihaloacetic acids and trihaloacetic acids in the presence of bromide (50 μg/L). However, UV irradiation did not shift the formation of DBPs from IOM to more brominated species, since the BSFs of trihalomethanes, dihaloacetic acids, trihaloacetic acids, and dihaloacetonitriles almost kept unchanged during UV-chlorine process. As for UV-chloramine process, UV irradiation decreased the BSFs of trihalomethanes, while increased the BSFs of dihaloacetic acid for both EOM and IOM. Overall, the UV pretreatment process is a potential technology in treating algae-rich water.

High-performance liquid chromatography study of the enantiomer separation of chrysanthemic acid and its analogous compounds on a terguride-based stationary phase.

PubMed

Dondi, M; Flieger, M; Olsovska, J; Polcaro, C M; Sinibaldi, M

1999-10-29

The direct enantioseparation of chrysanthemic acid [2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid] and its halogen-substituted analogues was systematically studied by HPLC using a terguride-based chiral stationary phase in combination with a UV diode array and chiroptical detectors. Isomers with (1R) configuration always eluted before those with (IS) configuration. The elution sequence of cis- and trans-isomers was strongly affected by mobile phase pH, whereas the enantioselectivity remained the same. Conditions for the separation of all the enantiomers were also examined. This method was used for monitor the hydrolytic degradation products of Cyfluthrin (Baythroid) in soil under laboratory conditions.

Stepwise Bay Annulation of Indigo for the Synthesis of Desymmetrized Electron Acceptors and Donor–Acceptor Constructs

DOE PAGES

Kolaczkowski, Matthew A.; He, Bo; Liu, Yi

2016-10-10

In this work, a selective stepwise annulation of indigo has been demonstrated as a means of providing both monoannulated and differentially double-annulated indigo derivatives. Disparate substitution of the electron accepting bay-annulated indigo system allows for fine control over both the electronic properties as well as donor-acceptor structural architectures. Optical and electronic properties were characterized computationally as well as through UV-vis absorption spectroscopy and cyclic voltammetry. Finally, this straightforward method provides a modular approach for the design of indigo-based materials with tailored optoelectronic properties.

Comparison of self-written waveguide techniques and bulk index matching for low-loss polymer waveguide interconnects

NASA Astrophysics Data System (ADS)

Burrell, Derek; Middlebrook, Christopher

2016-03-01

Polymer waveguides (PWGs) are used within photonic interconnects as inexpensive and versatile substitutes for traditional optical fibers. The PWGs are typically aligned to silica-based optical fibers for coupling. An epoxide elastomer is then applied and cured at the interface for index matching and rigid attachment. Self-written waveguides (SWWs) are proposed as an alternative to further reduce connection insertion loss (IL) and alleviate marginal misalignment issues. Elastomer material is deposited after the initial alignment, and SWWs are formed by injecting ultraviolet (UV) light into the fiber or waveguide. The coupled UV light cures a channel between the two differing structures. A suitable cladding layer can be applied after development. Such factors as longitudinal gap distance, UV cure time, input power level, polymer material selection and choice of solvent affect the resulting SWWs. Experimental data are compared between purely index-matched samples and those with SWWs at the fiber-PWG interface. It is shown that < 1 dB IL per connection can be achieved by either method and results indicate lowest potential losses associated with a fine-tuned self-writing process. Successfully fabricated SWWs reduce overall processing time and enable an effectively continuous low-loss rigid interconnect.

Synthesis, spectral characterization and antimicrobial studies of nano-sized oxovanadium(IV) complexes with Schiff bases derived from 5-(phenyl/substituted phenyl)-2-hydrazino-1,3,4-thiadiazole and indoline-2,3-dione.

PubMed

Sahani, M K; Yadava, U; Pandey, O P; Sengupta, S K

2014-05-05

A new class of oxovanadium(IV) complexes with Schiff bases derived by the condensation of 5-(phenyl/substituted phenyl)-2-hydrazino-1,3,4-thiadiazoles and indoline-2,3-dione have been prepared in ethanol in the presence of sodium acetate. Micro-analytical data, magnetic susceptibility, UV-Vis, IR, EPR and XRD spectral techniques were used to confirm the structures. Electronic absorption spectra of the complexes suggest a square-pyramidal geometry. The oxovanadium(IV) complexes have monoclinic crystal system and particle sizes were found to be in the range 18.0 nm to 24.0 nm (nano-size). In vitro antifungal activity of synthesized compounds was determined against fungi Aspergillus niger, Colletotrichum falcatum and Colletotrichum pallescence and in vitro antibacterial activity was determined by screening the compounds against Gram-negative (Escherichia coli and Salmonella typhi) and Gram-positive (Staphylococcus aureus and Bacillus subtilis) bacterial strains. The oxovanadium(IV) complexes have higher antimicrobial effect than free ligands. Copyright © 2014 Elsevier B.V. All rights reserved.

The ETD-like fragmentation for small molecules

USDA-ARS?s Scientific Manuscript database

Introduction (137) Flavonoids are a class of plant and fungus secondary metabolites (three-ring structure C6-C3-C6 with various substitutions) involved in many functions such as pigmentation, UV filtration, symbiotic nitrogen fixation, cell cycle inhibitors, and defense mechanisms. These polyphenoli...

Fungal Gene Mutation Analysis Elucidating Photoselective Enhancement of UV-C Disinfection Efficiency Toward Spoilage Agents on Fruit Surface.

PubMed

Zhu, Pinkuan; Li, Qianwen; Azad, Sepideh M; Qi, Yu; Wang, Yiwen; Jiang, Yina; Xu, Ling

2018-01-01

Short-wave ultraviolet (UV-C) treatment represents a potent, clean and safe substitute to chemical sanitizers for fresh fruit preservation. However, the dosage requirement for microbial disinfection may have negative effects on fruit quality. In this study, UV-C was found to be more efficient in killing spores of Botrytis cinerea in dark and red light conditions when compared to white and blue light. Loss of the blue light receptor gene Bcwcl1 , a homolog of wc-1 in Neurospora crassa , led to hypersensitivity to UV-C in all light conditions tested. The expression of Bcuve1 and Bcphr1 , which encode UV-damage endonuclease and photolyase, respectively, were strongly induced by white and blue light in a Bcwcl1 -dependent manner. Gene mutation analyses of Bcuve1 and Bcphr1 indicated that they synergistically contribute to survival after UV-C treatment. In vivo assays showed that UV-C (1.0 kJ/m 2 ) abolished decay in drop-inoculated fruit only if the UV-C treatment was followed by a dark period or red light, while in contrast, typical decay appeared on UV-C irradiated fruits exposed to white or blue light. In summary, blue light enhances UV-C resistance in B. cinerea by inducing expression of the UV damage repair-related enzymes, while the efficiency of UV-C application for fruit surface disinfection can be enhanced in dark or red light conditions; these principles seem to be well conserved among postharvest fungal pathogens.

Photostability and Performance of Polystyrene Films Containing 1,2,4-Triazole-3-thiol Ring System Schiff Bases.

PubMed

Ali, Gassan Q; El-Hiti, Gamal A; Tomi, Ivan Hameed R; Haddad, Raghad; Al-Qaisi, Alaa J; Yousif, Emad

2016-12-09

Series of 4-(4-substituted benzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4 H -1,2,4-triazole-3-thiols were synthesized and their structures were confirmed. The synthesized Schiff bases were used as photostabilizers for polystyrene against photodegradation. Polystyrene polymeric films containing synthesized Schiff bases (0.5% by weight) were irradiated (λ max = 365 nm and light intensity = 6.43 × 10 -9 ein·dm -3 ·s -1 ) at room temperature. The photostabilization effect of 1,2,4-triazole-3-thiols Schiff bases was determined using various methods. All the additives used enhanced the photostability of polystyrene films against irradiation compared with the result obtained in the absence of Schiff base. The Schiff bases can act as photostabilizers for polystyrene through the direct absorption of UV radiation and/or radical scavengers.

fac-Re(CO)3 complexes of 2,6-bis(4-substituted-1,2,3-triazol-1-ylmethyl)pyridine "click" ligands: synthesis, characterisation and photophysical properties.

PubMed

Anderson, Christopher B; Elliott, Anastasia B S; Lewis, James E M; McAdam, C John; Gordon, Keith C; Crowley, James D

2012-12-28

The syntheses of the 4-n-propyl and 4-phenyl substituted fac-Re(CO)(3) complexes of the tridentate "click" ligand (2,6-bis(4-substituted-1,2,3-triazol-1-ylmethyl)pyridine) are described. The complexes were obtained by refluxing methanol solutions of [Re(CO)(5)Cl], AgPF(6) and either the 4-propyl or 4-phenyl substituted ligand for 16 h. The ligands and the two rhenium(I) complexes were characterised by elemental analysis, HR-ESMS, ATR-IR, (1)H and (13)C NMR spectroscopy and the molecular structures of both complexes were confirmed by X-ray crystallography. The electronic structure of the fac-Re(CO)(3) "click" complexes was probed using UV-Vis, Raman and emission spectroscopy, cyclic voltammetry and DFT calculations. Altering the electronic nature of the ligand's substituent, from aromatic to alkyl, had little effect on the absorption/emission maxima and electrochemical properties of the complexes indicating that the 1,2,3-triazole unit may insulate the metal centre from the electronic modification at the ligands' periphery. Both Re(I) complexes were found to be weakly emitting with short excited state lifetimes. The electrochemistry of the complexes is defined by quasi-reversible Re oxidation and irreversible triazole-based ligand reduction processes.

Study of structural, electrical, magnetic and optical properties of BaFe12O19 and its modified systems with Ni and Ti

NASA Astrophysics Data System (ADS)

Nayak, Debabrata; Pattanayak, Ranjit; Raut, Subhajit; Panigrahi, Simanchalo

2018-02-01

In this work, BaFe12O19 (BaM) and its modified systems (by substitution of Ni and Ti) have been synthesized by solid-state reaction method. From Rietveld refinement of X-ray diffraction pattern, it is found that volume of unit cell increased slightly in case of modified systems. SEM images provided the information about the microstructure of BaM and its modified systems. The electric, magnetic and optical properties have been carried out with the help of complex impedance spectroscopy, VSM and UV spectrum, respectively. From electrical analysis, it is perceived that Ni-substitution system has shown co-contribution of grain and grain boundary effect due to increases of grain size. The M- H loops are explored that, with substitution of Ni and Ti both M s and H c are decreased. From the variation of band gap ( E g), it is observed that E g has been significantly decreased with substitution (least for Ni-substitution).

Arenium ions are not obligatory intermediates in electrophilic aromatic substitution

PubMed Central

Galabov, Boris; Koleva, Gergana; Simova, Svetlana; Hadjieva, Boriana; Schaefer, Henry F.; Schleyer, Paul von Ragué

2014-01-01

Our computational and experimental investigation of the reaction of anisole with Cl2 in nonpolar CCl4 solution challenges two fundamental tenets of the traditional SEAr (arenium ion) mechanism of aromatic electrophilic substitution. Instead of this direct substitution process, the alternative addition–elimination (AE) pathway is favored energetically. This AE mechanism rationalizes the preferred ortho and para substitution orientation of anisole easily. Moreover, neither the SEAr nor the AE mechanisms involve the formation of a σ-complex (Wheland-type) intermediate in the rate-controlling stage. Contrary to the conventional interpretations, the substitution (SEAr) mechanism proceeds concertedly via a single transition state. Experimental NMR investigations of the anisole chlorination reaction course at various temperatures reveal the formation of tetrachloro addition by-products and thus support the computed addition–elimination mechanism of anisole chlorination in nonpolar media. The important autocatalytic effect of the HCl reaction product was confirmed by spectroscopic (UV-visible) investigations and by HCl-augmented computational modeling. PMID:24972792

Band-gap tuning and magnetic properties of heterovalent ions (Ba, Sr and Ca) substituted BiFeO{sub 3} nanoparticles

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

Chauhan, Sunil, E-mail: sunilchauhanjiit@gmail.com; Kumar, Manoj; Katyal, S. C.

2016-05-23

A Comparative study of heterovalent Ba, Sr and Ca ions substitution on the structural, vibrational, optical and magnetic properties of BiFeO{sub 3} nanoparticles was carried out. The distorted rhombohedral structure was confirmed from both X-ray diffraction and Raman spectroscopy techniques in pure BiFeO{sub 3} and Bi{sub 0.85}A{sub 0.15}FeO{sub 3} (A= Ba, Sr and Ca) samples. UV-Visible spectroscopy results show that the band-gap of BiFeO{sub 3} nanoparticles can be tuned by heterovalent ions substitution from 2.12 eV for BiFeO{sub 3} to 2.10, 2.06 and 2.03 eV for Ca, Sr and Ba substituted BiFeO{sub 3} nanoparticles respectively. The magnetic measurements indicate enhancementmore » in magnetization for heterovalent A{sup 2+} substituted BiFeO{sub 3} samples and the magnetization increases with increase of ionic radius of the substituted ions.« less

A series of BCN nanosheets with enhanced photoelectrochemical performances

NASA Astrophysics Data System (ADS)

Li, Junqi; Lei, Nan; Hao, Hongjuan; Zhou, Jian

2017-03-01

A series of flake-like BCN compounds were produced by calcination at different reaction temperatures via thermal substitution of C atoms with B atoms of boric acid substructures in graphitic carbon nitrides (g-C3N4). The structural and optical properties of the samples were characterized by XRD, TEM, HRTEM, XPS and UV-vis absorption. The photoelectrochemical (PEC) performance of all samples were characterized through photocurrent and electrochemical impedance spectroscopy (EIS) measurement. The test results demonstrated that BCN nanosheets exhibited higher PEC performance with increasing substituted amount of boron.

Coumarin-BODIPY hybrids by heteroatom linkage: versatile, tunable and photostable dye lasers for UV irradiation.

PubMed

Esnal, I; Duran-Sampedro, G; Agarrabeitia, A R; Bañuelos, J; García-Moreno, I; Macías, M A; Peña-Cabrera, E; López-Arbeloa, I; de la Moya, S; Ortiz, M J

2015-03-28

Linking amino and hydroxycoumarins to BODIPYs through the amino or hydroxyl group lets the easy construction of unprecedented photostable coumarin-BODIPY hybrids with broadened and enhanced absorption in the UV spectral region, and outstanding wavelength-tunable laser action within the green-to-red spectral region (∼520-680 nm). These laser dyes allow the generation of a valuable tunable UV (∼260-350 nm) laser source by frequency doubling, which is essential to study accurately the photochemistry of biological molecules under solar irradiation. The tunability is achieved by selecting the substitution pattern of the hybrid. Key factors are the linking heteroatom (nitrogen vs. oxygen), the number of coumarin units joined to the BODIPY framework and the involved linking positions.

Fluorine substitution and nonconventional OH...pi intramolecular bond: high-resolution UV spectroscopy and ab initio calculations of 2-(p-fluorophenyl)ethanol.

PubMed

Karaminkov, Rosen; Chervenkov, Sotir; Neusser, Hans J

2008-05-21

The para-fluorinated flexible neurotransmitter analogue 2-phenylethanol has been investigated by highly resolved resonance-enhanced two-photon ionisation two-colour UV laser spectroscopy with mass resolution and ab initio structural optimisations and energy calculations. Two stable conformations, gauche and anti, separated by a high potential barrier have been identified in the cold molecular beam by rotational analysis of the vibronic band structures. The theoretically predicted higher-lying conformations most likely relax to these two structures during the adiabatic expansion. The lowest-energy gauche conformer is stabilised by an intramolecular nonconventional OH...pi-type hydrogen bond between the terminal OH group of the side chain and the pi electrons of the phenyl ring. The good agreement between the experimental and theoretical results demonstrates that even the substitution with a strongly electronegative atom of 2-phenylethanol at the para position has no noticeable effect on the strength and orientation of the OH...pi bond.

Development of novel cycloaliphatic siloxanes for thermal and UV-curable applications

NASA Astrophysics Data System (ADS)

Chakraborty, Ruby

Siloxanes have been extensively used as additives to modulate surface properties such as surface tension, hydrophobicity/hydrophobicity, and adhesion, etc. Although, polydimethyl -siloxane and polydiphenylsiloxane are the most commonly used siloxanes, the properties are at extremes in terms of glass transition temperature and flexibility. It is proposed that the ability to control the properties in between the these extremes can be provided by cycloaliphatic substitutions at the siloxane backbone. It is expected that this substitution might work due to the intermediate backbone rigidity. In order to achieve the above objectives, a synthetic route was developed to prepare cycloaliphatic (cyclopentane and cyclohexane) silane monomers followed by subsequent polymerization and functionalizations to obtain glycidyl epoxy, aliphatic amine and methacrylate telechelic siloxanes. The siloxanes were either thermally or UV-cured depending on end functionalizations. Chemical characterization of monomers, oligomers and polymers were performed using 1H, 13C, 29Si-NMR, FT-IR and GPC. The curing kinetics of photo-induced reactions were investigated through photo-differential scanning calorimetry (PDSC). The oxygen permeability, mechanical, coatings, and release properties of siloxanes were studied as a function of the backbone substitutions. The mechanical, coatings and released properties of cycloaliphatic siloxanes improved with respect to polydimethylsiloxanes. The thermal analysis of the cured films were carried out using differential scanning calorimetry (DSC). Viscoelastic properties of the cured siloxanes due to the variation of substitution at the siloxane backbone were measured using dynamic mechanical thermal analysis (DMTA). The cycloaliphatic substituted siloxanes showed an increased glass transition temperature and permeability but reduced crosslink density, conversion, and rate of curing with respect to polydimethylsiloxanes. Hybrids of siloxanes were prepared with linseed oil based alkyds to study the effect of variation of alkyd oil lengths and cycloaliphatic substitutions on siloxane backbone. The oil length of an alkyd resin is defined as the number of grams of oil used to produce 100 grams of resin. Three linseed oil based alkyds representing long, medium, and short oil lengths were grafted with siloxanes substituted with methyl, cyclopentyl, and cyclohexyl groups. The reaction was monitored through FTIR and 1H-NMR. The hybrids were formulated with standard drier package and thermally cured for detailed film characterization. Improvement in crosslink density, flexibility, and reverse impact resistance were found as function of oil length. However, tensile modulus, elongation, glass transition temperature, drying time and fracture toughness decreased with increase in oil length. For hybrids, the cycloaliphatic substituents at the siloxane backbone showed enhanced mechanical and coating properties as compared to hybrids with polydimethylsiloxanes. Random and block copolymer of polydimethylsiloxanes with polydicycloaliphatic-siloxanes were synthesized and compared with homopolymers of polydicycloaliphatic siloxanes. The chemical characterization of the copolymers and homopolymers were carried out through 1H, 13C, 29Si-NMR, and FT-IR. The glass transition temperatures (Tg) of the synthesized polymers were obtained through DSC and advanced rheometric expansion system (ARES). The Tg of random copolymers were found to be higher than the corresponding block copolymers. There was very small difference in T g between cycloaliphaticsiloxanes homopolymers and corresponding random copolymers. From the above results, it can be inferred that the cycloaliphatic substitutions at the siloxane backbone can be used as a means to obtain properties intermediate to polydimethyl- and polydiphenyl siloxanes.

Photoinduced Electron Transfer between Psoralens and DNA: Influence of DNA Sequence and Substitution.

PubMed

Fröbel, Sascha; Levi, Lucilla; Ulamec, Sabine M; Gilch, Peter

2016-05-04

Psoralens are heterocyclic compounds which are, among other uses, used to treat skin deseases in the framework of PUVA therapy. In the dark, they intercalate into DNA and can form photoadducts with thymines upon UV-A excitation, which harms the affected cells. We have recently discovered that after excitation of intercalated psoralens, an efficient photoinduced electron transfer (PET) from DNA occurs. Here, the PET is studied in detail by means of femtosecond transient absorption spectroscopy. Using DNA samples that contain either only GC or AT base pairs, we show that only guanine donates the electrons. Additionally, the substituent effects on PET are studied relying on three different psoralen derivatives. The substitution alters spectroscopic and electrochemical properties of the psoralens, which are determined by cyclic voltammetry and steady state spectroscopy. These experiments allow us to estimate the PET energetics, which are in line with the measured kinetics. Implications for the applications of psoralens are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of preparation and processing conditions on UV absorbing properties of hydroxyapatite-Fe2O3 sunscreen.

PubMed

C Teixeira, M A; Piccirillo, C; Tobaldi, D M; Pullar, R C; Labrincha, J A; Ferreira, M O; L Castro, P M; E Pintado, M M

2017-02-01

The development of innovative, safe and non-photocatalytic sunscreens is urgently needed, as it is essential to have sunscreen filters offering appropriate UV protection without damaging the environment and/or generating free radicals when in contact with the skin. Hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 , HAp) when substituted with iron has UV protection properties and is not photocatalytic; HAp was used to make a sunscreen filter by treating cod fish bones in an iron-containing solution, and then calcining them at 700°C. Here we present a systematic and advanced study on this material, to obtain a sunscreen with improved UV absorbing properties. Bones were treated with three different iron salts - Fe(II) chloride, Fe(II) lactate and Fe(III) nitrate - under various pH conditions. Results showed that Fe(II) chloride in basic pH led to the most effective iron inclusion. High energy ball milling or ultrasound were investigated to increase surface area and corresponding UV absorption; high energy ball milling treatment led to the best optical properties. The optimum powders were used to formulate UV protection creams, which showed Sun Protection Factor (SPF) values significantly superior to the control cream (up to 4.1). Moreover the critical wavelength (λ crit ) was >370nm (388-389nm) and UVA/UVB ratios were very close to 1. With these properties these sunscreens can be classified as broad UV protectors. Results also showed that combining these powders with other sunscreens (i.e. titanium dioxide), a synergic effect between the different components was also observed. This investigation showed that HAp-based sunscreens of marine origin are a valid alternative to commercial products, safe for the health of the customers and, being non-photocatalytic, do not pose a threat to the environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultraviolet radiation exposure from UV-transilluminators.

PubMed

Akbar-Khanzadeh, Farhang; Jahangir-Blourchian, Mahdi

2005-10-01

UV-transilluminators use ultraviolet radiation (UVR) to visualize proteins, DNA, RNA, and their precursors in a gel electrophoresis procedure. This study was initiated to evaluate workers' exposure to UVR during their use of UV-transilluminators. The levels of irradiance of UV-A, UV-B, and UV-C were determined for 29 UV-transilluminators at arbitrary measuring locations of 6, 25, 62, and 125 cm from the center of the UV-transilluminator's filter surface in the direction of the operator's head. The operators (faculty, research staff, and graduate students) worked within 62 cm of the transilluminators, with most subjects commonly working at < or =25 cm from the UV-transilluminator's filter surface. Daily exposure time ranged from 1 to 60 min. Actinic hazard (effective irradiance level of UVR) was also determined for three representative UV-transilluminators at arbitrary measuring locations of 2.5, 5, 10, 15, 20, 30, 40, and 50 cm from these sets' filter surface in the direction of the operator's head. The allowable exposure time for these instruments was less than 20 sec within 15 cm, less than 35 sec within 25 cm, and less than 2 min within 50 cm from the UV-transilluminators' filter surface. The results of this study suggest that the use of UV-transilluminators exposes operators to levels of UVR in excess of exposure guidelines. It is recommended that special safety training be provided for the affected employees and that exposure should be controlled by one or the combination of automation, substitution, isolation, posted warning signs, shielding, and/or personal protective equipment.

Development of high power UV irradiance meter calibration device

NASA Astrophysics Data System (ADS)

Xia, Ming; Gao, Jianqiang; Yin, Dejin; Li, Tiecheng

2016-09-01

With the rapid development of China's economy, many industries have more requirements for UV light applications, such as machinery manufacturing, aircraft manufacturing using high power UV light for detection, IT industry using high power UV light for curing component assembly, building materials, ink, paint and other industries using high power UV light for material aging test etc. In these industries, there are many measuring instruments for high power UV irradiance which are need to traceability. But these instruments are mostly imported instruments, these imported UV radiation meter are large range, wide wavelength range and high accuracy. They have exceeded our existing calibration capability. Expand the measuring range and improve the measurement accuracy of UV irradiance calibration device is a pressing matter of the moment. The newly developed high power UV irradiance calibration device is mainly composed of high power UV light, UV filter, condenser, UV light guide, optical alignment system, standard cavity absolute radiometer. The calibration device is using optical alignment system to form uniform light radiation field. The standard is standard cavity absolute radiometer, which can through the electrical substitution method, by means of adjusting and measuring the applied DC electric power at the receiver on a heating wire, which is equivalent to the thermo-electromotive force generated by the light radiation power, to achieve absolute optical radiation measurement. This method is the commonly used effective method for accurate measurement of light irradiation. The measuring range of calibration device is (0.2 200) mW/cm2, and the uncertainty of measurement results can reached 2.5% (k=2).

Encapsulation of natural ingredient for skin protection via nanoemulsion process

NASA Astrophysics Data System (ADS)

Asmatulu, Eylem; Usta, Aybala; Alzahrani, Naif; Patil, Vinay; Vanderwall, Adeesha

2017-04-01

Many of the sunscreens are used during the hot summer time to protect the skin surface. However, some of ingredients in the sunscreens, such as oxybenzone, retinyl palmitate and synthetic fragrances including parabens, phthalates and synthetic musk may disrupt the cells on the skin and create harmful effects to human body. Natural oils may be considered for substitution of harmful ingredients in sunscreens. Many natural oils (e.g., macadamia oil, sesame oil, almond oil and olive oil) have UV protective property and on top of that they have natural essences. Among the natural oils, olive oil has a long history of being used as a home remedy for skincare. Olive oil is used or substituted for cleanser, moisturizer, antibacterial agent and massage reliever for muscle fatigue. It is known that sun protection factor (SPF) of olive oil is around eight. There has been relatively little scientific work performed on the effect of olive oil on the skin as sunscreen. With nanoencapsulation technique, UV light protection of the olive oil can be extended which will provide better coverage for the skin throughout the day. In the present study, natural olive oil was incorporated with DI water and surfactant (sodium dodecyl sulfate - SDS) and sonicated using probe sonicators. Sonication time, and concentrations of olive oil, DI water and surfactant were investigated in detail. The produced nanoemulsions were characterized using dynamic light scattering, and UV-Vis spectroscopy. It is believed that the nanoencupsulation of olive oil could provide better skin protection by slow releasing and deeper penetration of the nanoemulsion on skin surface. Undergraduate engineering students were involved in the project and observed all the process during the laboratory studies, as well as data collection, analysis and presentation. This experience based learning will likely enhance the students' skills and interest in the scientific and engineering studies.

Synthesis of new visible light active photocatalysts of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M' = Nb, Ta): a band gap engineering strategy based on electronegativity of a metal component.

PubMed

Hur, Su Gil; Kim, Tae Woo; Hwang, Seong-Ju; Park, Hyunwoong; Choi, Wonyong; Kim, Sung Jin; Kim, Sun Jin; Choy, Jin-Ho

2005-08-11

We have synthesized new, efficient, visible light active photocatalysts through the incorporation of highly electronegative non-transition metal Pb or Sn ions into the perovskite lattice of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M = Sn, Pb; M' = Nb, Ta). X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that tetravalent Pb or Sn ions exist in the B-site of the perovskite lattice, along with In and Nb/Ta ions. According to diffuse UV-vis spectroscopic analysis, the Pb-containing quaternary metal oxides Ba(In(1/3)Pb(1/3)M'(1/3))O3 possess a much narrower band gap (E(g) approximately 1.48-1.50 eV) when compared to the ternary oxides Ba(In(1/2)M'(1/2))O3 (E(g) approximately 2.97-3.30 eV) and the Sn-containing Ba(In(1/3)Sn(1/3)M'(1/3))O3 derivatives (E(g) approximately 2.85-3.00 eV). Such a variation of band gap energy upon the substitution is attributable to the broadening of the conduction band caused by the dissimilar electronegativities of the B-site cations. In contrast to the ternary or the Sn-substituted quaternary compounds showing photocatalytic activity under UV-vis irradiation, the Ba(In(1/3)Pb(1/3)M'(1/3))O3 compounds induce an efficient photodegradation of 4-chlorophenol under visible light irradiation (lambda > 420 nm). The present results highlight that the substitution of electronegative non-transition metal cations can provide a very powerful way of developing efficient visible light harvesting photocatalysts through tuning of the band structure of a semiconductive metal oxide.

UV-blocking potential of oils and juices.

PubMed

Gause, S; Chauhan, A

2016-08-01

Sunscreens are commonly used to protect the body from damage caused by UV light. Some components of organic sunscreens have been shown to pass through the skin during wear which could raise toxicity concerns for these compounds. This study explores the potential for oils and fruit and vegetable juices to be substitutes for these compounds. The absorptivity of various oils (canola oil, citronella oil, coconut oil, olive oil, soya bean oil, vitamin E, as well as aloe vera) and fruit and vegetable juices (acerola, beet, grape, orange carrot, purple carrot and raspberry) was measured in vitro. The mean absorptivity was compared with FDA-approved UV absorbers to gauge the potential of the natural products. The most promising candidates were incorporated into formulations, and the UV transmittance of a 20-μm-thick film of the formulation was measured. The formulations were also imaged by light microscopy and scanning electron microscopy. The absorptivity of oils was at least two orders of magnitude lower compared to the commercial UV blockers. The fruit juice powders were more effective at UV blocking but still showed an order of magnitude lower absorptivity compared to commercial UV blockers. The UV blocking from most natural oils is insufficient to obtain a significant UV protection. Formulations containing 50wt% purple carrot showed good UV-blocking capabilities and represent a promising ingredient for sunscreen and cosmetic applications. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Spectral, coordination and thermal properties of 5-arylidene thiobarbituric acids

NASA Astrophysics Data System (ADS)

Masoud, Mamdouh S.; El-Marghany, Adel; Orabi, Adel; Ali, Alaa E.; Sayed, Reham

2013-04-01

Synthesis of 5-arylidine thiobarbituric acids containing different functional groups with variable electronic characters were described and their Co2+, Ni2+ and Cu2+ complexes. The stereochemistry and mode of bonding of 5-(substituted benzylidine)-2-TBA complexes were achieved based on elemental analysis, spectral (UV-VIS, IR, 1H NMR, MS), magnetic susceptibility and conductivity measurements. The ligands were of bidentate and tridentate bonding through S, N and O of pyrimidine nucleolus. All complexes were of octahedral configuration. The thermal data of the complexes pointed to their stability. The mechanism of the thermal decomposition is discussed. The thermodynamic parameters of the dissociation steps were evaluated and discussed.

Synthesis, structural elucidation and pharmacological properties of some 5-acetyl-3,4-dihydro-6-methyl-4-(substituted phenyl)-2(1H) -pyrimidinones.

PubMed

Yarim, M; Sarac, S; Ertan, M; Batu, O S; Erol, K

1999-06-30

In this study, the synthesis of some new 5-acetyl-3,4-dihydro-6-methyl-4-(substituted phenyl)-2(1H)-pyrimidinones has been reported. The compounds were prepared by the Biginelli reaction of acetylacetone with aromatic aldehydes and urea. The structures of the compounds were characterized by UV, IR, 1H NMR, 13C NRM, mass spectra and elementary analysis. The calcium antagonistic activity of these compounds was tested in vitro on rat ileum precontracted with 4 x 10(-3) M barium chloride.

Diaryl-substituted norbornadienes with red-shifted absorption for molecular solar thermal energy storage.

PubMed

Gray, Victor; Lennartson, Anders; Ratanalert, Phasin; Börjesson, Karl; Moth-Poulsen, Kasper

2014-05-25

Red-shifting the absorption of norbornadienes (NBDs), into the visible region, enables the photo-isomerization of NBDs to quadricyclanes (QCs) to be driven by sunlight. This is necessary in order to utilize the NBD-QC system for molecular solar thermal (MOST) energy storage. Reported here is a study on five diaryl-substituted norbornadienes. The introduced aryl-groups induce a significant red-shift of the UV/vis absorption spectrum of the norbornadienes, and device experiments using a solar-simulator set-up demonstrate the potential use of these compounds for MOST energy storage.

Development of a wide-field fluorescence imaging system for evaluation of wound re-epithelialization

NASA Astrophysics Data System (ADS)

Franco, Walfre; Gutierrez-Herrera, Enoch; Purschke, Martin; Wang, Ying; Tam, Josh; Anderson, R. Rox; Doukas, Apostolos

2013-03-01

Normal skin barrier function depends on having a viable epidermis, an epithelial layer formed by keratinocytes. The transparent epidermis, which is less than a 100 mum thick, is nearly impossible to see. Thus, the clinical evaluation of re-epithelialization is difficult, which hinders selecting appropriate therapy for promoting wound healing. An imaging system was developed to evaluate epithelialization by detecting endogenous fluorescence emissions of cellular proliferation over a wide field of view. A custom-made 295 nm ultraviolet (UV) light source was used for excitation. Detection was done by integrating a near-UV camera with sensitivity down to 300 nm, a 12 mm quartz lens with iris and focus lock for the UV regime, and a fluorescence bandpass filter with 340 nm center wavelength. To demonstrate that changes in fluorescence are related to cellular processes, the epithelialization of a skin substitute was monitored in vitro. The skin substitute or construct was made by embedding microscopic live human skin tissue columns, 1 mm in diameter and spaced 1 mm apart, in acellular porcine dermis. Fluorescence emissions clearly delineate the extent of lateral surface migration of keratinocytes and the total surface covered by the new epithelium. The fluorescence image of new epidermis spatially correlates with the corresponding color image. A simple, user-friendly way of imaging the presence of skin epithelium would improve wound care in civilian burns, ulcers and surgeries.

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

Brgoch, Jakoah; Klob, Simon D.; Denault, Kristin A.

The preparation of Eu 2+-substituted barium aluminum silicates is achieved using a rapid microwave-assisted preparation. The phase evolution of two BaAl 2Si 2O 8:Eu 2+ polymorphs, the higher temperature hexagonal phase (hexacelsian), and the lower temperature monoclinic phase (celsian), is explored by varying the ramp time and soak time. This preparation method significantly reduces the reaction time needed to form these phases compared to conventional solid state routes. The luminescent properties of the two phases are identified under UV excitation with the hexagonal phase emitting in the UV region (λ em = 372 nm) and the monoclinic phase emitting inmore » the blue region (λ em = 438 nm). The differences in optical properties of the two polymorphs are correlated to the coordination number and arrangement of the alkali earth site. The optical properties of the monoclinic phase can be further tuned through the substitution of Sr 2+, forming the solid solution (Ba 1–xSr x)Al 2Si 2O 8:Eu 2+. Changes in the crystal structure due to Sr 2+ substitution produce a surprising blue-shift in the emission spectrum, which is explained by a greater dispersion of bond lengths in the (Ba/Sr)–O polyhedra. The entire monoclinic solid solution exhibits excellent quantum yields of nearly 90 %, owing to the structural rigidity provided by the highly connected tetrahedral network.« less

Examining the base stacking interaction in a dinucleotide context via reversible cyclobutane dimer analogue formation under UV irradiation.

PubMed

Liu, Degang; Li, Lei

2013-11-14

Substituted tolyl groups are considered as close isosteres of the thymine (T) residue. They can be recognized by DNA polymerases as if they were thymine. Although these toluene derivatives are relatively inert toward radical additions, our recent finding suggests that the dinucleotide analogue TpTo (To = 2'-deoxy-1-(3-tolyl)-β-D-ribofuranose) supports an ortho photocycloaddition reaction upon UV irradiation, producing two cyclobutane pyrimidine dimer (CPD) analogues 2 and 3 . Our report here further shows that formation of these CPD species is reversible under UVC irradiation, resembling the photochemical property of the CPD species formed between two Ts. Analyzing the stability of these CPD analogues suggests that one ( 2 ) is more stable than the other ( 3 ). The TpTo conformer responsible for 2 formation is also more stable than that responsible for 3 formation, as indicated by the Gibbs free energy change calculated from the constructed Bordwell thermodynamic cycle. These different stabilities are not due to the varying photochemical properties, as proved by quantum yields determined from the corresponding photoreactions. Instead, they are ascribed to the different stacking interaction between the T and the To rings both in the TpTo dinucleotide as well as in the formed CPD analogues. Factors contributing to the ring stacking interactions are also discussed. Our proof-of-concept approach suggests that a carefully designed Bordwell cycle coupled with reversible CPD formations under UV irradiation can be very useful in studying DNA base interactions.

Examining the base stacking interaction in a dinucleotide context via reversible cyclobutane dimer analogue formation under UV irradiation

PubMed Central

Liu, Degang; Li, Lei

2013-01-01

Substituted tolyl groups are considered as close isosteres of the thymine (T) residue. They can be recognized by DNA polymerases as if they were thymine. Although these toluene derivatives are relatively inert toward radical additions, our recent finding suggests that the dinucleotide analogue TpTo (To = 2'-deoxy-1-(3-tolyl)-β-D-ribofuranose) supports an ortho photocycloaddition reaction upon UV irradiation, producing two cyclobutane pyrimidine dimer (CPD) analogues 2 and 3. Our report here further shows that formation of these CPD species is reversible under UVC irradiation, resembling the photochemical property of the CPD species formed between two Ts. Analyzing the stability of these CPD analogues suggests that one (2) is more stable than the other (3). The TpTo conformer responsible for 2 formation is also more stable than that responsible for 3 formation, as indicated by the Gibbs free energy change calculated from the constructed Bordwell thermodynamic cycle. These different stabilities are not due to the varying photochemical properties, as proved by quantum yields determined from the corresponding photoreactions. Instead, they are ascribed to the different stacking interaction between the T and the To rings both in the TpTo dinucleotide as well as in the formed CPD analogues. Factors contributing to the ring stacking interactions are also discussed. Our proof-of-concept approach suggests that a carefully designed Bordwell cycle coupled with reversible CPD formations under UV irradiation can be very useful in studying DNA base interactions. PMID:24223299

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Do dichromats see colours in this way? Assessing simulation tools without colorimetric measurements.

PubMed

Lillo Jover, Julio A; Álvaro Llorente, Leticia; Moreira Villegas, Humberto; Melnikova, Anna

2016-11-01

Simulcheck evaluates Colour Simulation Tools (CSTs, they transform colours to mimic those seen by colour vision deficients). Two CSTs (Variantor and Coblis) were used to know if the standard Simulcheck version (direct measurement based, DMB) can be substituted by another (RGB values based) not requiring sophisticated measurement instruments. Ten normal trichromats performed the two psychophysical tasks included in the Simulcheck method. The Pseudoachromatic Stimuli Identification task provided the h uv (hue angle) values of the pseudoachromatic stimuli: colours seen as red or green by normal trichromats but as grey by colour deficient people. The Minimum Achromatic Contrast task was used to compute the L R (relative luminance) values of the pseudoachromatic stimuli. Simulcheck DMB version showed that Variantor was accurate to simulate protanopia but neither Variantor nor Coblis were accurate to simulate deuteranopia. Simulcheck RGB version provided accurate h uv values, so this variable can be adequately estimated when lacking a colorimeter —an expensive and unusual apparatus—. Contrary, the inaccuracy of the L R estimations provided by Simulcheck RGB version makes it advisable to compute this variable from the measurements performed with a photometer, a cheap and easy to find apparatus.

Synthesis, crystal structure and biological activity of the Schiff base organotin(IV) complexes based on salicylaldehyde-o-aminophenol

NASA Astrophysics Data System (ADS)

Tan, Yu-Xing; Zhang, Zhi-Jian; Liu, Yang; Yu, Jiang-Xi; Zhu, Xiao-Ming; Kuang, Dai-Zhi; Jiang, Wu-Jiu

2017-12-01

Schiff base organotin(IV) complexes C1 ∼ C5b have been synthesized via the reaction of the substituted salicylaldehyde-o-aminophenol Schiff base ligands (L1 ∼ L3) with the dibenzyltin dichloride, n-butyltin trichloride or dibutyltin oxide, respectively. The complexes have been characterized by IR, UV-Vis, 1H NMR, 13C NMR spectra, elemental analysis and the crystal structures have been determined by X-ray diffraction. The anticancer activity of the Schiff base ligand and complexes C1 ∼ C5b against five species of cancer cell which are Hela, MCF7, HepG2, Colo205, NCIsbnd H460 were tested respectively, the tests showed that C1 ∼ C5b exhibited significant anticancer activity for the cancer cells in comparison with the ligand, and the activity was greater than carboplatin.

Photolytic removal of DBPs by medium pressure UV in swimming pool water.

PubMed

Hansen, Kamilla M S; Zortea, Raissa; Piketty, Aurelia; Vega, Sergio Rodriguez; Andersen, Henrik Rasmus

2013-01-15

Medium pressure UV is used for controlling the concentration of combined chlorine (chloramines) in many public swimming pools. Little is known about the fate of other disinfection by-products (DBPs) in UV treatment. Photolysis by medium pressure UV treatment was investigated for 12 DBPs reported to be found in swimming pool water: chloroform, bromodichloromethane, dibromochloromethane, bromoform, dichloroacetonitrile, bromochloroacetonitrile, dibromoacetronitrile, trichloroacetonitrile, trichloronitromethane, dichloropropanone, trichloropropanone, and chloral hydrate. First order photolysis constants ranged 26-fold from 0.020 min(-1) for chloroform to 0.523 min(-1) for trichloronitromethane. The rate constants generally increased with bromine substitution. Using the UV removal of combined chlorine as an actinometer, the rate constants were recalculated to actual treatment doses of UV applied in a swimming pool. In an investigated public pool the UV dose was equivalent to an applied electrical energy of 1.34 kWh m(-3) d(-1) and the UV dose required to removed 90% of trichloronitromethane was 0.4 kWh m(-3) d(-1), while 2.6 kWh m(-3) d(-1) was required for chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes ranged from 0.6 to 3.1 kWh m(-3) d(-1). It was predicted thus that a beneficial side-effect of applying UV for removing combined chlorine from the pool water could be a significant removal of trichloronitromethane, chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes. Copyright © 2012 Elsevier B.V. All rights reserved.

Development and validation of a general derivatization HPLC method for the trace analysis of acyl chlorides in lipophilic drug substances.

PubMed

Zheng, Xiangyuan; Luo, Lan; Zhou, Jie; Ruan, Xiaoling; Liu, Wenyuan; Zheng, Feng

2017-06-05

Acyl chlorides are important acylating agents in the synthesis of active pharmaceutical ingredients. Determining the residual acyl chlorides in drug substances is a challenge due to their high reactivity and the matrix interferences from drug substances and their related impurities. This paper describes a general derivatization HPLC method for the determination of aromatic and aliphatic acyl chlorides in lipophilic drug substances. Since most drug substances have weak absorptions in the visible range (above 380nm), the nitro-substituted anilines and nitro-substituted phenylhydrazines were selected as the derivatization reagents due to their weak basicity and red-shift of UV absorption spectra. The maximum wavelength and absorption intensity of nitro-substituted anilines decreased after derivatization with acyl chlorides, whereas the derivatization products of nitro-substituted phenylhydrazines showed the slight increases of maximum wavelength and absorbance intensity. Hence, 2-nitrophenylhydrazine was selected as the suitable derivatization reagent because the derivatives have the maximum UV wavelength absorbance at 395nm, which could largely minimize the matrix interferences. The optimization of the concentration of 2-nitrophenylhydrazine is important for the sensitivity and stability of derivatives. Other reaction conditions including reaction temperature, time and the influence of three competitive solvents (water, methanol and ethanol) on the reaction efficiency were also studied. After derivatization with 100μgmL -1 2-nitrophenylhydrazine at room temperature for 30min, the method was validated for high specificity and sensitivity with the detection limits in the range of 0.01-0.03μgmL -1 . The proposed method was applied as a generic method to determine the residual acyl chlorides in lipophilic drug substances. Copyright © 2017 Elsevier B.V. All rights reserved.

Specific amino acid residues in the beta sliding clamp establish a DNA polymerase usage hierarchy in Escherichia coli.

PubMed

Sutton, Mark D; Duzen, Jill M

2006-03-07

Escherichia coli dnaN159 strains encode a mutant form of the beta sliding clamp (beta159), causing them to display altered DNA polymerase (pol) usage. In order to better understand mechanisms of pol selection/switching in E. coli, we have further characterized pol usage in the dnaN159 strain. The dnaN159 allele contains two amino acid substitutions: G66E (glycine-66 to glutamic acid) and G174A (glycine-174 to alanine). Our results indicated that the G174A substitution impaired interaction of the beta clamp with the alpha catalytic subunit of pol III. In light of this finding, we designed two additional dnaN alleles. One of these dnaN alleles contained a G174A substitution (beta-G174A), while the other contained D173A, G174A and H175A substitutions (beta-173-175). Examination of strains bearing these different dnaN alleles indicated that each conferred a distinct UV sensitive phenotype that was dependent upon a unique combination of Delta polB (pol II), Delta dinB (pol IV) and/or Delta umuDC (pol V) alleles. Taken together, these findings indicate that mutations in the beta clamp differentially affect the functions of these three pols, and suggest that pol II, pol IV and pol V are capable of influencing each others' abilities to gain access to the replication fork. These findings are discussed in terms of a model whereby amino acid residues in the vicinity of those mutated in beta159 (G66 and G174) help to define a DNA polymerase usage hierarchy in E. coli following UV irradiation.

Unprecedented chemosensing behavior of novel tetra-substituted benzimidazole zinc(II) phthalocynine for selective detection of Bi3 + ion: Synthesis, characterization and ROS generation

NASA Astrophysics Data System (ADS)

Ullah, Azeem; Shah, Faheem; Khan, Imran; Anwar, Muhammad; Shah, Kiramat; Muhammad, Munira Taj; Ahmad, Farid

2018-03-01

In this work, synthesis of novel symmetrical 4-(2-bromo-4-(5-bromo-1H-benzo[d] imidazol-2-yl) phenoxy) tetra substituted zinc phthalocyanine has been reported. The novel benzimidazole zinc phthlocynine compound (3) has been characterized by MALDI-TOF MS, FT-IR, UV-vis, and 1H NMR spectroscopy. This new compound 3 displayed excellent selectivity towards Bi3 + ion in the presence of other competitive ions including Ca2 +, Cd2 +, Co2 + Cu2 +, Fe3 +, Hg2 +, Sn2 +, Mg2 +, Na+, Ni2 + and Pb2 + respectively. Upon addition of Bi3 + into the solution of compound 3 in DMSO, dramatic change was observed in the Q- and the B-bands in UV-visible spectra as a result of donor acceptor interactions. Reactive oxygen species (ROS) were also studied using 2,7-dichlorofluorescin diacetate (DCFH-DA) a fluorescent probe which is converted to highly fluorescent dichlorofluorescein (DCF) in the presence of ROS. This property of non-aggregating zinc phthalocyanine is promising as a photosensitizer in photodynamic therapy of cancer.

Kinetics of the substitution of dehydroacetic acid in tris (dehydroacetato) Fe(III) complex by 8-hydroxyquinoline, di- and tetra-hydroxyquinone

NASA Astrophysics Data System (ADS)

Fouad, D. M.; Ismail, N. M.; El-Gahami, M. A.; Ibrahim, S. A.

2007-06-01

The ligand substitution reactions of dehydroacetic acid (Hdha) in [Fe(dha) 3] with second ligand such as 8-hydroxyquinoline (Hquin), 1,4-dihydroxyanthraquinone (H 2dhaq) and 1,4,5,8-tetra-hydroxyanthraquinone (H 4thaq) were investigated spectrophotometrically by in low polarity solvents like benzene, chloroform and dichloromethane. It is deduced that the substitution reaction takes place through one successive step. The reaction was performed at four different temperatures (5-25) °C, and it exhibits a first order dependence on the concentration of the starting complex. The observed rate constant depends on the concentration of both leaving and entering ligands. The evaluation of the kinetic data gives activation parameters which support an associative mechanism in the transition states and the higher rate of substitution of the dha in Fe(dha) 3 complex is due to entropy effect. The solid complexes were synthesized and characterized by elemental analysis, IR and UV-vis spectral techniques.

Exploring the Limits of DNA Size: Naphtho-homologated DNA Bases and Pairs

PubMed Central

Lee, Alex H. F.; Kool, Eric T.

2008-01-01

A new design for DNA bases and base pairs is described in which the pyrimidine bases are widened by naphtho-homologation. Two naphtho-homologated deoxyribosides, dyyT (1) and dyyC (2) were synthesized and could be incorporated into oligonucleotides as suitably protected phosphoramidite derivatives. The deoxyribosides were found to be fluorescent, with emission maxima at 446 and 433 nm, respectively. Studies with single substitutions of 1 and 2 in the natural DNA context revealed exceptionally strong base stacking propensity for both. Sequences containing multiple substitutions of 1 and 2 paired opposite adenine and guanine were subsequently mixed and studied by several analytical methods. Data from UV mixing experiments, FRET measurements, fluorescence quenching experiments, and hybridizations on beads suggest that complementary “doublewide DNA” (yyDNA) strands may self-assemble into helical complexes with 1:1 stoichiometry. Data from thermal denaturation plots and CD spectra were less conclusive. Control experiments in one sequence context gave evidence that yyDNA helices, if formed, are preferentially antiparallel and are sequence selective. Hypothesized base pairing schemes are analogous to Watson-Crick pairing, but with glycosidic C1′-C1′ distances widened by over 45%, to ca. 15.2 Å. The possible self-assembly of the double-wide DNA helix establishes a new limit for the size of information-encoding, DNA-like molecules, and the fluorescence of yyDNA bases suggests uses as reporters in monomeric and oligomeric forms. PMID:16834396

Highly soluble 3,4-(dimethoxyphenylthio) substituted phthalocyanines: Synthesis, photophysical and photochemical studies

NASA Astrophysics Data System (ADS)

Öztürk, Cansu; Erdoğmuş, Ali; Durmuş, Mahmut; Uğur, Ahmet Lütfi; Kılıçarslan, Fatma Aytan; Erden, İbrahim

2012-02-01

The synthesis of a new 3,4-(dimethoxyphenylthio) substituted phthalonitrile ( 1) and its soluble metal free ( 2), zinc (II) ( 3), oxo-titanium (IV) ( 4) and nickel (II) ( 5) phthalocyanine derivatives are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, 1H NMR, UV-Vis, fluorescence spectroscopies and mass spectra. General trends are described for fluorescence, photodegradation and singlet oxygen quantum yields and fluorescence lifetimes of oxo-titanium (IV) and zinc (II) phthalocyanine compounds in dimethylsulfoxide (DMSO). The effects of the metal ion on the photophysical and photochemical parameters for these phthalocyanines ( 3 and 4) are also reported.

Substituent and solvent effects on the UV/vis absorption spectra of 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones

NASA Astrophysics Data System (ADS)

Mijin, Dušan Ž.; Ušćumlić, Gordana S.; Perišić-Janjić, Nada U.; Valentić, Nataša V.

2006-01-01

Absorption spectra of seventeen 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones have been recorded in 12 protic and aprotic solvents in the range 200-600 nm. The effects of substituents on the absorption spectra of these new azo dyes are interpreted by correlation of absorption frequencies with Hammett equation. The solute-solvent interactions were clarified on the basis of linear solvation energy relationships concept proposed by Kamlet and Taft. The 2-pyridone/2-hydroxypiridine tautomeric equilibration is found to depend upon substituents as well as on solvents.

Photocatalytic degradation of congo red using copper substituted cobalt ferrite

NASA Astrophysics Data System (ADS)

Kirankumar, V. S.; Hardik, B.; Sumathi, S.

2017-11-01

Co1-xCuxFe2O4 nanoparticles with x = 0 and 0.5 were synthesized through the combustion method. The as-made materials are face centered-cubic close-packed spinel structures. The characterization techniques such as powder XRD, FTIR, UV-DRS and SEM studies collectively verified that the formed products are cobalt ferrite and copper substituted cobalt ferrite nanoparticles. In addition, the mean crystalline size, lattice parameter and band gap energy of nanoparticles are calculated. The photocatalytic activity of the obtained Co1-xCuxFe2O4 spinel nanoparticles is evaluated by monitoring the degradation of congo red under visible light irradiation.

Using UHPLC and UV-vis Fingerprint Method to Evaluate Substitutes for Swertia mileensis: An Endangered Medicinal Plant.

PubMed

Li, Jie; Zhang, Ji; Jin, Hang; Wang, Yuan-Zhong; Huang, Heng-Yu

2017-01-01

Millions of people are killed by viral hepatitis every year in the world, whereas many relevant medicines are too expensive to purchase. Swertia mileensis , a medicinal plant for hepatitis in the system of traditional Chinese medicine, has been vanishing gradually because of overexploitation. To find substitutes of S. mileensis and reduce the cost of purchasing drugs for hepatitis patients, the similarity of phytochemical constituents between S. mileensis and other three Swertia species was compared. Both ultra high performance liquid chromatographies and ultraviolet-vis fingerprints of four Swertia species were developed. Methanol extracts of the stems and leaves were used as samples to establish the fingerprint. The calibration curve was drawn for quantitative analysis of swertiamarin. The data of ultra high performance liquid chromatographies were evaluated statistically using similarity analysis and principal component analysis. The result shows a significant difference at area of 204-290 nm in the ultraviolet fingerprint. Swertiamarin, the only one common peak, was defined in chromatographic fingerprints of four Swertia species. The quantitative analysis suggested that the highest concentration of swertiamarin is in S. davidii . The similarity indexes between different samples were almost under 0.60. In the principal component analysis, separate points not only represent the distinction among different species, but also perform chemical discrepancies in content between stems and leaves of one same species. S. angustifolia , S. davidii , and S. punicea are not suitable as substitutes of S. mileensis because of their remarkable differences in entirety and local part. In order to address issues about substitutes and high cost of purchasing drugs, more studies need to undertake. The UHPLC fingerprint method indicated the significant difference on chemical ingredients in four plants from Swertia .Swertiamarin is the unique common compounds for four plants, which exist are in leaves of S. davidii with the highest content.The obvious diversity in four plants was displayed from comprehensive point of view though similarity assay and PCA analysis.The UV fingerprint method offsets the defect that the UHPLC fingerprint reflected messages of secoiridoid glycosides only. Abbreviation used: UHPLC: Ultra high performance liquid chromatography, UV-vis: Ultraviolet-vis, HBV: Anti-hepatitis virus, DNA: Deoxyribonucleic acid, PCA: Principal component analysis, D-GaIN: D-Galactosamine, BCG: Bacille Calmette-Guerin, LPS: Lipopolysaccharide.

Using UHPLC and UV-vis Fingerprint Method to Evaluate Substitutes for Swertia mileensis: An Endangered Medicinal Plant

PubMed Central

Li, Jie; Zhang, Ji; Jin, Hang; Wang, Yuan-Zhong; Huang, Heng-Yu

2017-01-01

Background: Millions of people are killed by viral hepatitis every year in the world, whereas many relevant medicines are too expensive to purchase. Swertia mileensis, a medicinal plant for hepatitis in the system of traditional Chinese medicine, has been vanishing gradually because of overexploitation. Objective: To find substitutes of S. mileensis and reduce the cost of purchasing drugs for hepatitis patients, the similarity of phytochemical constituents between S. mileensis and other three Swertia species was compared. Materials and Methods: Both ultra high performance liquid chromatographies and ultraviolet-vis fingerprints of four Swertia species were developed. Methanol extracts of the stems and leaves were used as samples to establish the fingerprint. The calibration curve was drawn for quantitative analysis of swertiamarin. The data of ultra high performance liquid chromatographies were evaluated statistically using similarity analysis and principal component analysis. Results: The result shows a significant difference at area of 204–290 nm in the ultraviolet fingerprint. Swertiamarin, the only one common peak, was defined in chromatographic fingerprints of four Swertia species. The quantitative analysis suggested that the highest concentration of swertiamarin is in S. davidii. The similarity indexes between different samples were almost under 0.60. In the principal component analysis, separate points not only represent the distinction among different species, but also perform chemical discrepancies in content between stems and leaves of one same species. Conclusions: S. angustifolia, S. davidii, and S. punicea are not suitable as substitutes of S. mileensis because of their remarkable differences in entirety and local part. In order to address issues about substitutes and high cost of purchasing drugs, more studies need to undertake. SUMMARY The UHPLC fingerprint method indicated the significant difference on chemical ingredients in four plants from Swertia.Swertiamarin is the unique common compounds for four plants, which exist are in leaves of S. davidii with the highest content.The obvious diversity in four plants was displayed from comprehensive point of view though similarity assay and PCA analysis.The UV fingerprint method offsets the defect that the UHPLC fingerprint reflected messages of secoiridoid glycosides only. Abbreviation used: UHPLC: Ultra high performance liquid chromatography, UV-vis: Ultraviolet-vis, HBV: Anti-hepatitis virus, DNA: Deoxyribonucleic acid, PCA: Principal component analysis, D-GaIN: D-Galactosamine, BCG: Bacille Calmette-Guerin, LPS: Lipopolysaccharide PMID:28216877

Photophysical properties of a novel axially substituted tetra-α-(pentyloxy) Titanium(IV) Phthalocyanine - Hematoxylin

NASA Astrophysics Data System (ADS)

Jiang, Yufeng; Lv, Huafei; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Huang, Yide; Wang, Yuhua; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2017-06-01

Metal phthalocyanines (MPcs) are a very important class of widespread application compounds. They are not only used as dyes but also used as catalysts, data storage, electron charge carriers in photocopiers, photoconductors in chemical sensors, and photo-antenna devices in photosysthesis, photovoltaic cells. A particular application of Pcs is that it was used as a photosensitizers (PS) for treatment of certain cancer by photodynamic therapy of cancer and non-cancer diseases. However, the molecular aggregation of phthalocyanines, which is an intrinsic property of these large π-π conjugated systems, provides an efficient non-radioactive energy relaxation pathway, thereby shortening the excited state lifetimes, and reducing the photosensitizing and target efficiency. To overcome these problems, the introduction of axial ligands to phthalocyanine can prevent the formation of aggregation to some extend. In this paper, hematoxylin axially substituted tetra-α-(pentoxy) titanium (IV) phthalocyanine (TiPc(OC5H11)4-Hematoxylin) were characterized by elemental analysis, IR, 1H NMR, UV-Vis, fluorescence spectra. No obviously Q band change was observed after the hematoxylin was substituted at the peripheral position of substituted phthalocyanine ring. Because of the rigidity structure of the hematoxylin, the fluorescence intensity of hematoxylin peripheral substituted phthalocyanine decreased compared with free substituted phthalocyanines. The fluorescence lifetimes of axially substituted phthalocyanine was fitted to be 3.613 ns. This compound may be considered as a promising photosensitizer for PDT.

Photocatalytic CO2 reduction by Cr-substituted Ba2(In2-xCrx)O5·(H2O)δ (0.04 ≤ x ≤ 0.60)

NASA Astrophysics Data System (ADS)

Yoon, Songhak; Gaul, Michael; Sharma, Sitansh; Son, Kwanghyo; Hagemann, Hans; Ziegenbalg, Dirk; Schwingenschlogl, Udo; Widenmeyer, Marc; Weidenkaff, Anke

2018-04-01

Cr-substituted polycrystalline Ba2(In2-xCrx)O5·(H2O)δ powders (0.04 ≤ x ≤ 0.60) were synthesized by solid state reaction to investigate the relation of crystal structure, thermochemical, magnetic, and optical properties. The Cr-substitution results in an unit cell expansion and formation of the higher-symmetric tetragonal phase together with increased oxygen and hydrogen contents. Magnetic property measurements reveal that the diamagnetic pristine Ba2In2O5·(H2O)δ becomes magnetically ordered upon Cr-substitution. By UV-vis spectroscopy a gradual shift of the absorption-edge energy to lower values was observed. Numerical calculations showed that the observed bandgap narrowing was ascribed to the Cr induced states near the Fermi level. The correlation between the changes of crystal chemistry, magnetic, and optical properties of Cr-substituted Ba2(In2-xCrx)O5·(H2O)δ can be explained by the replacement of In by Cr. Consequently, an enhanced photocatalytic CO2 reduction activity was observed with increasing Cr substitution, compatible with the state-of-the-art high surface area TiO2 photocatalyst (P-25).

Integrated photocatalytic filtration array for indoor air quality control.

PubMed

Denny, Frans; Permana, Eric; Scott, Jason; Wang, Jing; Pui, David Y H; Amal, Rose

2010-07-15

Photocatalytic and filtration technologies were integrated to develop a hybrid system capable of removing and oxidizing organic pollutants from an air stream. A fluidized bed aerosol generator (FBAG) was adapted to prepare TiO(2)-loaded ventilation filters for the photodegradation of gas phase ethanol. Compared to a manually loaded filter, the ethanol photodegradation rate constant for the FBAG coated filter increased by 361%. Additionally, the presence of the photogenerated intermediate product, acetaldehyde, was reduced and the time for mineralization to CO(2) was accelerated. These improvements were attributed to the FBAG system providing a more uniform distribution of TiO(2) particles across the filter surface leading to greater accessibility by the UV light. A dual-UV-lamp system, as opposed to a single-lamp system, enhanced photocatalytic filter performance demonstrating the importance of high light irradiance and light distribution across the filter surface. Substituting the blacklight blue lamps with a UV-light-emitting-diode (UV-LED) array led to further improvement as well as suppressed the electrical energy per order (EE/O) by a factor of 6. These improvements derived from the more uniform distribution of light irradiance as well as the higher efficiency of UV-LEDs in converting electrical energy to photons.

Syntheses and characterizations of transition-metal-substituted aluminophosphate molecular sieves |(C3N2H5) 8|[M8Al16P24O96] (M = Co, Mn, Zn) with zeotype LAU topology.

PubMed

Song, Xiaowei; Li, Jiyang; Guo, Yanan; Pan, Qinhe; Gan, Lin; Yu, Jihong; Xu, Ruren

2009-01-05

Three transitional-metal-substituted aluminophosphate molecular sieves, |(C3N2H5)8|[M8Al16P24O96] (denoted MAPO-LAU, M = Co, Mn, Zn), have been synthesized under solvothermal conditions in the presence of imidazole as the structure-directing agent. Their structures are determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, thermogravimetric, and diffuse reflectance spectroscopy (UV-vis) analyses. The structure of MAPO-LAU is based on the strict alternation of MO4/AlO4 tetrahedra and PO4 tetrahedra through vertex oxygen atoms. Their frameworks are analogous to the zeotype LAU structure in which 33% of the aluminum sites are replaced by transitional-metal ions. The protonated imidazole cations resided in the 10-ring channels. These compounds show photoluminescent properties due to the existence of imidazole molecules in the structures. Magnetic measurements reveal that there is very weak antiferromagnetic interaction among the metal centers of MnAPO-LAU.

5-Fluoro pyrimidines: labels to probe DNA and RNA secondary structures by 1D 19F NMR spectroscopy

PubMed Central

Puffer, Barbara; Kreutz, Christoph; Rieder, Ulrike; Ebert, Marc-Olivier; Konrat, Robert; Micura, Ronald

2009-01-01

19F NMR spectroscopy has proved to be a valuable tool to monitor functionally important conformational transitions of nucleic acids. Here, we present a systematic investigation on the application of 5-fluoro pyrimidines to probe DNA and RNA secondary structures. Oligonucleotides with the propensity to adapt secondary structure equilibria were chosen as model systems and analyzed by 1D 19F and 1H NMR spectroscopy. A comparison with the unmodified analogs revealed that the equilibrium characteristics of the bistable DNA and RNA oligonucleotides were hardly affected upon fluorine substitution at C5 of pyrimidines. This observation was in accordance with UV spectroscopic melting experiments which demonstrated that single 5-fluoro substitutions in double helices lead to comparable thermodynamic stabilities. Thus, 5-fluoro pyrimidine labeling of DNA and RNA can be reliably applied for NMR based nucleic acid secondary structure evaluation. Furthermore, we developed a facile synthetic route towards 5-fluoro cytidine phosphoramidites that enables their convenient site-specific incorporation into oligonucleotides by solid-phase synthesis. PMID:19843610

5-Fluoro pyrimidines: labels to probe DNA and RNA secondary structures by 1D 19F NMR spectroscopy.

PubMed

Puffer, Barbara; Kreutz, Christoph; Rieder, Ulrike; Ebert, Marc-Olivier; Konrat, Robert; Micura, Ronald

2009-12-01

(19)F NMR spectroscopy has proved to be a valuable tool to monitor functionally important conformational transitions of nucleic acids. Here, we present a systematic investigation on the application of 5-fluoro pyrimidines to probe DNA and RNA secondary structures. Oligonucleotides with the propensity to adapt secondary structure equilibria were chosen as model systems and analyzed by 1D (19)F and (1)H NMR spectroscopy. A comparison with the unmodified analogs revealed that the equilibrium characteristics of the bistable DNA and RNA oligonucleotides were hardly affected upon fluorine substitution at C5 of pyrimidines. This observation was in accordance with UV spectroscopic melting experiments which demonstrated that single 5-fluoro substitutions in double helices lead to comparable thermodynamic stabilities. Thus, 5-fluoro pyrimidine labeling of DNA and RNA can be reliably applied for NMR based nucleic acid secondary structure evaluation. Furthermore, we developed a facile synthetic route towards 5-fluoro cytidine phosphoramidites that enables their convenient site-specific incorporation into oligonucleotides by solid-phase synthesis.

Continuous twin screw granulation of controlled release formulations with various HPMC grades.

PubMed

Vanhoorne, V; Janssens, L; Vercruysse, J; De Beer, T; Remon, J P; Vervaet, C

2016-09-25

HPMC is a popular matrix former to formulate tablets with extended drug release. Tablets with HPMC are preferentially produced by direct compression. However, granulation is often required prior to tableting to overcome poor flowability of the formulation. While continuous twin screw granulation has been extensively evaluated for granulation of immediate release formulations, twin screw granulation of controlled release formulations including the dissolution behavior of the formulations received little attention. Therefore, the influence of the HPMC grade (viscosity and substitution degree) and the particle size of theophylline on critical quality attributes of granules (continuously produced via twin screw granulation) and tablets was investigated in the current study. Formulations with 20 or 40% HPMC, 20% theophylline and lactose were granulated with water at fixed process parameters via twin screw granulation. The torque was influenced by the viscosity and substitution degree of HPMC, but was not a limiting factor for the granulation process. An optimal L/S ratio was selected for each formulation based on the granule size distribution. The granule size distributions were influenced by the substitution degree and concentration of HPMC and the particle size of theophylline. Raman and UV spectroscopic analysis on 8 sieve fractions of granules indicated an inhomogeneous distribution of theophylline over the size fractions. However, this phenomenon was not correlated with the hydration rate or viscosity of HPMC. Controlled release of theophylline could be obtained over 24h with release profiles close to zero-order. The release of theophylline could be tailored via selection of the substitution degree and viscosity of HPMC. Copyright © 2016 Elsevier B.V. All rights reserved.

Radiation Induced Degradation of the White Thermal Control Paints Z-93 and Z-93P

NASA Technical Reports Server (NTRS)

Edwards, D. L.; Zwiener, J. M.; Wertz, G. E.; Vaughn, J. A.; Kamenetzky, R. R.; Finckenor, M. M.; Meshishnek, M. J.

1996-01-01

This paper details a comparison analysis of the zinc oxide pigmented white thermal control paints Z-93 and Z-93P. Both paints were simultaneously exposed to combined space environmental effects and analyzed using an in-vacuo reflectance technique. The dose applied to the paints was approximately equivalent to 5 years in a geosynchronous orbit. This comparison analysis showed that Z-93P is an acceptable substitute for Z-93. Irradiated samples of Z-93 and Z-93P were subjected to additional exposures of ultraviolet (UV) radiation and analyzed using the in-vacuo reflectance technique to investigate UV activated reflectance recovery. Both samples showed minimal UV activated reflectance recovery after an additional 190 equivalent sun hour (ESH) exposure. Reflectance response utilizing nitrogen as a repressurizing gas instead of air was also investigated. This investigation found the rates of reflectance recovery when repressurized with nitrogen are slower than when repressurized with air.

Radiation Induced Degradation of White Thermal Control Paint

NASA Technical Reports Server (NTRS)

Edwards, D. L.; Zwiener, J. M.; Wertz, G. E.; Vaughn, Jason A.; Kamenetzky, Rachel R.; Finckenor, M. M.; Meshishnek, M. J.

1999-01-01

This paper details a comparison analysis of the zinc-oxide pigmented white thermal control paints Z-93 and Z-93P. Both paints were simultaneously exposed to combined space environmental effects and analyzed using an in-vacuo reflectance technique. The dose applied to the paints was approximately equivalent to 5 yr in a geosynchronous orbit. This comparison analysis showed that Z-93P is an acceptable substitute for Z-93. Irradiated samples of Z-93 and Z-93P were subjected to additional exposures of ultraviolet (UV) radiation and analyzed using the in-vacuo reflectance technique to investigate UV activated reflectance recovery. Both samples showed minimal UV activated reflectance recovery after an additional 190 equivalent Sun hour (ESH) exposure. Reflectance response utilizing nitrogen as a repressurizing gas instead of air was also investigated. This investigation found the rates of reflectance recovery when repressurized with nitrogen are slower than when repressurized with air.

Reversible photochromic system based on rhodamine B salicylaldehyde hydrazone metal complex.

PubMed

Li, Kai; Xiang, Yu; Wang, Xiaoyan; Li, Ji; Hu, Rongrong; Tong, Aijun; Tang, Ben Zhong

2014-01-29

Photochromic molecules are widely applied in chemistry, physics, biology, and materials science. Although a few photochromic systems have been developed before, their applications are still limited by complicated synthesis, low fatigue resistance, or incomplete light conversion. Rhodamine is a class of dyes with excellent optical properties including long-wavelength absorption, large absorption coefficient, and high photostability in its ring-open form. It is an ideal chromophore for the development of new photochromic systems. However, known photochromic rhodamine derivatives, such as amides, exhibit only millisecond lifetimes in their colored ring-open forms, making their application very limited and difficult. In this work, rhodamine B salicylaldehyde hydrazone metal complex was found to undergo intramolecular ring-open reactions upon UV irradiation, which led to a distinct color and fluorescence change both in solution and in solid matrix. The complex showed good fatigue resistance for the reversible photochromism and long lifetime for the ring-open state. Interestingly, the thermal bleaching rate was tunable by using different metal ions, temperatures, solvents, and chemical substitutions. It was proposed that UV light promoted isomerization of the rhodamine B derivative from enol-form to keto-form, which induced ring-opening of the rhodamine spirolactam in the complex to generate color. The photochromic system was successfully applied for photoprinting and UV strength measurement in the solid state. As compared to other reported photochromic molecules, the system in this study has its advantages of facile synthesis and tunable thermal bleaching rate, and also provides new insights into the development of photochromic materials based on metal complex and spirolactam-containing dyes.

Control of Photoluminescence of Carbon Nanodots via Surface Functionalization using Para-substituted Anilines

NASA Astrophysics Data System (ADS)

Kwon, Woosung; Do, Sungan; Kim, Ji-Hee; Seok Jeong, Mun; Rhee, Shi-Woo

2015-07-01

Carbon nanodots (C-dots) are a kind of fluorescent carbon nanomaterials, composed of polyaromatic carbon domains surrounded by amorphous carbon frames, and have attracted a great deal of attention because of their interesting properties. There are still, however, challenges ahead such as blue-biased photoluminescence, spectral broadness, undefined energy gaps and etc. In this report, we chemically modify the surface of C-dots with a series of para-substituted anilines to control their photoluminescence. Our surface functionalization endows our C-dots with new energy levels, exhibiting long-wavelength (up to 650 nm) photoluminescence of very narrow spectral widths. The roles of para-substituted anilines and their substituents in developing such energy levels are thoroughly studied by using transient absorption spectroscopy. We finally demonstrate light-emitting devices exploiting our C-dots as a phosphor, converting UV light to a variety of colors with internal quantum yields of ca. 20%.

Optical properties of Y and Ti co-substituted BiFeO{sub 3} multiferroics

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

Singh, Vikash, E-mail: rk.dwivedi@jiit.ac.in; Sharma, Subhash, E-mail: rk.dwivedi@jiit.ac.in; Kumar, Manoj, E-mail: rk.dwivedi@jiit.ac.in

2014-04-24

Pure and co substituted Bi{sub 1−x}Y{sub x}Fe{sub 1−x}Ti{sub x}O{sub 3} (x ≤ 0.24) ceramics were synthesized by solid state reaction method. X-ray diffraction patterns of Y and Ti codoped samples have shown single phase formation. Increasing Y and Ti concentration reveals structural transition from rhombohedral phase (R3c) for x ≤ 0.16 to orthorhombic phase (Pnma) for x = 0.24. FT-IR spectra exhibit broad absorption bands, which may be due to the overlapping of Fe-O and Bi-O vibrations. UV-visible spectroscopy results show strong absorption of light in the spectral range of 400-720 nm, indicating optical band gap in the visible regionmore » for these samples. These interesting optical properties of co-substituted BFO samples in visible region may find potential applications in optoelectronic devices.« less

Impact of Gd3+/graphene substitution on the physical properties of magnesium ferrite nanocomposites

NASA Astrophysics Data System (ADS)

Ateia, Ebtesam E.; Mohamed, Amira T.; Elsayed, Kareem

2018-04-01

Magnesium nano ferrite with composition MgFe2O4, MgGd0.05Fe1.95O4 and MgFe2O4 - 5 wt% GO was synthesized using a citrate auto-combustion method. The crystal structure, morphology, and magnetic properties of the investigated samples were studied. High Resolution Transmission Electron Microscopy (HRTEM) images show that the substitution of small amounts of Gd3+/GO causes a considerable reduction of the grain size. Studies on the magnetic properties demonstrate that the coercivity of GO-substituted magnesium nano ferrites is enhanced from 72 Oe to 203 Oe and the magnetocrystalline anisotropy constant increases from 1171 to 3425 emu Oe/gm at 300 K. The direct effects of graphene on morphology, crystal structure as well as the magnetic properties reveal that the studied sample are suitable for turbidity color and removal. The magnetic entropy change is estimated from magnetization data using Maxwell relation. The calculated Curie temperature from the Curie-Weiss law and the maximum entropy change are in good agreement with each other. Based on UV diffuse reflectance spectroscopy studies, the optical band gaps are in the range of 1.4-2.15 eV. In addition, the combination of small particle size and good magnetic properties makes the investigated samples act as a potential candidates for superior catalysts, adsorbents, and electromagnetic wave absorbers.

The Effect of Fluorine Substitution on the Molecular Interactions and Performance in Polymer Solar Cells.

PubMed

Kim, In-Bok; Jang, Soo-Young; Kim, Yeong-A; Kang, Rira; Kim, In-Sik; Ko, Do-Kyeong; Kim, Dong-Yu

2017-07-19

Fluorine (F) substitution on conjugated polymers in polymer solar cells (PSCs) has a diverse effect on molecular properties and device performance. We present a series of three D-A type conjugated polymers (PBT, PFBT, and PDFBT) based on dithienothiophene and benzothiadiazole units with different numbers of F atoms to explain the influence of F substitution by comparing the molecular interactions of the polymers and the recombination kinetics in PSCs. The preaggregation behavior of PFBT and PDFBT in o-DCB at the UV-vis absorption spectra proves that both polymers have strong intermolecular interactions. Besides, more closely packed structures and change into face-on orientation of fluorinated polymers are observed in polymer:PC 71 BM blends by GIXD which is beneficial for charge transport and, ultimately, for current density in PSCs (4.3, 13.0, and 14.5 mA cm -2 for PBT, PFBT, and PDFBT, respectively). Also, the introduction of F atoms on conjugated backbones affects the recombination kinetics by suppressing bimolecular recombination, thereby improving the fill factor (0.41, 0.68, and 0.69 for PBT, PFBT, and PDFBT, respectively). Consequently, the PCE of PSCs reached 7.3% without any additional treatment (annealing, solvent additive, etc.) in the polymer containing difluorinated BT (PDFBT) that is much higher than nonfluorinated BT (PBT ∼ 1%) and monofluorinated BT (PFBT ∼ 6%).

Conformationally-restricted bicarbazoles with phenylene bridges displaying deep-blue emission and high triplet energies: systematic structure-property relationships.

PubMed

Wright, Iain A; Al-Attar, Hameed A; Batsanov, Andrei S; Monkman, Andrew P; Bryce, Martin R

2018-05-07

The synthesis is reported of twelve new symmetrical carbazole dimers in which the carbazole units are linked via 1,4-phenylene spacers. There are two distinct series of compounds based on the position on the carbazole ring where the phenylene spacer is attached: this is either at carbazole C(3) (series 1a-1f) or at C(2) (series 2a-2f). The central phenylene ring is substituted with either two methyl, two methoxy or two cyano substituents which impart an intramolecular torsional angle between the phenylene and carbazole rings, thereby limiting the extent of π-conjugation between the carbazole units, and raising the triplet energies of the molecules to E T 2.6-3.0 eV, as determined from their phosphorescence spectra at 80 K. Structure-property relationships were studied by UV-vis and fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. A notable observation is that substitution at the 2-position of carbazole (linear conjugation) exerts control over the position of the HOMO, while substitution at the 3-position of carbazole (meta conjugation) allows greater control over the LUMO. X-ray crystal structures are reported for two of the bicarbazoles. Compound 2d is shown to be a suitable host for the sky-blue emitter FIrpic in PhOLEDs, with improved device performance compared to CBP as host.

V-doped SnS2: a new intermediate band material for a better use of the solar spectrum.

PubMed

Wahnón, Perla; Conesa, José C; Palacios, Pablo; Lucena, Raquel; Aguilera, Irene; Seminovski, Yohanna; Fresno, Fernando

2011-12-07

Intermediate band materials can boost photovoltaic efficiency through an increase in photocurrent without photovoltage degradation thanks to the use of two sub-bandgap photons to achieve a full electronic transition from the valence band to the conduction band of a semiconductor structure. After having reported in previous works several transition metal-substituted semiconductors as able to achieve the electronic structure needed for this scheme, we propose at present carrying out this substitution in sulfides that have bandgaps of around 2.0 eV and containing octahedrally coordinated cations such as In or Sn. Specifically, the electronic structure of layered SnS(2) with Sn partially substituted by vanadium is examined here with first principles quantum methods and seen to give favourable characteristics in this respect. The synthesis of this material in nanocrystalline powder form is then undertaken and achieved using solvothermal chemical methods. The insertion of vanadium in SnS(2) is found to produce an absorption spectrum in the UV-Vis-NIR range that displays a new sub-bandgap feature in agreement with the quantum calculations. A photocatalytic reaction-based test verifies that this sub-bandgap absorption produces highly mobile electrons and holes in the material that may be used for the solar energy conversion, giving experimental support to the quantum calculations predictions.

In situ modification of cell-culture scaffolds by photocatalysis of visible-light-responsive TiO2 film

NASA Astrophysics Data System (ADS)

Kono, Sho; Furusawa, Kohei; Kurotobi, Atsushi; Hattori, Kohei; Yamamoto, Hideaki; Hirano-Iwata, Ayumi; Tanii, Takashi

2018-02-01

We propose a novel process to modify the cell affinity of scaffolds in a cell-culture environment using the photocatalytic activity of visible-light (VL)-responsive TiO2. The proposed process is the improved version of our previous demonstration in which ultraviolet (UV)-responsive TiO2 was utilized. In that demonstration, we showed that cell-repellent molecules on TiO2 were decomposed and replaced with cell-permissive molecules upon UV exposure in the medium where cells are being cultured. However, UV irradiation involves taking the risk of inducing damage to the cells. In this work, a TiO2 film was sputter-deposited on a quartz coverslip at 640 °C without O2 gas injection to create a rutile structure containing oxygen defects, which is known to exhibit photocatalytic activity upon VL exposure. We show that the cell adhesion site and migration area can be controlled with the photocatalytic activity of the VL-responsive TiO2 film, while the cellular oxidative stress is reduced markedly by the substitution of VL for UV.

A litmus-type colorimetric and fluorometric volatile organic compound sensor based on inkjet-printed polydiacetylenes on paper substrates.

PubMed

Yoon, Bora; Park, In Sung; Shin, Hyora; Park, Hye Jin; Lee, Chan Woo; Kim, Jong-Man

2013-05-14

Inkjet-printed paper-based volatile organic compound (VOC) sensor strips imaged with polydiacetylenes (PDAs) are developed. A microemulsion ink containing bisurethane-substituted diacetylene (DA) monomers, 4BCMU, was inkjet printed onto paper using a conventional inkjet office printer. UV irradiation of the printed image allowed fabrication of blue-colored poly-4BCMU on the paper and the polymer was found to display colorimetric responses to VOCs. Interestingly, a blue-to-yellow color change was observed when the strip was exposed to chloroform vapor, which was accompanied by the generation of green fluorescence. The principal component analysis plot of the color and fluorescence images of the VOC-exposed polymers allowed a more precise discrimination of VOC vapors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel water soluble morpholine substituted Zn(II) phthalocyanine: Synthesis, characterization, DNA/BSA binding, DNA photocleavage and topoisomerase I inhibition.

PubMed

Barut, Burak; Demirbaş, Ümit; Özel, Arzu; Kantekin, Halit

2017-12-01

In this study, novel peripherally tetra 3-morpholinophenol substituted zinc(II) phthalocyanine (4) and its water soluble form quaternized zinc(II) phthalocyanine (ZnQ) were synthesized for the first time. These novel compounds were characterized by a combination of different spectroscopic techniques such as FT-IR, 1 H NMR, 13 C NMR, UV-vis and mass. The DNA binding of ZnQ was investigated using UV-vis absorption titration, competitive ethidium bromide, thermal denaturation and viscosity experiments that the ZnQ bound to CT-DNA via intercalation mode. ZnQ indicated photocleavage activity on supercoiled pBR322 plasmid DNA via formation of singlet oxygen under irradiation at 700nm. Besides, the topoisomerase I inhibitory effect experiments showed that ZnQ inhibited topoisomerase I enzyme in a concentration-dependent manner. The bovine serum albumin (BSA) binding experiments indicated that ZnQ bound to proteins through a static quenching mechanism. All of these results claim that ZnQ has potential agent for photodynamic therapy owing to its nucleic acid interactions and photobiological or photochemical properties. Copyright © 2017 Elsevier B.V. All rights reserved.

Novel mutations in β-tubulin gene in Trichoderma harzianum mutants resistant to methyl benzimidazol-2-yl carbamate.

PubMed

Li, M; Zhang, H Y; Liang, B

2013-01-01

Twelve-low resistant (LR) mutants of Trichoderma harzianum with the capability of grow fast at 0.8 μg/mL methyl benzimidazol-2-yl carbamate (MBC) were obtained using UV mutagenesis. MR and HR mutants which could grow fast at 10 and 100 μg/mL MBC, respectively, were isolated by step-up selection protocols in which UV-treated mutants were induced and mycelial sector screening was made in plates with growth medium. Subsequently, β-tubulin genes of 14 mutants were cloned to describe-the molecular lesion likely to be responsible-for MBC resistance. Comparison of the β-tubulin sequences of the mutant and sensitive strains of T. harzianum revealed 2 new MBC-binding sites differed from those in other plant pathogens. A single mutation at-amino acid 168, having Phe (TTC) instead of Ser (TCC)', was demonstrated for the HR mutant; a double mutation in amino acid 13 resulting in the substitution of Gly (GGC) by Val (GTG) was observed in β-tubulin gene of MR mutant. On the other hand, no substitutions were identified in the β-tubulin gene and its 5'-flanking regions in 12 LR mutants of T. harzianum.

Optical amplification and stability of spiroquaterphenyl compounds and blends

NASA Astrophysics Data System (ADS)

Fuhrmann-Lieker, T.; Lambrecht, J.; Hoinka, N.; Kiurski, M.; Wiske, A.; Hagelstein, G.; Yurttagül, Y.; Abdel-Awwad, M.; Wilke, H.; Messow, F.; Hillmer, H.; Salbeck, J.

2015-02-01

In this contribution, we present a systematic investigation on a series of spiroquaterphenyl compounds optimised for solid state lasing in the near ultraviolet (UV). Amplified spontaneous emission (ASE) thresholds in the order of 1 μJ/cm^2 are obtained in neat (undiluted) films and blends, with emission peaks at 390±1 nm for unsubstituted and meta-substituted quaterphenyls and 400±4 nm for para-ether substituted quaterphenyls. Mixing with a transparent matrix retains a low threshold, shifts the emission to lower wavelengths and allows a better access to modes having their intensity maximum deeper in the film. Chemical design and blending allow an independent tuning of optical and processing properties such as the glass transition.

[New iron-porphyrin/vanadium-substituted polyoxometalate catalyst: synthesis, characterization and catalytic activity].

PubMed

Dong, Xiao-li; Zhang, Zhen-cheng; An, Qing-da; Zhang, Shao-yin; Wang, Shao-jun

2007-12-01

A new kind of iron-porphyrin/vanadium-substituted polyoxometalate coordination compound was synthesized by the ion exchange reaction of FeTTMAPPI and H5PMo10V2o40 in solution. The new catalyst was characterized by IR spectrometry and UV-Vis spectrometry. As an excellent catalyst, its effects on benzene hydroxylation and catalytic capabilities were studied with H2O2 solution as the oxidant. The results indicated that the products contained the conjugated structure of porphyrin and the cage structure of polyoxometalate, the V atom in polyoxometalate is the main centre of catalytic activity, meanwhile the presence of iron-porphyrin could increase its catalytic activity greatly.

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.

Four-Component Damped Density Functional Response Theory Study of UV/Vis Absorption Spectra and Phosphorescence Parameters of Group 12 Metal-Substituted Porphyrins.

PubMed

Fransson, Thomas; Saue, Trond; Norman, Patrick

2016-05-10

The influences of group 12 (Zn, Cd, Hg) metal-substitution on the valence spectra and phosphorescence parameters of porphyrins (P) have been investigated in a relativistic setting. In order to obtain valence spectra, this study reports the first application of the damped linear response function, or complex polarization propagator, in the four-component density functional theory framework [as formulated in Villaume et al. J. Chem. Phys. 2010 , 133 , 064105 ]. It is shown that the steep increase in the density of states as due to the inclusion of spin-orbit coupling yields only minor changes in overall computational costs involved with the solution of the set of linear response equations. Comparing single-frequency to multifrequency spectral calculations, it is noted that the number of iterations in the iterative linear equation solver per frequency grid-point decreases monotonously from 30 to 0.74 as the number of frequency points goes from one to 19. The main heavy-atom effect on the UV/vis-absorption spectra is indirect and attributed to the change of point group symmetry due to metal-substitution, and it is noted that substitutions using heavier atoms yield small red-shifts of the intense Soret-band. Concerning phosphorescence parameters, the adoption of a four-component relativistic setting enables the calculation of such properties at a linear order of response theory, and any higher-order response functions do not need to be considered-a real, conventional, form of linear response theory has been used for the calculation of these parameters. For the substituted porphyrins, electronic coupling between the lowest triplet states is strong and results in theoretical estimates of lifetimes that are sensitive to the wave function and electron density parametrization. With this in mind, we report our best estimates of the phosphorescence lifetimes to be 460, 13.8, 11.2, and 0.00155 s for H2P, ZnP, CdP, and HgP, respectively, with the corresponding transition energies being equal to 1.46, 1.50, 1.38, and 0.89 eV.

Solid state synthesis of chitosan and its unsaturated derivatives for laser microfabrication of 3D scaffolds

NASA Astrophysics Data System (ADS)

Akopova, T. A.; Demina, T. S.; Bagratashvili, V. N.; Bardakova, K. N.; Novikov, M. M.; Selezneva, I. I.; Istomin, A. V.; Svidchenko, E. A.; Cherkaev, G. V.; Surin, N. M.; Timashev, P. S.

2015-07-01

Chitosans with various degrees of deacetylation and molecular weights and their allyl substituted derivatives were obtained through a solvent-free reaction under shear deformation in an extruder. Structure and physical-chemical analysis of the samples were carried out using nuclear magnetic resonance (NMR), ultraviolet (UV) and infrared radiation (IR) spectroscopy. Photosensitive materials based on the synthesized polymers were successfully used for microfabrication of 3D well-defined architectonic structures by laser stereolithography. Study on the metabolic activity of NCTC L929 cultured in the presence of the cured chitosan extracts indicates that the engineered biomaterials could support adhesion, spreading and growth of adherent-dependent cells, and thus could be considered as biocompatible scaffolds.

Synthesis and characterization of Ca{sup 2+} substituted barium niobate nanopaticles for photocatalytic and luminescence applications

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

Dudhe, C.M.; Nagdeote, S.B.; Palikundwar, U.A., E-mail: chandraguptadudhe@gmail.com

2016-09-15

Highlights: • Nanoparticles of Ca{sup 2+} (30 mol%) substituted BaNb{sub 2}O{sub 6} were synthesized. • Ca{sup 2+} ions occupy newer 8d Wyckoff positions rather than 4c. • Self-activated photoluminescence was observed. • Excellent H{sub 2} generation tendency from pure water under UV light was also observed. - Abstract: Ca{sup 2+} substituted barium niobate i.e. Ca{sub x}Ba{sub 1-x}Nb{sub 2}O{sub 6} (x = 0.3) compound in nanoparticles form was synthesized by a simple co-precipitation method for the first time and its structural characterization has been done by using powder X-ray diffraction data. Other characterizations were done by using transmission electron microscopy, energymore » dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ca{sub x}Ba{sub 1-x}Nb{sub 2}O{sub 6} (x = 0.3) compound stabilizes in the orthorhombic phase (Pbcn space group) with the lattice parameters a = 14.984 Å, b = 5.761 Å and c = 5.216 Å. A representative TEM image shows the irregular sphere like morphology of the synthesized particles with the size ranging from 70 to 120 nm. The optical band gap energy was found to be 3.74 eV. It was observed that the synthesized nanoparticles exhibit excellent H{sub 2} evolution tendency and self–activated photoluminescence under the excitation of UV light. These activities were assigned to the nanocrystalline nature of the synthesized material.« less

A Dicobalt Complex with an Unsymmetrical Quinonoid Bridge Isolated in Three Units of Charge: A Combined Structural, (Spectro)electrochemical, Magnetic and Spectroscopic Study.

PubMed

van der Meer, Margarethe; Rechkemmer, Yvonne; Frank, Uta; Breitgoff, Frauke D; Hohloch, Stephan; Su, Cheng-Yong; Neugebauer, Petr; Marx, Raphael; Dörfel, María; van Slageren, Joris; Sarkar, Biprajit

2016-09-19

Quinonoid ligands are excellent bridges for generating redox-rich dinuclear assemblies. A large majority of these bridges are symmetrically substituted, with examples of unsymmetrically substituted quinonoid bridges being extremely rare. We present here a dicobalt complex in its various redox states with an unsymmetrically substituted quinonoid bridging ligand. Two homovalent forms and one mixed-valent form have been isolated and characterized by single crystal X-ray diffraction. The complex displays a large comproportionation constant for the mixed-valent state which is three orders of magnitude higher than that observed for the analogous complex with a symmetrically substituted bridge. Results from electrochemistry, UV/Vis/NIR spectroelectrochemistry, SQUID magnetometry, multi-frequency EPR spectroscopy and FIR spectroscopy are used to probe the electronic structures of these complexes. FIR provides direct evidence of exchange coupling. The results presented here display the advantages of using an unsymmetrically substituted bridge: site specific redox chemistry, high thermodynamic stabilization of the mixed-valent form, isolation and crystallization of various redox forms of the complex. This work represents an important step on the way to generating heterodinuclear complexes for use in cooperative catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modulation of DNA-Polyamide Interaction by β-alanine Substitutions: A Study of Positional Effects on Binding Affinity, Kinetics and Thermodynamics

PubMed Central

Wang, Shuo; Aston, Karl; Koeller, Kevin J.; Harris, G. Davis; Rath, Nigam P.

2014-01-01

Hairpin polyamides (PAs) are an important class of sequence-specific DNA minor groove binders, and frequently employ a flexible motif, β-alanine (β), to reduce the molecular rigidity to maintain the DNA recognition register. To better understand the diverse effects β can have on DNA-PA binding affinity, selectivity, and especially kinetics, which have rarely been reported, we have initiated a detailed study for an eight-heterocyclic hairpin PA and its β derivatives with their cognate and mutant sequences. With these derivatives, all internal pyrroles of the parent PA are systematically substituted with single or double βs. A set of complementary experiments have been conducted to evaluate the molecular interactions in detail: UV-melting, biosensor-surface plasmon resonance, circular dichroism and isothermal titration calorimetry. The β substitutions generally weaken the binding affinities of these PAs with cognate DNA, and have large and diverse influences on PA binding kinetics in a position- and number-dependent manner. The DNA base mutations have also shown positional effects on binding of a single PA. Besides the β substitutions, the monocationic Dp group [3-(dimethylamino) propylamine] in parent PA has been modified into a dicationic Ta group (3, 3'-Diamino-N-methyldipropylamine) to minimize the frequently observed PA aggregation with ITC experiments. The results clearly show that the Ta modification not only maintains the DNA binding mode and affinity of PA, but also significantly reduces PA aggregation and allows the complete thermodynamic signature of eight-ring hairpin PA to be determined for the first time. This combined set of results significantly extends our understanding of the energetic basis of specific DNA recognition by PAs. PMID:25141096

Design, Synthesis and Optoelectronic Properties of Unsymmetrical Oxadiazole Based Indene Substituted Derivatives as Deep Blue Fluoroscent Materials.

PubMed

Belavagi, Ningaraddi S; Deshapande, Narahari; Pujar, G H; Wari, M N; Inamdar, S R; Khazi, Imtiyaz Ahmed M

2015-09-01

A series of novel unsymmetrically substituted indene-oxadiazole derivatives (3a-f) have been designed and synthesized by employing palladium catalysed Suzuki cross coupling reaction in high yields. The structural integrity of all the novel compounds was established by (1)H, (13)C NMR and LC/MS analysis. These compounds are amorphous in nature and are remarkably stable to long term storage under ambient conditions. The optoelectronic properties have been studied in detail using UV-Vis absorption and Fluorescence spectroscopy. All compounds emit intense blue to green-blue fluoroscence with high quantum yields. Time resolved measurments have shown life times in the range of 1.28 to 4.51 ns. The density functional theory (DFT) calculations were carried out for all the molecules to understand their structure-property relationships. Effect of concentration studies has been carried out in different concentrations for both absorption and emission properties and from this we have identified the optimized fluoroscence concentrations for all these compounds. The indene substituted anthracene-oxadiazole derivative (3f) showed significant red shift (λmax (emi) = 490 nm) and emits intense green-blue fluoroscence with largest stokes shift of 145 nm. This compound also exhibited highest fluoroscence life time (τ) of 4.51 ns, which is very close to the standard dye coumarin-540A (4.63 ns) and better than fluorescein-548 (4.10 ns). The results demonstrated that the novel unsymmetrical indene-substituted oxadiazole derivatives could play important role in organic optoelectronic applications, such as organic light-emitting diodes (OLEDs) or as models for investigating the fluorescent structure-property relationship of the indene-functionalized oxadiazole derivatives.

The role of proline-containing peptide triads in β-sheet formation: A kinetic study.

PubMed

Takor, Gaius A; Higashiya, Seiichiro; Sikirzhytski, Vitali K; Seeley, Jason P; Lednev, Igor K; Welch, John T

2015-06-01

The design of biomimetic materials through molecular self-assembly is a growing area of modern nanotechnology. With problems of protein folding, self-assembly, and sequence-structure relationships as essential in nanotechnology as in biology, the effect of the nucleation of β-hairpin formation by proline on the folding process has been investigated in model studies. Previously such studies were limited to investigations of the influence of proline on the formation of turns in short peptide sequences. The effect of proline-based triads on the folding of an 11-kDa amyloidogenic peptide GH6[(GA)3GY(GA)3GE]8 GAH6 (YE8) was investigated by selective substitution of the proline-substituted triads at the γ-turn sites. The folding and fibrillation of the singly proline-substituted polypeptides, e.g., GH6-[(GA)3GY(GA)3GE]7(GA)3GY(GA)3PD-GAH6 (8PD), and doubly proline-substituted polypeptides, e.g., GH6-[(GA)3GY(GA)3GE]3(GA)3GY(GA)3PD[(GA)3GY(GA)3GE]3(GA)3GY(GA)3PD-GAH6 (4,8PD), were directly monitored by circular dichroism and deep UV resonance Raman and fluorescence spectroscopies. These findings were used to identify the essential folding domains, i.e., the minimum number of β-strands necessary for stable folding. These experimental findings may be especially useful in the design and construction of peptidic materials for a wide range of applications as well as in understanding the mechanisms of folding critical to fibril formation. © 2015 Wiley Periodicals, Inc.

Photophysicochemical, calf thymus DNA binding and in vitro photocytotoxicity properties of tetra-morpholinoethoxy-substituted phthalocyanines and their water-soluble quaternized derivatives.

PubMed

Koçan, Halit; Kaya, Kerem; Özçeşmeci, İbrahim; Sesalan, B Şebnem; Göksel, Meltem; Durmuş, Mahmut; Burat, Ayfer Kalkan

2017-12-01

In this study, morpholinoethoxy-substituted metal-free (3), zinc(II) (4) and indium(III) (5) phthalocyanines were synthesized. These phthalocyanines were converted to their water-soluble quaternized derivatives (3Q-5Q) using excess methyl iodide as a quaternization agent. All these phthalocyanines (Pcs) were characterized by elemental analysis and different spectroscopic methods such as FT-IR, 1 H NMR, UV-Vis and mass spectrometry. The photophysical and photochemical properties such as fluorescence and generation of singlet oxygen were investigated for determination of these phthalocyanines as photosensitizers in photodynamic therapy (PDT) applications. The binding properties of quaternized phthalocyanines (3Q-5Q) to calf thymus DNA (CT-DNA) were investigated by UV-Vis and fluorescence spectrophotometric methods. The quenching effect of all quaternized phthalocyanines on the fluorescence intensity of SYBR Green-DNA complex was determined. The mixtures of 3Q, 4Q or 5Q and DNA solutions were used to determine the change in T m of double helix DNA with thermal denaturation profile. In addition, thermodynamic parameters considering their aggregation in buffer solution, which shows the spontaneity of the reactions between DNA and quaternized Pcs were investigated. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method. Peripherally tetra-substituted neutral and quaternized metal-free and metallophthalocyanines (MPcs) (Zn, In) bearing morpholinoethoxy groups were prepared. The binding of quaternized compounds (3Q-5Q) to CT-DNA were examined using UV-Vis, fluorescence spectra, thermal denaturation profiles and K SV values. Besides, thermodynamic studies indicated that binding of 3Q-5Q to DNA was spontaneous. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method.

Low temperature and UV curable sol-gel coatings for long lasting optical fiber biosensors

NASA Astrophysics Data System (ADS)

Otaduy, D.; Villar, A.; Gomez-Herrero, E.; Goitandia, A. M.; Gorritxategi, E.; Quintana, I.

2010-04-01

The use of optical fibers as sensing element is increasing in clinical, pharmaceutical and industrial applications. Excellent light delivery, long interaction length, low cost and ability not only to excite the target molecules but also to capture the emitted light from the targets are the hallmarks of optical fiber as biosensors. In biosensors based on fiber optics the interaction with the analyte can occur within an element of the optical fiber. One of the techniques for this kind of biosensors is to remove the fiber optic cladding and substitute it for biological coatings that will interact with the parameter to sensorize. The deposition of these layers can be made by sol-gel technology. The sol-gel technology is being increasingly used mainly due to the high versatility to tailor their optical features. Incorporation of suitable chemical and biochemical sensing agents have allowed determining pH, gases, and biochemical species, among others. Nonetheless, the relatively high processing temperatures and short lifetime values mean severe drawbacks for a successful exploitation of sol-gel based coated optical fibres. With regard to the latter, herein we present the design, preparation and characterization of novel sol-gel coated optical fibres. Low temperature and UV curable coating formulations were optimized to achieve a good adhesion and optical performance. The UV photopolymerizable formulation was comprised by glycidoxypropyltrimethoxysilane (GLYMO), Tetraethylorthosilicate (TEOS) and an initiator. While the thermoset coating was prepared by using 3-aminopropyltrimethoxysilane, GLYMO, and TEOS as main reagents. Both curable sol-gel coated fibres were analysed by FTIR, SEM and optical characterization. Furthermore, in the present work a new technique for silica cladding removal has been developed by ultra-short pulses laser processing, getting good dimensional accuracy and surface integrity.

Assessment of degradation byproducts and NDMA formation potential during UV and UV/H2O2 treatment of doxylamine in the presence of monochloramine.

PubMed

Farré, Maria José; Radjenovic, Jelena; Gernjak, Wolfgang

2012-12-04

UV-C radiation is the U.S. EPA recommended technology to remove N-nitrosodimethylamine (NDMA) during drinking and recycled water production. Frequently, H(2)O(2) is added to the treatment to remove other recalcitrant compounds and to prevent NDMA reformation. However, the transformation of NDMA precursors during the UV and UV/H(2)O(2) process and the consequences for NDMA formation potential are currently not well understood, in particular in the presence of monochloramine. In this study, doxylamine has been chosen as a model compound to elucidate its degradation byproducts in the UV and UV/H(2)O(2) process and correlate those with changes to the NDMA formation potential. This study shows that during UV treatment in the presence and absence of monochloramine, NDMA formation potential can be halved. However, an increase of more than 30% was observed when hydrogen peroxide was added. Ultrafast liquid chromatography coupled to quadrupole-linear ion trap mass spectrometer was used for screening and structural elucidation of degradation byproducts identifying 21 chemical structures from the original parent compound. This work shows that further oxidation of NDMA precursors does not necessarily lead to a decrease in NDMA formation potential. Degradation byproducts with increased electron density in the vicinity of the dimethylamino moiety, for example induced by hydroxylation, may have a higher yield of nucleophilic substitution and subsequent NDMA formation compared to the parent compound during chloramination. This work demonstrates the need to consider the formation of oxidation byproducts and associated implications for the control and management of NDMA formation in downstream processes and distribution when integrating oxidative treatments into a treatment train generating either drinking water or recycled water for potable reuse.

Cryogenic radiometers and intensity-stabilized lasers for Eos radiometric calibrations

NASA Technical Reports Server (NTRS)

Foukal, P.; Hoyt, C.; Jauniskis, L.

1991-01-01

Liquid helium-cooled electrical substitution radiometers (ESRs) provide irradiance standards with demonstrated absolute accuracy at the 0.01 percent level, spectrally flat response between the UV and IR, and sensitivity down to 0.1 nW/sq cm. We describe an automated system developed for NASA - Goddard Space Flight Center, consisting of a cryogenic ESR illuminated by servocontrolled laser beams. This system is designed to provide calibration of single-element and array detectors over the spectral range between 257nm in the UV to 10.6 microns in the IR. We also describe a cryogenic ESR optimized for black body calibrations that has been installed at NIST, and another that is under construction for calibrations of the CERES scanners planned for Eos.

[Analysis of UV-visible absorption spectrum on the decolorization of industrial wastewater by disinfection].

PubMed

Huang, Xin; Wang, Long-Yong; Gao, Nai-Yun; Li, Wei-Guo

2012-10-01

The UV-Visible absorption spectrum of industrial wastewater was explored to introduce a substituting method determining the color of water, and to compare the decolorization efficacy of different disinfectants. The results show that the visible absorption spectrum(350-600 nm), instead of ultraviolet absorption spectrum, should be applied to characterize the color of wastewater. There is a good correlation between the features of visible absorption spectrum and the true color of wastewater. Both ozone and chlorine dioxide has a better decolorization performance than chlorine. However, the color of chlorine dioxide itself has a negative effect on decolorization. The changes in the features of visible absorption spectrum effectively reflect the variations in the color of wastewater after disinfection.

Diaminomaleonitrile-based azo receptors: Synthesis, DFT studies and their antibacterial activities

NASA Astrophysics Data System (ADS)

Khanmohammadi, Hamid; Arab, Vajihe; Rezaeian, Khatereh; Talei, Gholam Reza; Pass, Maryam; Shabani, Nafiseh

2017-02-01

New unsymmetric diaminomaleonitrile-based azo receptors (H3Ln, n = 1-3) have been synthesized via condensation reaction of 5-(4-X-phenyl)-azo-salicyladehyde (X = NO2, OMe and CH3) with 2-amino-3-(5-bromo-2-hydroxybenzylamino)maleonitrile. The solvatochromic behaviors of the molecules were probed by studying their UV-Vis spectra in five pure organic solvents of different polarities. The p-NO2 substituted receptor shows a dramatic color change from yellow to blue upon the addition of fluoride ion in CH3CN. This capability was studied by systematic TD-DFT calculations. These compounds were assayed for their in vitro antibacterial activities against Gram-positive (S. aureus, S. epidermidis and L. monocytogenes) and Gram-negative (E. coli, P. aeruginosa and K. pneumonia.) bacteria by disc diffusion method. The results indicated that the compounds show good inhibition against Gram positive bacteria namely L. monocytogenes as compared to standard drugs.

Spectroscopy of Isolated Prebiotic Nucleobases

NASA Technical Reports Server (NTRS)

Svadlenak, Nathan; Callahan, Michael P.; Ligare, Marshall; Gulian, Lisa; Gengeliczki, Zsolt; Nachtigallova, Dana; Hobza, Pavel; deVries, Mattanjah

2011-01-01

We use multiphoton ionization and double resonance spectroscopy to study the excited state dynamics of biologically relevant molecules as well as prebiotic nucleobases, isolated in the gas phase. Molecules that are biologically relevant to life today tend to exhibit short excited state lifetimes compared to similar but non-biologically relevant analogs. The mechanism is internal conversion, which may help protect the biologically active molecules from UV damage. This process is governed by conical intersections that depend very strongly on molecular structure. Therefore we have studied purines and pyrimidines with systematic variations of structure, including substitutions, tautomeric forms, and cluster structures that represent different base pair binding motifs. These structural variations also include possible alternate base pairs that may shed light on prebiotic chemistry. With this in mind we have begun to probe the ultrafast dynamics of molecules that exhibit very short excited states and search for evidence of internal conversions.

Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

PubMed

Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

2018-06-01

In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

Structural dependence of the multi-functionalized carbon nanotubes to the substituents on the grafted diazo compounds

NASA Astrophysics Data System (ADS)

Amiri, Rahebeh; Rasouli, Sousan; Ghasemi, Alireza; Eghbali, Babak; Mohammadi, Soutodeh

2014-05-01

Systematic studies on the covalent functionalization of multi-walled carbon nanotubes were performed by a series of azo molecules with different substituents. For this investigation, 4-substituted diazonium reagents have been used in the reaction with the functionalized multi-walled carbon nanotubes. We analyzed the effect of the substituted groups on the diazo component affinity in the grafting. Also, the structural differences of the final products were evaluated by visual dispersion test, UV-Vis absorption. Fourier transforms infrared, Raman, and several complementary techniques (scanning electron microscopy, thermal gravimetric analysis, and colorimetry test). Nuclear magnetic resonance spectroscopy has been used to confirm the allylic protons attached to the surface of carbon nanotubes after functionalization.

New mutations affecting induced mutagenesis in yeast.

PubMed

Lawrence, C W; Krauss, B R; Christensen, R B

1985-01-01

Previously isolated mutations in baker's yeast, Saccharomyces cerevisiae, that impair induced mutagenesis were all identified with the aid of tests that either exclusively or predominantly detect base-pair substitutions. To avoid this bias, we have screened 11 366 potentially mutant clones for UV-induced reversion of the frameshift allele, his4-38, and have identified 10 mutants that give much reduced yields of revertants. Complementation and recombination tests show that 6 of these carry mutations at the previously known REV1, REV1 and REV3 loci, while the remaining 4 define 3 new genes, REV4 (2 mutations), REV5 and REV6. The rev4 mutations are readily suppressed in many genetic backgrounds and, like the rev5 mutation, impart only a limited deficiency for induced mutagenesis: it is likely, therefore that the REV4+ and REV5+ gene functions are only remotely concerned with this process. The rev6 mutants have a more general deficiency, however, as well as marked sensitivity to UV and an increased spontaneous mutation rate, properties that suggest the REV6 gene is directly involved in mutation induction. The REV5 gene is located about 1 cM proximal to CYC1 on chromosome X.

Cobalt doping of the MOF-5 framework and its effect on gas-adsorption properties.

PubMed

Botas, Juan A; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Orcajo, M Gisela

2010-04-20

Partial isomorphic substitution of Zn in IRMOF metal clusters by cobalt ions is described for the first time. Specifically, different numbers of Co(2+) ions have been incorporated during solvothermal crystallization into the Zn-based MOF-5 (IRMOF-1) framework, which is one of the most studied MOF materials. The amount of Zn that can be substituted seems to be limited, being no more than 25% of total metal content, that is, no more than one Co atom inside every metal cluster formed by four transition-metal ions, on average. Several characterization techniques, including X-ray diffraction, DR UV-visible spectroscopy, N(2) adsorption isotherms, and thermogravimetrical analysis, strongly support the effective incorporation of Co into the material framework. As-synthesized CoMOF-5 has cobalt ions in octahedral coordination, changing to tetrahedral by simple evacuation, presumably by the removal of two diethylformamide molecules per Co ion. Moreover, the H(2), CH(4), and CO(2) uptake of MOF-5 materials systematically increases with the Co content, particularly at high pressure. Such an increase is moderate anyway, considering that Co is incorporated into unexposed metal sites that are less accessible to gas molecules.

A visible light photocatalyst: effects of vanadium substitution on ETS-10.

PubMed

Marie Shough, Anne; Lobo, Raul F; Doren, Douglas J

2007-10-07

Hybrid density functional theory/molecular mechanics (DFT/MM) methods have been used to investigate the effects of vanadium substitution in ETS-10. Models have been developed to contain varying concentrations of V(IV) and V(V) within the O-M-O (M = Ti, V) chain. Most of the V-substituted models have a localized mid-gap state. The occupation of this localized state depends upon the dopant oxidation state, leading to the addition of multiple low energy transitions. A linear correlation has been identified between band gap energies estimated using ground state orbital energies and those calculated using the more accurate and computationally demanding time-dependent DFT (TDDFT) method for a variety of transition metal substituted models of ETS-10. Consistent with experimental data for V substitution, our models predict a decrease in the optical band gap with increasing [V], due to a lowering of the delocalized d-orbital states at the bottom of the conduction band with increasing V d-orbital character. This effect is more pronounced in the case of V(V) substitution than V(IV). Excitation energies for the V-doped models, calculated with TDDFT methods correlate well with experimental data, allowing for the assignment of specific optical transitions to experimental UV-Vis spectra. The electronic structure of V-substituted ETS-10 at high V concentration demonstrates band gap energies within the visible range of the spectrum. Additionally, at high [V] the band gap energy and presence of low energy electron traps can be controlled by the relative concentration of V(IV) and V(V) along the O-M-O chain, establishing V-substituted ETS-10 as a promising visible light photocatalyst.

Microplate assay for screening the antibacterial activity of Schiff bases derived from substituted benzopyran-4-one.

PubMed

Amin, Rehab M; Abdel-Kader, Nora S; El-Ansary, Aida L

2012-09-01

Schiff bases (SB(1)-SB(3)) were synthesized from the condensation of 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one with 2-aminopyridine (SB(1)), p-phenylenediamine (SB(2)) and o-phenylenediamine (SB(3)), while Schiff bases (SB(4)-SB(6)) were synthesized by condensation of 5,7-dihydroxy-6-formyl-2-methylbenzopyran-4-one with 2-aminopyridine (SB(4)), p-phenylenediamine (SB(5)) and o-phenylenediamine (SB(6)). Schiff bases were characterized using elemental analysis, IR, UV-Vis, (1)H NMR, (13)C NMR and mass spectroscopy. These compounds were screened for antibacterial activities by micro-plate assay technique. Escherichia coli and Staphylococcus capitis were exposed to different concentrations of the Schiff bases. Results showed that the antibacterial effect of these Schiff bases on Gram-negative bacteria were higher than that on Gram-positive bacteria moreover, the Schiff bases containing substituent OCH(3) on position five have higher antibacterial activity than that containing hydroxy group on the same position. Copyright © 2012 Elsevier B.V. All rights reserved.

Characterization of drug authenticity using thin-layer chromatography imaging with a mobile phone.

PubMed

Yu, Hojeong; Le, Huy M; Kaale, Eliangiringa; Long, Kenneth D; Layloff, Thomas; Lumetta, Steven S; Cunningham, Brian T

2016-06-05

Thin-layer chromatography (TLC) has a myriad of separation applications in chemistry, biology, and pharmacology due to its simplicity and low cost. While benchtop laboratory sample application and detection systems for TLC provide accurate quantitation of TLC spot positions and densities, there are many applications where inexpensive and portable instruments would greatly expand the applicability of the technology. In this work, we demonstrate identity verification and concentration determination of pharmaceutical compounds via TLC using a custom 3D-printed cradle that interfaces with an ordinary mobile phone. The cradle holds the mobile phone's internal, rear-facing camera in a fixed position relative to a UV lamp and a TLC plate that includes a phosphor in the stationary phase. Analysis of photographs thus reveals the locations and intensities of principal spots of UV--absorbing drugs. Automated image analysis software determines the center location and density of dark spots, which, using integrated calibration spots of known drug compounds and concentrations, can be used to determine if a drug has been diluted or substituted. Two independent image processing approaches have been developed that may be selected based upon the processing capabilities of the smartphone. Each approach is able to discern 5% drug concentration differences. Using single-component solutions of nevirapine, amodiaquine, and paracetamol that have been manually applied, the mobile phone-based detection instrument provides measurements that are equivalent to those obtained with a commercially available lab-based desktop TLC densitometer. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and biological activity of hydrazide hydrazones and their corresponding 3-acetyl-2,5-disubstituted-2,3-dihydro-1,3,4-oxadiazoles

USDA-ARS?s Scientific Manuscript database

Various new 3-acetyl-2,5-disubstituted-2,3-dihydro-1,3,4-oxadiazoles (11-20) were prepared by the reaction of aryl substituted hydrazones of 4-fluorobenzoic acid hydrazide (1-10) with acetic anhydride. The structures of the newly synthesized compounds 11-20, were confirmed by UV, IR and 1H NMR spec...

Synthesis, characterization and biological activities of some Ru(II) complexes with substituted chalcones and their applications as chemotherapeutics against breast cancer

NASA Astrophysics Data System (ADS)

Singh, Ashok K.; Saxena, Gunjan; Dixit, Shivani; Hamidullah; Singh, Sachin K.; Singh, Sudheer K.; Arshad, M.; Konwar, Rituraj

2016-05-01

Four new Ru(II) DMSO complexes with substituted chalcone ligands viz. (E)-1-(2-hydroxyphenyl)-3-(4-methoxyphenyl)prop-2-en-1-one (HL1), (E)-1-(2-hydroxyphenyl)-3-(4-nitrophenyl)prop-2-en-1-one (HL2), (E)-3-(4-(dimethylamino)phenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one (HL3) and (E)-1-(2-hydroxyphenyl)-3-(4-Chlorophenyl)prop-2-en-1-one (HL4) have been synthesized, and characterized by micro-analyses, IR, 1H NMR, UV-Vis and ESI-MS and screened for anti-cancer activity against breast cancer cell lines (MCF-7 and MDA MB-231). Compounds HL4 and [Ru(HL1) (O-DMSO)3(S-DMSO)]Cl (M1R) showed significant anti-breast cancer activity as evident from cytotoxicity, morphological and nuclear changes, DNA fragmentation and cell cycle arrest in breast cancer cells. UV-Vis and CD-spectra analysis showed HL4 and M1R interfered with DNA absorption spectra possibly due to DNA binding whereas these compounds were devoid of DNA topoisomerase inhibiting activity. Thus, these Ru(II) compounds have been established as new leads for future optimization by improving anti-cancer potency and safety.

Effect of F ions on physical and optical properties of fluorine substituted zinc arsenic tellurite glasses

NASA Astrophysics Data System (ADS)

Kareem Ahmmad, Shaik; kondaul, Edu; Rahman, Syed

2015-02-01

The effect of substitution of fluoride ions for oxide ions on the physical and optical properties of glass system (20-x) ZnO-xZnF2-40As2O3-40TeO2 where x = 0, 4, 8,12,16,20 mole % were investigated. The samples prepared by melt quenching method under controlled condition. The amorphous nature of these glasses was checked by X-ray diffraction technique. The density was measured according to Archimedes principle. The room temperature absorption spectra of all glass samples were determined using UV-Vis-NIR spectrometer. The thermal behaviour, glass transition temperature and stability of glass samples were studied by a differential scanning calorimetric (DSC). The density reduction of present glasses with ZnF2 concentrations may be due to the low density of ZnF2 compared with that of ZnO. Breaking the oxide network, the cross linking degree of the glass former could be reduced which results in decrease of both Tg and Tx. In the present glass system when F ions replaced by oxygen ions UV-Vis absorption cut-off wavelength decreases. This resulted form the conversion of structural unit in the glass from TeO4 to Te(O,F)4 and then to Te(O, F)3.

Facile synthesis of fluoro, methoxy, and methyl substituted ferrocene-based urea complexes as potential therapeutic agents.

PubMed

Asghar, Faiza; Badshah, Amin; Lal, Bhajan; Zubair, Shumaila; Fatima, Saira; Butler, Ian S

2017-06-01

In the present work, the synthesis, characterization (FT-IR, multinuclear ( 1 H and 13 C) NMR, AAS, Raman, and elemental analysis), DNA binding (cyclic voltammetry, UV-Vis spectroscopy and viscometry), and in vitro biological assessment of nine new ferrocene-based ureas are reported. The desulphurization of ferrocenyl thioureas to the corresponding oxo analogues using aqueous sodium hydroxide and mercuric chloride led to the ferrocenyl ureas (F1-F9) in high yields. The DNA binding studies performed by cyclic voltammetry and UV-Vis spectroscopy produced results that are in close agreement with one another for the binding constants (K) and an electrostatic mode of interaction was observed. The nature and the extent of interaction with DNA was further investigated by viscometry. The DFT/B3LYP method was used to determine the charge distribution and HOMO/LUMO energies of the optimized structure. The DFT calculated HOMO and LUMO energies correlate well with the experimentally determined redox potential values. The synthesized ferrocenyl derivatives exhibited good scavenging activity against 1,1-diphenyl-2-picrylhydrazyl radical (DPPH). These complexes were also scanned for their in vitro cytotoxicity against human carcinoma cell line THP-1 (leukemia cells). The results showed a moderate level of cytotoxicity against the subjected cancer cell line as compared with the standard chemotherapeutic drug (cisplatin). Copyright © 2017 Elsevier Inc. All rights reserved.

Changes in air quality and tropospheric composition due to depletion of stratospheric ozone and interactions with changing climate: implications for human and environmental health.

PubMed

Madronich, S; Shao, M; Wilson, S R; Solomon, K R; Longstreth, J D; Tang, X Y

2015-01-01

UV radiation is an essential driver for the formation of photochemical smog, which includes ground-level ozone and particulate matter (PM). Recent analyses support earlier work showing that poor outdoor air quality is a major environmental hazard as well as quantifying health effects on regional and global scales more accurately. Greater exposure to these pollutants has been linked to increased risks of cardiovascular and respiratory diseases in humans and is associated globally with several million premature deaths per year. Ozone also has adverse effects on yields of crops, leading to loss of billions of US dollars each year. These detrimental effects also may alter biological diversity and affect the function of natural ecosystems. Future air quality will depend mostly on changes in emission of pollutants and their precursors, but changes in UV radiation and climate will contribute as well. Significant reductions in emissions, mainly from the energy and transportation sectors, have already led to improved air quality in many locations. Air quality will continue to improve in those cities/states that can afford controls, and worsen where the regulatory infrastructure is not available. Future changes in UV radiation and climate will alter the rates of formation of ground-level ozone and photochemically-generated particulate matter and must be considered in predictions of air quality. The decrease in UV radiation associated with recovery of stratospheric ozone will, according to recent global atmospheric model simulations, lead to increases in ground-level ozone at most locations. If correct, this will add significantly to future ground-level ozone trends. However, the spatial resolution of these global models is insufficient to inform policy at this time, especially for urban areas. UV radiation affects the atmospheric concentration of hydroxyl radicals, ˙OH, which are responsible for the self-cleaning of the atmosphere. Recent measurements confirm that, on a local scale, ˙OH radicals respond rapidly to changes in UV radiation. However, on large (global) scales, models differ in their predictions by nearly a factor of two, with consequent uncertainties for estimating the atmospheric lifetime and concentrations of key greenhouse gases and air pollutants. Projections of future climate need to consider these uncertainties. No new negative environmental effects of substitutes for ozone depleting substances or their breakdown-products have been identified. However, some substitutes for the ozone depleting substances will continue to contribute to global climate change if concentrations rise above current levels.

The Impact of Environmental and Endogenous Damage on Somatic Mutation Load in Human Skin Fibroblasts

PubMed Central

Saini, Natalie; Chan, Kin; Grimm, Sara A.; Dai, Shuangshuang; Fargo, David C.; Kaufmann, William K.; Taylor, Jack A.; Lee, Eunjung; Cortes-Ciriano, Isidro; Park, Peter J.; Schurman, Shepherd H.; Malc, Ewa P.; Mieczkowski, Piotr A.

2016-01-01

Accumulation of somatic changes, due to environmental and endogenous lesions, in the human genome is associated with aging and cancer. Understanding the impacts of these processes on mutagenesis is fundamental to understanding the etiology, and improving the prognosis and prevention of cancers and other genetic diseases. Previous methods relying on either the generation of induced pluripotent stem cells, or sequencing of single-cell genomes were inherently error-prone and did not allow independent validation of the mutations. In the current study we eliminated these potential sources of error by high coverage genome sequencing of single-cell derived clonal fibroblast lineages, obtained after minimal propagation in culture, prepared from skin biopsies of two healthy adult humans. We report here accurate measurement of genome-wide magnitude and spectra of mutations accrued in skin fibroblasts of healthy adult humans. We found that every cell contains at least one chromosomal rearrangement and 600–13,000 base substitutions. The spectra and correlation of base substitutions with epigenomic features resemble many cancers. Moreover, because biopsies were taken from body parts differing by sun exposure, we can delineate the precise contributions of environmental and endogenous factors to the accrual of genetic changes within the same individual. We show here that UV-induced and endogenous DNA damage can have a comparable impact on the somatic mutation loads in skin fibroblasts. Trial Registration ClinicalTrials.gov NCT01087307 PMID:27788131

A calix[4]arene derivative and its selective interaction with drugs (clofibric acid, diclofenac and aspirin).

PubMed

Danil de Namor, Angela F; Al Nuaim, Maan; Villanueva Salas, Jose A; Bryant, Sophie; Howlin, Brendan

2017-03-30

The synthesis and characterisation of a partially substituted calix[4]arene, namely, 5,11,17,23-tetra-tert-butyl,25,27-bis[aminoethoxy] 26,28-dihydroxycalix[4]arene are reported. Its interaction with commonly used pharmaceuticals (clofibric acid, diclofenac and aspirin) was investigated by spectroscopic ( 1 H NMR and UV), electrochemical (conductance measurements) and thermal (titration calorimetry) techniques. It is concluded on the basis of the experimental work and molecular simulation studies that the receptor interacts selectively with these drugs. Preliminary studies on the selective extraction of these pharmaceuticals from water by the calix receptor are reported and the potential for a carrier mediated sensor based on this ligand for 'on site' monitoring of pharmaceuticals is discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Mesophyll distribution of 'antioxidant' flavonoid glycosides in Ligustrum vulgare leaves under contrasting sunlight irradiance.

PubMed

Agati, Giovanni; Stefano, Giovanni; Biricolti, Stefano; Tattini, Massimiliano

2009-10-01

Flavonoids have the potential to serve as antioxidants in addition to their function of UV screening in photoprotective mechanisms. However, flavonoids have long been reported to accumulate mostly in epidermal cells and surface organs in response to high sunlight. Therefore, how leaf flavonoids actually carry out their antioxidant functions is still a matter of debate. Here, the distribution of flavonoids with effective antioxidant properties, i.e. the orthodihydroxy B-ring-substituted quercetin and luteolin glycosides, was investigated in the mesophyll of Ligustrum vulgare leaves acclimated to contrasting sunlight irradiance. In the first experiment, plants were grown at 20 % (shade) or 100% (sun) natural sunlight. Plants were exposed to 100 % sunlight irradiance in the presence or absence of UV wavelengths, in a second experiment. Fluorescence microspectroscopy and multispectral fluorescence microimaging were used in both cross sections and intact leaf pieces to visualize orthodihydroxy B-ring-substituted flavonoids at inter- and intracellular levels. Identification and quantification of individual hydroxycinnamates and flavonoid glycosides were performed via HPLC-DAD. Quercetin and luteolin derivatives accumulated to a great extent in both the epidermal and mesophyll cells in response to high sunlight. Tissue fluorescence signatures and leaf flavonoid concentrations were strongly related. Monohydroxyflavone glycosides, namely luteolin 4'-O-glucoside and two apigenin 7-O-glycosides were unresponsive to changes in sunlight irradiance. Quercetin and luteolin derivatives accumulated in the vacuoles of mesophyll cells in leaves growing under 100 % natural sunlight in the absence of UV wavelengths. The above findings lead to the hypothesis that flavonoids play a key role in countering light-induced oxidative stress, and not only in avoiding the penetration of short solar wavelengths in the leaf.

Mesophyll distribution of ‘antioxidant’ flavonoid glycosides in Ligustrum vulgare leaves under contrasting sunlight irradiance

PubMed Central

Agati, Giovanni; Stefano, Giovanni; Biricolti, Stefano; Tattini, Massimiliano

2009-01-01

Background and Aims Flavonoids have the potential to serve as antioxidants in addition to their function of UV screening in photoprotective mechanisms. However, flavonoids have long been reported to accumulate mostly in epidermal cells and surface organs in response to high sunlight. Therefore, how leaf flavonoids actually carry out their antioxidant functions is still a matter of debate. Here, the distribution of flavonoids with effective antioxidant properties, i.e. the orthodihydroxy B-ring-substituted quercetin and luteolin glycosides, was investigated in the mesophyll of Ligustrum vulgare leaves acclimated to contrasting sunlight irradiance. Methods In the first experiment, plants were grown at 20 % (shade) or 100% (sun) natural sunlight. Plants were exposed to 100 % sunlight irradiance in the presence or absence of UV wavelengths, in a second experiment. Fluorescence microspectroscopy and multispectral fluorescence microimaging were used in both cross sections and intact leaf pieces to visualize orthodihydroxy B-ring-substituted flavonoids at inter- and intracellular levels. Identification and quantification of individual hydroxycinnamates and flavonoid glycosides were performed via HPLC-DAD. Key Results Quercetin and luteolin derivatives accumulated to a great extent in both the epidermal and mesophyll cells in response to high sunlight. Tissue fluorescence signatures and leaf flavonoid concentrations were strongly related. Monohydroxyflavone glycosides, namely luteolin 4′-O-glucoside and two apigenin 7-O-glycosides were unresponsive to changes in sunlight irradiance. Quercetin and luteolin derivatives accumulated in the vacuoles of mesophyll cells in leaves growing under 100 % natural sunlight in the absence of UV wavelengths. Conclusions The above findings lead to the hypothesis that flavonoids play a key role in countering light-induced oxidative stress, and not only in avoiding the penetration of short solar wavelengths in the leaf. PMID:19633310

Aggregation of Trp > Glu point mutants of human gamma-D crystallin provides a model for hereditary or UV-induced cataract.

PubMed

Serebryany, Eugene; Takata, Takumi; Erickson, Erika; Schafheimer, Nathaniel; Wang, Yongting; King, Jonathan A

2016-06-01

Numerous mutations and covalent modifications of the highly abundant, long-lived crystallins of the eye lens cause their aggregation leading to progressive opacification of the lens, cataract. The nature and biochemical mechanisms of the aggregation process are poorly understood, as neither amyloid nor native-state polymers are commonly found in opaque lenses. The βγ-crystallin fold contains four highly conserved buried tryptophans, which can be oxidized to more hydrophilic products, such as kynurenine, upon UV-B irradiation. We mimicked this class of oxidative damage using Trp→Glu point mutants of human γD-crystallin. Such substitutions may represent a model of UV-induced photodamage-introduction of a charged group into the hydrophobic core generating "denaturation from within." The effects of Trp→Glu substitutions were highly position dependent. While each was destabilizing, only the two located in the bottom of the double Greek key fold-W42E and W130E-yielded robust aggregation of partially unfolded intermediates at 37°C and pH 7. The αB-crystallin chaperone suppressed aggregation of W130E, but not W42E, indicating distinct aggregation pathways from damage in the N-terminal vs C-terminal domain. The W130E aggregates had loosely fibrillar morphology, yet were nonamyloid, noncovalent, showed little surface hydrophobicity, and formed at least 20°C below the melting temperature of the native β-sheets. These features are most consistent with domain-swapped polymerization. Aggregation of partially destabilized crystallins under physiological conditions, as occurs in this class of point mutants, could provide a simple in vitro model system for drug discovery and optimization. © 2016 The Protein Society.

Silver nanoparticles-based colorimetric array for the detection of Thiophanate-methyl

NASA Astrophysics Data System (ADS)

Zheng, Mingda; Wang, Yingying; Wang, Chenge; Wei, Wei; Ma, Shuang; Sun, Xiaohan; He, Jiang

2018-06-01

A simple and selective colorimetric sensor based on citrate capped silver nanoparticles (Cit-AgNPs) is proposed for the detection of Thiophanate-methyl (TM) with high sensitivity and selectivity. The method based on the color change of Cit-AgNPs from yellow to cherry red with the addition of TM to Cit-AgNPs that caused a red-shift on the surface plasmon resonance (SPR) band from 394 nm to 525 nm due to the hydrogen-bonding and substitution. The density functional theory (DFT) method was also calculated the interactions between the TM and citrate ions. Under the optimized conditions, a linear relationship between the absorption ratio (A525nm/A394nm) and TM concentration was found in the range of 2-100 μM with correlation coefficient (R2) of 0.988. The detection limit of TM was 0.12 μM by UV-vis spectrometer. Moreover, the applicability of colorimetric sensor is successfully verified by the detection of TM in environmental samples with good recoveries.

Near-ultraviolet laser diodes for brilliant ultraviolet fluorophore excitation.

PubMed

Telford, William G

2015-12-01

Although multiple lasers are now standard equipment on most modern flow cytometers, ultraviolet (UV) lasers (325-365 nm) remain an uncommon excitation source for cytometry. Nd:YVO4 frequency-tripled diode pumped solid-state lasers emitting at 355 nm are now the primary means of providing UV excitation on multilaser flow cytometers. Although a number of UV excited fluorochromes are available for flow cytometry, the cost of solid-state UV lasers remains prohibitively high, limiting their use to all but the most sophisticated multilaser instruments. The recent introduction of the brilliant ultraviolet (BUV) series of fluorochromes for cell surface marker detection and their importance in increasing the number of simultaneous parameters for high-dimensional analysis has increased the urgency of including UV sources in cytometer designs; however, these lasers remain expensive. Near-UV laser diodes (NUVLDs), a direct diode laser source emitting in the 370-380 nm range, have been previously validated for flow cytometric analysis of most UV-excited probes, including quantum nanocrystals, the Hoechst dyes, and 4',6-diamidino-2-phenylindole. However, they remain a little-used laser source for cytometry, despite their significantly lower cost. In this study, the ability of NUVLDs to excite the BUV dyes was assessed, along with their compatibility with simultaneous brilliant violet (BV) labeling. A NUVLD emitting at 375 nm was found to excite most of the available BUV dyes at least as well as a UV 355 nm source. This slightly longer wavelength did produce some unwanted excitation of BV dyes, but at sufficiently low levels to require minimal additional compensation. NUVLDs are compact, relatively inexpensive lasers that have higher power levels than the newest generation of small 355 nm lasers. They can, therefore, make a useful, cost-effective substitute for traditional UV lasers in multicolor analysis involving the BUV and BV dyes. Published 2015 Wiley Periodicals Inc. on behalf of ISAC.

Comparing three UV wavelengths for pre‐exposing Gafchromic EBT2 and EBT3 films

PubMed Central

Gotanda, Rumi; Gotanda, Tatsuhiro; Akagawa, Takuya; Tanki, Nobuyoshi; Kuwano, Tadao; Yabunaka, Kouichi

2015-01-01

Gafchromic films are used for X‐ray dose measurements during diagnostic examinations and have begun to be used for three‐dimensional X‐ray dose measurements using the high‐resolution characteristics of Gafchromic films for computed tomography. However, the problem of unevenness in Gafchromic film active layers needs to be resolved. Double exposures using X‐rays are performed during therapeutic radiology, although this is difficult for a diagnostic examination because of a heel effect. Thus, it has been suggested that ultraviolet (UV) radiation be used as a substitute for X‐rays. However, the appropriate UV wavelength has not been determined. Thus, we conducted this study to decide an appropriate UV wavelength. UV peak wavelengths of 245 nm (UV‐A), 310 nm (UV‐B), and 365 nm (UV‐C) were used to irradiate EBT2 and EBT3 films. Each UV wavelength was irradiated for 5, 15, 30, and 60 min, and irradiation was then repeated every 60 min up to 360 min. Gafchromic films were scanned after every irradiation using a flatbed scanner. Images were split into RGB images, and red images were analyzed using ImageJ, version 1.44, image analysis software. A region of interest (ROI) one‐half inch in diameter was placed in the center of subtracted Gafchromic film images, and UV irradiation times were plotted against mean pixel values. There were reactions in the front and back of Gafchromic EBT3 and the back of Gafchromic EBT2 with UV‐A and UV‐B. However, UV‐C resulted in some reactions in both sides of Gafchromic EBT2 and EBT3. The UV‐A and UV‐B wavelengths should be used. PACS number(s): 87.53 Bn PMID:26699578

The phylogenetic distribution of ultraviolet sensitivity in birds

PubMed Central

2013-01-01

Background Colour vision in birds can be categorized into two classes, the ultraviolet (UVS) and violet sensitive (VS). Their phylogenetic distributions have traditionally been regarded as highly conserved. However, the complicated nature of acquiring spectral sensitivities from cone photoreceptors meant that until recently, only a few species had actually been studied. Whether birds are UVS or VS can nowadays be inferred from a wide range of species via genomic sequencing of the UV/violet SWS1 cone opsin gene. Results We present genomic sequencing results of the SWS1 gene from 21 avian orders. Amino acid residues signifying UV sensitivity are found in the two most important spectral tuning sites 86 and 90 of Pteroclidiformes and Coraciiformes, in addition to the major clades, Palaeognathae, Charadriiformes, Trogoniformes, Psittaciformes and Passeriformes, where they where previously known to occur. We confirm that the presumed UVS-conferring amino acid combination F86, C90 and M93 is common to Palaeognathae and unique to this clade, despite available spectrometric evidence showing the ostrich retina to be VS. Conclusions By mapping our results together with data from previous studies on a molecular phylogeny we show that avian colour vision shifted between VS and UVS at least 14 times. Single nucleotide substitutions can explain all these shifts. The common ancestor of birds most likely had a VS phenotype. However, the ancestral state of the avian SWS1 opsin’s spectral tuning sites cannot be resolved, since the Palaeognathae are F86, C90 while the Neognathae are ancestrally S86, S90. The phylogenetic distribution of UVS and VS colour vision in birds is so complex that inferences of spectral sensitivities from closely related taxa should be used with caution. PMID:23394614

Synthesis, spectroscopic, and molecular structure characterizations of some azo derivatives of 2-hydroxyacetophenone

NASA Astrophysics Data System (ADS)

Albayrak, Çiğdem; Gümrükçüoğlu, İsmail E.; Odabaşoğlu, Mustafa; İskeleli, Nazan Ocak; Ağar, Erbil

2009-08-01

Some novel azo compounds were prepared by the reaction of 2-hydroxyacetophenone with aniline and its substituted derivatives. The structures of synthesized azo compounds were determined by IR, UV-Vis, 1H NMR and 13C NMR spectroscopic techniques and the structures of some of these compounds were also determined by X-ray diffraction studies. Structural analysis using IR in solid state shows that the azo form is favoured in the azo compounds whereas UV-Vis analysis of the azo compounds in solution has shown that there is a azo and ionic form. The azo compounds in the basic solvents dimethylformamide (DMF) and dimethylsulfoxide (DMSO) are both azo and ionic form while these compounds in ethyl alcohol (EtOH) and chloroform (CHCl 3) are only azo form.

Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties

NASA Astrophysics Data System (ADS)

Atmaca, Göknur Yaşa; Dizman, Cemil; Eren, Tarık; Erdoğmuş, Ali

2015-02-01

The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, 1H and 11B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ = 0.41, 0.39).

An efficient green synthesis of 2-arylbenzothiazole analogues as potent antibacterial and anticancer agents.

PubMed

Chhabra, Mohit; Sinha, Sohini; Banerjee, Swagata; Paira, Priyankar

2016-01-01

We have demonstrated a novel and green approach for the synthesis of 2-substituted benzothiazole analogues. A number of 2-aryl and heteroaryl benzothiazole scaffolds were synthesized using Amberlite IR-120 resin under microwave irradiation. The catalytic role and reusability of the resin was well established here. 2-Substituted benzothiazole analogues (3a-l) were also tested against several bacterial strains (Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Salmonella) and cancer cell lines (MCF-7 and HeLa). The stability of compound 2-phenyl benzothiazole (3a) and 2-pyridin-2-yl-benzothiazole (3k) in GSH (0.01mM dissolved in DMSO) was measured by UV-Vis spectroscopy. Compound 3k also shows remarkable fluorescence in MeOH. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of size controllable cu-phthalocyanine nanofibers by simple solvent diffusion method and their electrochemical properties.

PubMed

Gao, Junshan; Cheng, Chuanwei; Zhou, Xuechao; Li, Yingying; Xu, Xiaoqi; Du, Xiguang; Zhang, Haiqian

2010-02-15

Tetra (2-isopropyl-5-methylphenoxy) substituted Cu-phthalocyanine nanofibers were obtained in large scale by a simple solvent diffusion method. The sizes of the fibers can be finely tuned under different solvent temperature. FE-SEM micrographs indicate that the length of the fibers changed from several hundreds micrometers to several hundreds nanometers and the width changed from several micrometers to several decade nanometers. XRD measurement showed a highly long-range ordered lamellar arrangement of the substituted Cu-phthalocyanine molecules in the microfiber and the UV-vis absorption spectrum of the fibers indicated an H-aggregate of the phthalocyanine molecules. The CV curves elucidate the CuPc fibers can be fabricated Faraday pseudocapacitor. Crown Copyright 2009. Published by Elsevier Inc. All rights reserved.

Substituent and solvent effects on the UV/Vis absorption spectra of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones

NASA Astrophysics Data System (ADS)

Ušćumlić, Gordana S.; Mijin, Dusanˇ Z. ˇ; Valentić, Nataša V.; Vajs, Vlatka V.; Sušić, Biljana M.

2004-10-01

Absorption spectra of ten 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones have been recorded in fifteen solvents in the range 200-600 nm. The substituents at the phenyl nucleus are as follows: OH, OCH 3, CH 3, C 2H 5, H, Cl, Br, I, COOH and NO 2. The effects of substituents on the absorption spectra of investigated compounds are interpreted by correlation of absorption frequencies with simple Hammett equation. The effects of solvent polarity and solvent/solute hydrogen bonding interactions are analyzed by means of linear solvation energy relationships concept proposed by Kamlet and Taft. The azo-hydrazone tuatomeric equilibration is found to depend upon substituents as well as on solvents.

Structural Characterization of Cross-Linked Hemoglobins Developed as Potential Transfusion Substitutes

DTIC Science & Technology

1990-05-30

phase HPLC using an IBM Instruments Inc. model LC 9533 ternary liquid chromatograph attached to a model F9522 fixed UV module and a model F9523...acid analyses are done by separation and quantitation of phenylthiocarbamyl amino acid derivatives using a second IBM model LC 9533 ternary liquid...computer which controls the HPLC and an IBM Instruments Inc. model LC 9505 automatic sampler. The hemoglobin present in the effluent from large

Atomic Oxygen Durability Evaluation of a UV Curable Ceramer Protective Coating

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Karniotis, Christina A.; Dworak, David; Soucek, Mark

2004-01-01

The exposure of most silicones to atomic oxygen in low Earth orbit (LEO) results in the oxidative loss of methyl groups with a gradual conversion to oxides of silicon. Typically there is surface shrinkage of oxidized silicone protective coatings which leads to cracking of the partially oxidized brittle surface. Such cracks widen and branch crack with continued atomic oxygen exposure ultimately allowing atomic oxygen to reach any hydrocarbon polymers under the silicone coating. A need exists for a paintable silicone coating that is free from such surface cracking and can be effectively used for protection of polymers and composites in LEO. A new type of silicone based protective coating holding such potential was evaluated for atomic oxygen durability in an RF atomic oxygen plasma exposure facility. The coating consisted of a UV curable inorganic/organic hybrid coating, known as a ceramer, which was fabricated using a methyl substituted polysiloxane binder and nanophase silicon-oxo-clusters derived from sol-gel precursors. The polysiloxane was functionalized with a cycloaliphatic epoxide in order to be cured at ambient temperature via a cationic UV induced curing mechanism. Alkoxy silane groups were also grafted onto the polysiloxane chain, through hydrosilation, in order to form a network with the incorporated silicon-oxo-clusters. The prepared polymer was characterized by H-1 and Si-29 NMR, FT-IR, and electrospray ionization mass spectroscopy. The paper will present the results of atomic oxygen protection ability of thin ceramer coatings on Kapton H as evaluated over a range of atomic oxygen fluence levels.

Substitution and Redox Chemistry of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)].

PubMed

Prokopuk, Nicholas; Kennedy, Vance O.; Stern, Charlotte L.; Shriver, Duward F.

1998-09-21

Two sequential electrochemical reductions occur for the cluster anion [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) at 0.89 and 0.29 V vs Ag/AgCl, with the generation [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) and [Ta(6)Cl(12)(OSO(2)CF(3))(6)](4)(-). Chemical reduction of [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) by ferrocene produces [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) with the concomitant shift of the nu(SO(2)) stretch from 1002 to 1018 cm(-)(1). Reaction of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)] (1) with [Bu(4)N]X (X = Cl, Br, I, NCS) occurs by reduction and substitution, yielding [Bu(4)N](3)[Ta(6)Cl(12)X(6)], where the clusters with X = Br, I, and NCS are new. Spectroscopic (IR and UV-vis) evidence indicates that the reduced cluster core {Ta(6)Cl(12)}(2+) is produced in reaction mixtures of 1 with the halide and pseudohalide ions. Concomitant substitution of the triflate ligands of 1 by X(-) occurs and the rates for the overall reduction and substitution increase in the order X(-) = Cl(-) < Br(-) < NCS(-) < I(-) < CN(-). Reduction of 1 with ferrocene followed by addition of [Bu(4)N]O(2)CCH(3) produces the new cluster [Ta(6)Cl(12)(O(2)CCH(3))(6)](3)(-) isolated as the tetrabutylammonium salt. Cyclic voltammetry and UV-vis spectroscopy on the new clusters [Bu(4)N](3)[Ta(6)Cl(12)X(6)] (X = Br, I, NCS, and O(2)CCH(3)) are reported. Crystal data for [Bu(4)N](3)[Ta(6)Cl(12)(NCS)(6)].CH(2)Cl(2): monoclinic, space group, P2(1)/c (No. 14); a = 25.855(6) Å, b = 21.843(6) Å, c = 16.423(3) Å; beta = 100.03(2) degrees; V = 9133(3) Å(3); Z = 4.

Synthesis, characterization and photocatalytic properties of Mg1-xZnxAl2O4 spinel nanoparticles

NASA Astrophysics Data System (ADS)

Li, Hui; Liu, Yuqin; Tang, Junkai; Deng, Yanxi

2016-08-01

Mg1-xZnxAl2O4 spinel nanoparticles with x = 0, 0.05, 0.10, 0.15 and 0.20 were prepared via the chemical coprecipitation method. The obtained samples were characterised by thermal gravimetric and differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, UV-Vis diffuse reflection spectrum, transmission electron microscopy and 27Al MAS-NMR spectroscopy. Mg1-xZnxAl2O4 spinel powders with the mean crystallite size of around 11 nm-14 nm were obtained. The crystallinity of the MgAl2O4 samples increases with the increase in the calcination temperature. At the same calcination temperature, higher amount of Zn2+ substitution leads to the higher level of crystallinity, but has no apparent influence on the mean crystallite size of the samples. The photocatalytic activity of the obtained Mg1-xZnxAl2O4 spinel nanoparticles was evaluated by monitoring the degradation of methylene blue under UV light. The degradation rates of methylene blue using the MgAl2O4 nanoparticles prepared at the calcination temperatures of 700 °C and 800 °C are much higher than those prepared at 900 °C and 1000 °C. The photocatalytic activities of the spinel powders with lower level of Zn2+ substitution such as Mg0.95Zn0.05Al2O4 are inferior to that of MgAl2O4. Results of 27Al MAS-NMR spectroscopy analysis and the first principle total density of state calculations reveal that this is probably due to the substitutions of Zn2+ decreasing the degree of Al3+ ions inversion over the sites of tetrahedral and octahedral coordination. With the increase in the amounts of Zn2+ substitution, the effects of Zn2+ additions on the photocatalytic activities become gradually predominant, leading to the increases in the degradation rates. The methylene blue degraded by 99% within 4 h using the Mg0.8Zn0.2Al2O4 spinel powders.

Mechanistic considerations on the wavelength-dependent variations of UVR genotoxicity and mutagenesis in skin: the discrimination of UVA-signature from UV-signature mutation.

PubMed

Ikehata, Hironobu

2018-05-31

Ultraviolet radiation (UVR) predominantly induces UV-signature mutations, C → T and CC → TT base substitutions at dipyrimidine sites, in the cellular and skin genome. I observed in our in vivo mutation studies of mouse skin that these UVR-specific mutations show a wavelength-dependent variation in their sequence-context preference. The C → T mutation occurs most frequently in the 5'-TCG-3' sequence regardless of the UVR wavelength, but is recovered more preferentially there as the wavelength increases, resulting in prominent occurrences exclusively in the TCG sequence in the UVA wavelength range, which I will designate as a "UVA signature" in this review. The preference of the UVB-induced C → T mutation for the sequence contexts shows a mixed pattern of UVC- and UVA-induced mutations, and a similar pattern is also observed for natural sunlight, in which UVB is the most genotoxic component. In addition, the CC → TT mutation hardly occurs at UVA1 wavelengths, although it is detected rarely but constantly in the UVC and UVB ranges. This wavelength-dependent variation in the sequence-context preference of the UVR-specific mutations could be explained by two different photochemical mechanisms of cyclobutane pyrimidine dimer (CPD) formation. The UV-signature mutations observed in the UVC and UVB ranges are known to be caused mainly by CPDs produced through the conventional singlet/triplet excitation of pyrimidine bases after the direct absorption of the UVC/UVB photon energy in those bases. On the other hand, a novel photochemical mechanism through the direct absorption of the UVR energy to double-stranded DNA, which is called "collective excitation", has been proposed for the UVA-induced CPD formation. The UVA photons directly absorbed by DNA produce CPDs with a sequence context preference different from that observed for CPDs caused by the UVC/UVB-mediated singlet/triplet excitation, causing CPD formation preferentially at thymine-containing dipyrimidine sites and probably also preferably at methyl CpG-associated dipyrimidine sites, which include the TCG sequence. In this review, I present a mechanistic consideration on the wavelength-dependent variation of the sequence context preference of the UVR-specific mutations and rationalize the proposition of the UVA-signature mutation, in addition to the UV-signature mutation.

Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process.

PubMed

Xiang, Yingying; Fang, Jingyun; Shang, Chii

2016-03-01

The UV/chlorine advanced oxidation process (AOP), which forms reactive species such as hydroxyl radicals (HO) and reactive chlorine species (RCS) such as chlorine atoms (Cl) and Cl2(-), is being considered as an alternative to the UV/H2O2 AOP for the degradation of emerging contaminants. This study investigated the kinetics and pathways of the degradation of a recalcitrant pharmaceutical and personal care product (PPCP)-ibuprofen (IBP)-by the UV/chlorine AOP. The degradation of IBP followed the pseudo first-order kinetics. The first-order rate constant was 3.3 times higher in the UV/chlorine AOP than in the UV/H2O2 AOP for a given chemical molar dosage at pH 6. The first-order rate constant decreased from 3.1 × 10(-3) s(-1) to 5.5 × 10(-4) s(-1) with increasing pH from 6 to 9. Both HO and RCS contributed to the degradation, and the contribution of RCS increased from 22% to 30% with increasing pH from 6 to 9. The degradation was initiated by HO-induced hydroxylation and Cl-induced chlorine substitution, and sustained through decarboxylation, demethylation, chlorination and ring cleavage to form more stable products. Significant amounts of chlorinated intermediates/byproducts were formed from the UV/chlorine AOP, and four chlorinated products were newly identified. The yield of total organic chlorine (TOCl) was 31.6 μM after 90% degradation of 50 μM IBP under the experimental conditions. The known disinfection by-products (DBPs) comprised 17.4% of the TOCl. The effects of water matrix in filtered drinking water on the degradation were not significant, demonstrating the practicality of the UV/chlorine AOP for the control of some refractory PPCPs. However, the toxicity of the chlorinated products should be further assessed. Copyright © 2015 Elsevier Ltd. All rights reserved.

UV-Vis Spectroscopy and Dynamic Light Scattering Study of Gold Nanorods Aggregation

PubMed Central

Kanjanawarut, Roejarek; Yuan, Bo

2013-01-01

Gold nanorods (AuNRs) were used as spectroscopic sensing elements to detect specific DNA sequences with a single-base mismatch sensitivity. The assay was based on the observation that the stabilizing repulsive forces between CTA+-coated AuNRs can be removed by citrate ions, which causes aggregation among AuNRs; whereas nucleic acids of different structures[ i.e., peptide nucleic acid (PNA), single-stranded DNA (ssDNA), PNA-DNA complex, and double-stranded DNA (dsDNA)] can retard the aggregation. Moreover, the dsDNA PNA-DNA duplexes provide larger retardation than that by unhybridized ssDNA and PNA probe. This assay can differentiate single-base mismatched targets with base substitution at different locations (center and end) with AuNRs of a larger aspect ratio. Besides ultraviolet–visable spectroscopy measurement of particle assembly-induced plasmonic coupling that in turn provides a spectroscopic detection of the specific DNA, dynamic light scattering and transmission electron microscope (TEM) were used to measure smaller degree of aggregation that can reveal sodium citrate– and dsDNA–AuNRs interactions in fine detail. PMID:23902360

UV-vis spectroscopy and dynamic light scattering study of gold nanorods aggregation.

PubMed

Kanjanawarut, Roejarek; Yuan, Bo; XiaoDi, Su

2013-08-01

Gold nanorods (AuNRs) were used as spectroscopic sensing elements to detect specific DNA sequences with a single-base mismatch sensitivity. The assay was based on the observation that the stabilizing repulsive forces between CTA(+)-coated AuNRs can be removed by citrate ions, which causes aggregation among AuNRs; whereas nucleic acids of different structures[ i.e., peptide nucleic acid (PNA), single-stranded DNA (ssDNA), PNA-DNA complex, and double-stranded DNA (dsDNA)] can retard the aggregation. Moreover, the dsDNA PNA-DNA duplexes provide larger retardation than that by unhybridized ssDNA and PNA probe. This assay can differentiate single-base mismatched targets with base substitution at different locations (center and end) with AuNRs of a larger aspect ratio. Besides ultraviolet-visable spectroscopy measurement of particle assembly-induced plasmonic coupling that in turn provides a spectroscopic detection of the specific DNA, dynamic light scattering and transmission electron microscope (TEM) were used to measure smaller degree of aggregation that can reveal sodium citrate- and dsDNA-AuNRs interactions in fine detail.

Electropolymerizable peripherally tetra-{2-[3-(diethylamino)phenoxy]ethoxy} substituted as well as axially (4-phenylpiperazin-1-yl)propanoxy-disubstituted silicon phthalocyanines and their electrochemistry.

PubMed

Biyiklioglu, Zekeriya; Alp, Hakan

2015-11-21

A novel type of peripherally tetra-substituted as well as axially disubstituted silicon(iv) phthalocyanine containing electropolymerizable ligands was designed and synthesized for the first time. Axial bis-hydroxy silicon phthalocyanine 2 was prepared from 2(3),9(10),16(17),23(24)-tetrakis-{2-[3-(diethylamino)phenoxy]ethoxy}phthalocyanine 1 in dichloromethane by using 1.8-diazabicyclo[5.4.0]undec-7-ene (DBU) and trichlorosilane. Peripherally tetra and axially di-substituted silicon phthalocyanine 4 was synthesized from 2(3),9(10),16(17),23(24)-tetrakis-{2-[3-(diethylamino)phenoxy]ethoxy}silicon(iv)phthalocyanine dihydroxide 2 with 1-(3-chloropropyl)-4-phenylpiperazine 3 in toluene in the presence of NaH at 120 °C. These complexes were fully characterized by various spectroscopy techniques such as (1)H-NMR, (13)C-NMR, IR, UV-Vis, and MALDI-TOF spectroscopy and elemental analysis as well. Electropolymerization properties of silicon(IV) phthalocyanine complexes were investigated by cyclic and square wave voltammetry. Electrochemical studies reveal that silicon(IV) phthalocyanine complexes were electropolymerized on the working electrode during the anodic potential scan. This study is the first example of electropolymerization of both peripherally tetra and axially di-substituted silicon phthalocyanines on the same molecule.

Luminescence properties of Sm3+-doped alkaline earth ortho-stannates

NASA Astrophysics Data System (ADS)

Stanulis, Andrius; Katelnikovas, Artūras; Enseling, David; Dutczak, Danuta; Šakirzanovas, Simas; Bael, Marlies Van; Hardy, An; Kareiva, Aivaras; Jüstel, Thomas

2014-05-01

A series of Sm3+ doped M2SnO4 (M = Ca, Sr and Ba) samples were prepared by a conventional high temperature solid-state reaction route. All samples were characterized by powder X-ray diffraction (XRD) analysis, photoluminescence (PL), photoluminescence thermal quenching (TQ) and fluorescence lifetime (FL) measurements. The morphology of synthesized phosphor powders was examined by scanning electron microscopy (SEM). Moreover, luminous efficacies (LE) and color points of the CIE 1931 color space diagram were calculated and discussed. Synthesized powders showed bright orange-red emission under UV excitation. Based on the results obtained we demonstrate that Sm3+ ions occupy Ca and Sr sites in the Ca2SnO4 and Sr2SnO4 ortho-stannate structures, respectively. In contrast, Sm3+ substitutes Sn in the barium ortho-stannate Ba2SnO4 structure.

Probing AGN Structure on Microarcsecond Scales: The Space Telescope and Optical Reverberation Mapping Program

NASA Astrophysics Data System (ADS)

De Rosa, Gisella

2015-08-01

The unknown dynamics of the broad line region (BLR) gas represents a serious gap in our understanding of active galactic nuclei (AGNs) and, consequently, of the black-hole/host-galaxy co-evolution. By using time resolution as a substitute for spatial resolution, reverberation mapping (RM) is the only technique that allows us to infer both the geometry and the kinematics of the BLR gas, shading light on the BLR role on accretion/feedback processes. In 2014, the AGN STORM team used HST/COS for a RM program for which we obtained 170 UV spectra of the Seyfert 1 galaxy NGC 5548 at a near daily cadence. These data and contemporaneous observations with Swift and ground-based telescopes make this the most intensive RM program ever undertaken. I will report first results of this unique RM experiment.

Is nevtral NEUTRAL? Visual similarity effects in the early phases of written-word recognition.

PubMed

Marcet, Ana; Perea, Manuel

2017-08-01

For simplicity, contemporary models of written-word recognition and reading have unspecified feature/letter levels-they predict that the visually similar substituted-letter nonword PEQPLE is as effective at activating the word PEOPLE as the visually dissimilar substituted-letter nonword PEYPLE. Previous empirical evidence on the effects of visual similarly across letters during written-word recognition is scarce and nonconclusive. To examine whether visual similarity across letters plays a role early in word processing, we conducted two masked priming lexical decision experiments (stimulus-onset asynchrony = 50 ms). The substituted-letter primes were visually very similar to the target letters (u/v in Experiment 1 and i/j in Experiment 2; e.g., nevtral-NEUTRAL). For comparison purposes, we included an identity prime condition (neutral-NEUTRAL) and a dissimilar-letter prime condition (neztral-NEUTRAL). Results showed that the similar-letter prime condition produced faster word identification times than the dissimilar-letter prime condition. We discuss how models of written-word recognition should be amended to capture visual similarity effects across letters.

Tautomerism, molecular structure, intramolecular hydrogen bond, and enol-enol equilibrium of para halo substituted 4,4,4-trifluoro-1-phenyl-1,3-butanedione; Experimental and theoretical studies

NASA Astrophysics Data System (ADS)

Darugar, V. R.; Vakili, M.; Nekoei, A. R.; Tayyari, S. F.; Afzali, R.

2017-12-01

Para halo, X = F, Cl, and Br, substitution effect on tautomerism, keto-enol content, molecular structure, intramolecular hydrogen bonding, and enol-enol equilibrium constants of 4,4,4-trifluoro-1-phenyl-1,3-butanedione, known as trifluorobenzoylacetone (TFBA), have been investigated by means of density functional theory calculations and NMR, IR, and UV-Vis spectroscopic methods. Comparing the calculated and experimental results suggests coexisting of two stable cis-enol forms of titled molecules in comparable proportions in the sample. The theoretical and experimental results show that the equilibrium constants between both stable cis-enol forms of the studied molecules are similar, about 1.1-1.2. According to the AIM calculated results performed at the B3LYP/6-311++G∗∗ level, the target para halo molecules have a hydrogen bond strength of about 18.6 kcal/mol, as a medium hydrogen bond, similar to that of TFBA. The theoretical and experimental results indicate that there is no considerable difference between the hydrogen bond strength of the X-substituted titled molecules.

Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions† †Electronic supplementary information (ESI) available: Formulae for calculating aggregation parameters and fitting of kinetic constants and copies of NMR spectra. See DOI: 10.1039/c6cp00493h Click here for additional data file.

PubMed Central

Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian

2016-01-01

A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

Comparative study of carotenoids, catalase and radical formation in human and animal skin.

PubMed

Haag, S F; Bechtel, A; Darvin, M E; Klein, F; Groth, N; Schäfer-Korting, M; Bittl, R; Lademann, J; Sterry, W; Meinke, M C

2010-01-01

Animal skin is widely used in dermatological free radical research. Porcine ear skin is a well-studied substitute for human skin. The use of bovine udder skin is rare but its high carotenoid content makes it particularly appropriate for studying the redox state of the skin. Yet, information on the suitability of animal skin for the study of external hazard effects on the redox state of human skin has been lacking. In this study, we investigated the activity of the antioxidant enzyme catalase and the carotenoid content defining the redox status as well as UV-induced radical formation of human, porcine ear and bovine udder skin ex vivo. In human skin only low levels of radical formation were detected following UV irradiation, whereas bovine skin contains the highest amount of carotenoids but the lowest amount of catalase. Porcine ear skin does not exhibit a carotenoid signal but its catalase activity is close to human skin. Therefore, radical formation can neither be correlated to the amount of catalase nor to the amount of carotenoids in the skin. All skin types can be used for electron paramagnetic resonance-based detection of radicals, but porcine skin was found to be the most suitable type. Copyright 2010 S. Karger AG, Basel.

Photochemical studies on aromatic γ,δ-epoxy ketones: efficient synthesis of benzocyclobutanones and indanones.

PubMed

Shao, Yutian; Yang, Chao; Gui, Weijun; Liu, Yang; Xia, Wujiong

2012-04-11

Irradiation of terminal aromatic γ,δ-epoxy ketones with a 450 W UV lamp led to Norrish type II cyclization/semi-pinacol rearrangement cascade reaction which formed the benzocyclobutanones containing a full-carbon quaternary center, whereas irradiation of substituted aromatic γ,δ-epoxy ketones led to the indanones through a photochemical epoxy rearrangement and 1,5-biradicals cyclization tandem reaction. This journal is © The Royal Society of Chemistry 2012

Self-assembly of Zn(salphen) complexes: steric regulation, stability studies and crystallographic analysis revealing an unexpected dimeric 3,3'-t-Bu-substituted Zn(salphen) complex.

PubMed

Martínez Belmonte, Marta; Wezenberg, Sander J; Haak, Robert M; Anselmo, Daniele; Escudero-Adán, Eduardo C; Benet-Buchholz, Jordi; Kleij, Arjan W

2010-05-21

The self-assembly features of a series of (non)symmetrical Zn(salphen) complexes have been studied in detail by X-ray crystallography, NMR and UV-vis techniques. The combined data demonstrate that the stability of these dimeric assemblies and the relative position of each monomeric unit within the dinuclear structure depend on the location and combination of the aromatic ring substituents.

Class Projects in Physical Organic Chemistry: The Hammett Equation

NASA Astrophysics Data System (ADS)

Marrs, Peter S.

2001-04-01

This paper provides a brief introduction to the Hammett equation. A laboratory experiment is described that requires students to determine the pKa of three para-substituted phenols through the use of UV-spectroscopy. A student's individual data are combined with other students' data to provide a class set. The students analyze the class set of data to determine whether sp or sp- is more appropriate for the reaction studied, and they also determine r for the reaction.

Optical properties of novel environmentally benign biologically active ferrocenyl substituted chromophores: A detailed insight via experimental and theoretical approach

NASA Astrophysics Data System (ADS)

Khan, Salman A.; Asiri, Abdullah M.; Al-Ghamdi, Najat Saeed M.; Zayed, Mohie E. M.; Sharma, Kamlesh; Parveen, Humaira

2017-07-01

Series of ferrocenyl substituted chromophores were synthesized via a reaction of acetyl ferrocene and a variety of aldehyde under microwave irradiation. The structure of synthesized compounds were established by spectroscopic (FT-IR, 1H NMR, 13C NMR, ESI-MS) and elemental analysis. UV-Vis and fluorescence spectroscopy measurements provided that all compounds have good absorbent and fluorescent properties. Fluorescence polarity studies demonstrated that these compounds were sensitive to the polarity of the microenvironment provided by different solvents. In addition, spectroscopic and physicochemical parameters, including singlet absorption, extinction coefficient, Stokes shift, oscillator strength and dipole moment, were investigated in order to explore the analytical potential of the synthesized compounds. The anti-bacterial activity of these compounds were first studied in vitro by the disk diffusion assay against two Gram-positive and two Gram-negative bacteria. The minimum inhibitory concentration was then determined with the reference of standard drug chloramphenicol. The results displayed that compound 3 was better inhibitors for both types of the bacteria (Gram-positive and Gram-negative) than chloramphenicol. Based on the density functional theory; total energy, the atomic orbital contribution to frontier orbitals: LUMO and HOMO, of all synthesized compounds were calculated to support the antibacterial activities.

3-[(E)-(acridin-9‧-ylmethylidene)amino]-1-substituted thioureas and their biological activity

NASA Astrophysics Data System (ADS)

Bečka, Michal; Vilková, Mária; Salem, Othman; Kašpárková, Jana; Brabec, Viktor; Kožurková, Mária

2017-06-01

This paper describes the synthesis of a novel series of acridine thiosemicarbazones through a two-step reaction between various isothiocyanates and hydrazine followed by treatment with acridin-9-carbaldehyde. The properties of this series of seven new derivatives are studied using NMR and biochemical techniques, and the DNA-binding properties of the compounds are determined using spectrophotometric studies (UV-vis absorption, fluorescence, and circular/linear dichroism) and viscometry. The binding constants K are estimated as being in the range of 2.2 to 7.8 × 104 M- 1 and the percentage of hypochromism was found to be 22.11-49.75% (from UV-vis spectral titration). Electrophoretic experiments prove that the novel compounds demonstrate moderate inhibitory effects against Topo I activity at a concentration of 60 × 10- 6 M.

Tunable blue-green emission and energy transfer properties in β-Ca3(PO4)2:Eu(2+), Tb(3+) phosphors with high quantum efficiencies for UV-LEDs.

PubMed

Li, Kai; Zhang, Yang; Li, Xuejiao; Shang, Mengmeng; Lian, Hongzhou; Lin, Jun

2015-03-14

A series of Eu(2+) and Tb(3+) singly-doped and co-doped β-Ca3(PO4)2 phosphors have been synthesized via the high-temperature solid-state reaction method. Thermogravimetric (TG) analysis, fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) patterns and Rietveld refinements, photoluminescence (PL) spectra including temperature-dependent PL and quantum efficiency, and fluorescence decay lifetimes have been used to characterise the as-prepared samples. Under UV excitation, β-Ca3(PO4)2:Eu(2+) presents a broad emission band centered at 415 nm, which can be decomposed into five symmetrical bands peaking at 390, 408, 421, 435 and 511 nm based on the substitution of five kinds of Ca(2+) sites by Eu(2+) ions. β-Ca3(PO4)2:Tb(3+) shows characteristic emission lines under Tb(3+) 4f-5d transition excitation around 223 nm. In β-Ca3(PO4)2:Eu(2+), Tb(3+) phosphors, similar excitation spectra monitored at 415 and 547 nm have been observed, which illustrates the possibility of energy transfer from Eu(2+) to Tb(3+) ions. The variations in the emission spectra and decay lifetimes further demonstrate the existence of energy transfer from Eu(2+) to Tb(3+) ions under UV excitation. The energy transfer mechanism has been confirmed to be dipole-quadrupole, which can be validated via the agreement of critical distances obtained from the concentration quenching (12.11 Å) and spectrum overlap methods (9.9-13.2 Å). The best quantum efficiency can reach 90% for the β-Ca3(PO4)2:0.01Eu(2+), 0.15Tb(3+) sample under 280 nm excitation. These results show that the developed phosphors may possess potential applications in UV-pumped white light-emitting diodes.

Stability and thermophysical studies on deep eutectic solvent based carbon nanotube nanofluid

NASA Astrophysics Data System (ADS)

Chen, Yan Yao; Walvekar, Rashmi; Khalid, Mohammad; Shahbaz, Kaveh; Gupta, T. C. S. M.

2017-07-01

Commercial coolants such as water, ethylene glycol and triethylene glycol possess very low thermal conductivity, high vapor pressure, corrosion issues and low thermal stability thus limiting the thermal enhancement of the nanofluids. Thus, a new type of base fluid known as deep eutectic solvents (DESs) is proposed in this work as a potential substitute for the conventional base fluid due to their unique solvent properties such as low vapor pressure, high thermal stability, biodegradability and non-flammability. In this work, 33 different DESs derived from phosphonium halide salt and ammonium halide salts were synthesised. Carbon nantubes (CNTs) with different concentrations (0.01 wt%-0.08 wt%) were dispersed into DESs with the help of sonication. Stability of the nanofluids were determined using both qualitative (visual observation) and quantitative (UV spectroscopy) approach. In addition, thermo-physical properties such as thermal conductivity, specific heat, viscosity and density were investigated. The stability results indicated that phosphonium based DESs have higher stability (up to 4 d) as compared to ammonium-based DESs (up to 3 d). Thermal enhancement of 30% was observed for ammonium based DES-CNT nanofluid whereas negative thermal enhancement was observed in phosphonium based DES-CNT nanofluid.

Formulation of colchicine ointment for the treatment of acute gout.

PubMed

Maduri, Sairam; Atla, Venkateshwar Reddy

2012-11-01

In spite of being the fastest acting drug available for the control of an acute gout attack, colchicine is generally considered a last alternative in gout therapy. This is mainly due to the severe adverse effects associated with its administration through the enteral and parenteral routes, as well as its high risk/benefit ratio. The preparation of dosage forms of colchicine that can be administered by alternative routes is therefore a beneficial exercise. Among the formulable substitute dosage forms of colchicine, its ointment seems to be the best option available due to its ability to deliver the drug transdermally as well as its ease of preparation and evaluation. In this study, we prepared and tested 0.2% and 0.5% colchicine ointments for their effectiveness in delivering colchicine transdermally. Colchicine ointment was prepared using a self-formulated water-in-oil type of emulsion ointment base, with the colchicine dissolved in the water portion of the ointment base. In vitro drug release studies were carried out using the Franz diffusion test apparatus and an ultraviolet (UV)-visible spectrophotometer was used to quantify the drug in the samples. Rabbits were used as test animals for in vivo studies and the blood samples were analysed using the UV-visible spectrophotometer. Colchicine was found to be well-absorbed transdermally, although absorption was not 100%. No side effects were associated with its 0.2% formulation. Ointments containing colchicine in low concentrations may be a feasible and effective treatment option for the prevention and treatment of acute gout attacks.

Time-of-flight mass spectrometry assessment of fluconazole and climbazole UV and UV/H2O2 degradability: Kinetics study and transformation products elucidation.

PubMed

Castro, Gabriela; Casado, Jorge; Rodríguez, Isaac; Ramil, María; Ferradás, Aida; Cela, Rafael

2016-01-01

The efficiency of UV irradiation for the removal of the antimycotic drugs fluconazole (FCZ) and climbazole (CBZ) from water samples is evaluated. Degradation experiments, at laboratory scale, were carried out with spiked aliquots of ultrapure water solutions and treated wastewater samples using low-pressure mercury lamps emitting at 254 nm. Time course of precursor pollutants and identification of arising transformation products (TPs) was performed by injection of different reaction time aliquots in a liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) system. Chemical structures of identified TPs were proposed from their full-product ion spectra, acquired using different collision energies. During UV irradiation experiments, the half-lives (t1/2) of FCZ and CBZ were similar in ultrapure water solutions and wastewater samples; however, the first species was more recalcitrant than the second one. Four TPs were identified in case of FCZ resulting from substitution of fluorine atoms by hydroxyl moieties and intramolecular cyclization with fluorine removal. CBZ interacted with UV radiation through reductive dechlorination, hydroxylation and cleavage of the ether bond; moreover, five additional primary TPs, with the same empirical formula as CBZ, were also noticed. Given the relatively long t1/2 of FCZ under direct photolysis (ca. 42 min), UV irradiation was combined with H2O2 addition to promote formation of reactive hydroxyl radicals. Under such conditions, the degradation rate of FCZ was enhanced significantly and no TPs were detected. These latter conditions allowed also the effective removal of CBZ TPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evolution of ultraviolet vision in the largest avian radiation - the passerines.

PubMed

Ödeen, Anders; Håstad, Olle; Alström, Per

2011-10-24

Interspecific variation in avian colour vision falls into two discrete classes: violet sensitive (VS) and ultraviolet sensitive (UVS). They are characterised by the spectral sensitivity of the most shortwave sensitive of the four single cones, the SWS1, which is seemingly under direct control of as little as one amino acid substitution in the cone opsin protein. Changes in spectral sensitivity of the SWS1 are ecologically important, as they affect the abilities of birds to accurately assess potential mates, find food and minimise visibility of social signals to predators. Still, available data have indicated that shifts between classes are rare, with only four to five independent acquisitions of UV sensitivity in avian evolution. We have classified a large sample of passeriform species as VS or UVS from genomic DNA and mapped the evolution of this character on a passerine phylogeny inferred from published molecular sequence data. Sequencing a small gene fragment has allowed us to trace the trait changing from one stable state to another through the radiation of the passeriform birds. Their ancestor is hypothesised to be UVS. In the subsequent radiation, colour vision changed between UVS and VS at least eight times. The phylogenetic distribution of SWS1 cone opsin types in Passeriformes reveals a much higher degree of complexity in avian colour vision evolution than what was previously indicated from the limited data available. Clades with variation in the colour vision system are nested among clades with a seemingly stable VS or UVS state, providing a rare opportunity to understand how an ecologically important trait under simple genetic control may co-evolve with, and be stabilised by, associated traits in a character complex.

Intercalation of p-methycinnamic acid anion into Zn-Al layered double hydroxide to improve UV aging resistance of asphalt

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

Peng, Chao; State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070; Dai, Jing

2015-02-15

A UV absorber, p-methycinnamic acid (PMCA), was intercalated into Zn-Al layered double hydroxide (LDH) by calcination recovery. Fourier transform infrared spectroscopy showed that the PMCA anions completely replaced the CO{sub 3}{sup 2−} anions in the interlayer galleries of Zn-Al-LDH containing PMCA anions (Zn-Al-PMCA-LDH). X-ray diffraction and transmission electron microscopy showed that the interlayer distance increased from 0.78 nm to 1.82 nm after the substitution of PMCA anions for CO{sub 3}{sup 2−} anions. The similar diffraction angles of the CO{sub 3}{sup 2−} anion-containing Zn-Al-LDH (Zn-Al-CO{sub 3}{sup 2−}-LDH) and the Zn-Al-CO{sub 3}{sup 2−}-LDH/styrene–butadiene–styrene (SBS) modified asphalt implied that the asphalt molecules domore » not enter into the LDH interlayer galleries to form separated-phase structures. The different diffraction angles of Zn-Al-PMCA-LDH and Zn-Al-PMCA-LDH/SBS modified asphalt indicated that the asphalt molecules penetrated into the LDH interlayer galleries to form an expanded-phase structure. UV-Vis absorbance analyses showed that Zn-Al-PMCA-LDH was better able to block UV light due to the synergistic effects of PMCA and Zn-Al-LDH. Conventional physical tests and atomic force microscopy images of the SBS modified asphalt, Zn-Al-CO{sub 3}{sup 2−}-LDH/SBS modified asphalt and Zn-Al-PMCA-LDH/SBS modified asphalt before and after UV aging indicated that Zn-Al-PMCA-LDH improved the UV aging resistance of SBS modified asphalts.« less

Theoretical investigation of the electronic structure of a substituted nickel phthalocyanine

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

Kaur, Prabhjot, E-mail: prabhphysics@gmail.com; Sachdeva, Ritika; Singh, Sukhwinder

2016-05-23

The optimized geometry and electronic structure of an organic compound nickel phthalocyanine tetrasulfonic acid tetra sodium salt have been investigated using density functional theory. We have also optimized the structure of nickel phthalocyanine tetrasulfonic acid tetra sodium salt in dimethyl sulfoxide to study effects of solvent on the electronic structure and transitions. Experimentally, the electronic transitions have been studied using UV-VIS spectroscopic technique. It is observed that the electronic transitions obtained from the theoretical studies generally agree with the experiment.

Comparison of Ground-Based and Satellite-Derived Solar UV Index Levels at Six South African Sites.

PubMed

Cadet, Jean-Maurice; Bencherif, Hassan; Portafaix, Thierry; Lamy, Kévin; Ncongwane, Katlego; Coetzee, Gerrie J R; Wright, Caradee Y

2017-11-14

South Africa has been measuring the ground-based solar UV index for more than two decades at six sites to raise awareness about the impacts of the solar UV index on human health. This paper is an exploratory study based on comparison with satellite UV index measurements from the OMI/AURA experiment. Relative UV index differences between ground-based and satellite-derived data ranged from 0 to 45% depending on the site and year. Most of time, these differences appear in winter. Some ground-based stations' data had closer agreement with satellite-derived data. While the ground-based instruments are not intended for long-term trend analysis, they provide UV index information for public awareness instead, with some weak signs suggesting such long-term trends may exist in the ground-based data. The annual cycle, altitude, and latitude effects clearly appear in the UV index data measured in South Africa. This variability must be taken into account for the development of an excess solar UV exposure prevention strategy.

Comparison of Ground-Based and Satellite-Derived Solar UV Index Levels at Six South African Sites

PubMed Central

Cadet, Jean-Maurice; Bencherif, Hassan; Portafaix, Thierry; Lamy, Kévin; Ncongwane, Katlego; Coetzee, Gerrie J. R.; Wright, Caradee Y.

2017-01-01

South Africa has been measuring the ground-based solar UV index for more than two decades at six sites to raise awareness about the impacts of the solar UV index on human health. This paper is an exploratory study based on comparison with satellite UV index measurements from the OMI/AURA experiment. Relative UV index differences between ground-based and satellite-derived data ranged from 0 to 45% depending on the site and year. Most of time, these differences appear in winter. Some ground-based stations’ data had closer agreement with satellite-derived data. While the ground-based instruments are not intended for long-term trend analysis, they provide UV index information for public awareness instead, with some weak signs suggesting such long-term trends may exist in the ground-based data. The annual cycle, altitude, and latitude effects clearly appear in the UV index data measured in South Africa. This variability must be taken into account for the development of an excess solar UV exposure prevention strategy. PMID:29135965

The Effect of Ultraviolet Light on the "Liquid Wood"

NASA Astrophysics Data System (ADS)

Dumitru, Nedelcu; Sabina, Zǎgan; Ticuta, Negreanu-Pirjol; Remus, Zǎgan; Constantin, Cǎrausu

2014-08-01

To preserve resources, the goal is to use biobased materials containing the maximum possible amount of renewable biomass-based derivatives to secure a sustainable future. Bioplastics, biocomposites, biological fibres and related biomaterials will serve as substitutes for materials and products traditionally made from petroleum resources. To support this need, in 1998, Fraunhofer Institute of Chemistry and Tecnaro GmbH Company (founded by Jurgen Pfitzer and Helmut Nagele in Germany) investigated and developed a new compound made of wood components that can be processed as a thermoplastic material. It is well known that bioplastic and biocomposite materials represent another important group of bio-materials that include plastics reinforced with natural fibers and wood-plastic composites (WPCs). The aim of this research is to identify the behavior of "Liquid Wood" after UV irradiation. The materials used were Arbofill Fichte, Arboblend V2 Nature and Arboform L, V3 Nature. The samples were obtained by injection and the experimental study plan followed the Taguchi method with six input parameters and two levels for each of them. Three samples from each material were tested in an ultraviolet environment using different time of exposure in order to establish the material characteristics. After the irradiation process the material did not turn to yellow, which suggests that the composition of the sample liquid timber inhibitors have stability and the number of α-carbonyl (C = O) groups is sufficiently low. After the graphs analyzing can be inferred relatively similar performance of the samples in the first stage both UV and the VIS, indicating that the activity is almost absent. In UV is clearly observed the peak amplitude (maximum absorbance) at different wavelengths (λ). So, in terms of peak intensity the samples follow the order: Arboform L, V3 Nature; Arbofill Fichte and Arboblend V2 Nature.

Use of a heated graphite scrubber as a means of reducing interferences in UV-absorbance measurements of atmospheric ozone

NASA Astrophysics Data System (ADS)

Turnipseed, Andrew A.; Andersen, Peter C.; Williford, Craig J.; Ennis, Christine A.; Birks, John W.

2017-06-01

A new solid-phase scrubber for use in conventional ozone (O3) photometers was investigated as a means of reducing interferences from other UV-absorbing species and water vapor. It was found that when heated to 100-130 °C, a tubular graphite scrubber efficiently removed up to 500 ppb ozone and ozone monitors using the heated graphite scrubber were found to be less susceptible to interferences from water vapor, mercury vapor, and aromatic volatile organic compounds (VOCs) compared to conventional metal oxide scrubbers. Ambient measurements from a graphite scrubber-equipped photometer and a co-located Federal equivalent method (FEM) ozone analyzer showed excellent agreement over 38 days of measurements and indicated no loss in the scrubber's ability to remove ozone when operated at 130 °C. The use of a heated graphite scrubber was found to reduce the interference from mercury vapor to ≤ 3 % of that obtained using a packed-bed Hopcalite scrubber. For a series of substituted aromatic compounds (ranging in volatility and absorption cross section at 253.7 nm), the graphite scrubber was observed to consistently exhibit reduced levels of interference, typically by factors of 2.5 to 20 less than with Hopcalite. Conventional solid-phase scrubbers also exhibited complex VOC adsorption and desorption characteristics that were dependent upon the relative humidity (RH), volatility of the VOC, and the available surface area of the scrubber. This complex behavior involving humidity is avoided by use of a heated graphite scrubber. These results suggest that heated graphite scrubbers could be substituted in most ozone photometers as a means of reducing interferences from other UV-absorbing species found in the atmosphere. This could be particularly important in ozone monitoring for compliance with the United States (U.S.) Clean Air Act or for use in VOC-rich environments such as in smog chambers and monitoring indoor air quality.

Ion yields in UV-MALDI mass spectrometry as a function of excitation laser wavelength and optical and physico-chemical properties of classical and halogen-substituted MALDI matrixes.

PubMed

Soltwisch, Jens; Jaskolla, Thorsten W; Hillenkamp, Franz; Karas, Michael; Dreisewerd, Klaus

2012-08-07

The laser wavelength constitutes a key parameter in ultraviolet-matrix-assisted laser desorption ionization-mass spectrometry (UV-MALDI-MS). Optimal analytical results are only achieved at laser wavelengths that correspond to a high optical absorption of the matrix. In the presented work, the wavelength dependence and the contribution of matrix proton affinity to the MALDI process were investigated. A tunable dye laser was used to examine the wavelength range between 280 and 355 nm. The peptide and matrix ion signals recorded as a function of these irradiation parameters are displayed in the form of heat maps, a data representation that furnishes multidimensional data interpretation. Matrixes with a range of proton affinities from 809 to 866 kJ/mol were investigated. Among those selected are the standard matrixes 2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxycinnamic acid (HCCA) as well as five halogen-substituted cinnamic acid derivatives, including the recently introduced 4-chloro-α-cyanocinnamic acid (ClCCA) and α-cyano-2,4-difluorocinnamic acid (DiFCCA) matrixes. With the exception of DHB, the highest analyte ion signals were obtained toward the red side of the peak optical absorption in the solid state. A stronger decline of the molecular analyte ion signals generated from the matrixes was consistently observed at the low wavelength side of the peak absorption. This effect is mainly the result of increased fragmentation of both analyte and matrix ions. Optimal use of multiply halogenated matrixes requires adjustment of the excitation wavelength to values below that of the standard MALDI lasers emitting at 355 (Nd:YAG) or 337 nm (N(2) laser). The combined data provide new insights into the UV-MALDI desorption/ionization processes and indicate ways to improve the analytical sensitivity.

Mixed-ligand Ru(II) complexes with 2,2'-bipyridine and aryldiazo-beta-diketonato auxillary ligands: synthesis, physico-chemical study and antitumour properties.

PubMed

Mishra, Lallan; Yadaw, Ajay K; Bhattacharya, Subrato; Dubey, Santosh K

2005-05-01

The complexes of Ru(II)-2,2'-bipyridyl with substituted diazopentane-2,4-diones (L1H-L5H) were synthesized and characterized by elemental analyses, conductance, FAB (fast atom bombardment) mass and spectral (IR, UV/Vis (UV/visible), NMR) studies. Molecular geometry optimization of the complexes was also made. None of the complexes luminesce. However, facilitated oxidation of Ru(II) to Ru(III) was evidenced from their lower reduction potential data. The ligands and their complexes were tested for their antitumour activity against a variety of tumour cell lines. Though activity is found to vary with the type of tumour cell lines used, yet complex 5 with naphtyldiazopentane-2,4-dione as co-ligand was found to be a potential compound as it showed in general significant activity against all cell lines studied.

Aluminium and titanium modified mesoporous TUD-1: A bimetal acid catalyst for Biginelli reaction

NASA Astrophysics Data System (ADS)

Pasupathi, M.; Santhi, N.; Pachamuthu, M. P.; Alamelu Mangai, G.; Ragupathi, C.

2018-05-01

Using a simple, non-surfactant template triethanolamine (TEA), bimetal (Al3+ and Ti4+ ions) incorporated mesoporous catalyst AlTiTUD-1 (Si/Al+Ti = 50) was synthesized. The catalyst was characterized by XRD (Low and High angle), N2 Sorption, FTIR, SEM, TEM, DR UV Visible, and pyridine adsorbed FT-IR techniques. The XRD and N2 sorption studies confirmed its amorphous, mesoporous nature, which possessed a BET surface area of 590 m2 g-1 and pore diameter of 4.4 nm. The Al3+ and Ti4+ co-ordination within the TUD-1 was evaluated by DR UV-Vis. Pyridine adsorbed FTIR revealed both Bronsted (B) and Lewis (L) acidity, which is responsible for the catalytic activity. The acid catalyst showed a good catalytic performance in Biginelli type multicomponent coupling reaction for the substituted aldehydes, ethyl acetoacetate and thiourea to yield about 70% in reflux condition.

Sugar Substitutes

MedlinePlus

... Substitutes Share Print Sugar substitutes are chemical or plant-based substances used to sweeten or enhance the ... made with saccharin. Stevia sweeteners Stevia is a plant-based sugar substitute that has no calories. The ...

Comparative studies on the interaction of caffeic acid, chlorogenic acid and ferulic acid with bovine serum albumin

NASA Astrophysics Data System (ADS)

Li, Shuang; Huang, Kelong; Zhong, Ming; Guo, Jun; Wang, Wei-zheng; Zhu, Ronghua

2010-10-01

The substitution of the hydrogen on aromatic and esterification of carboxyl group of the phenol compounds plays an important role in their bio-activities. In this paper, caffeic acid (CaA), chlorogenic acid (ChA) and ferulic acid (FA) were selected to investigate the binding to bovine serum albumin (BSA) using UV absorption spectroscopy, fluorescence spectroscopy and synchronous fluorescence spectroscopy. It was found that the methoxyl group substituting for the 3-hydroxyl group of CaA decreased the affinity for BSA and the esterification of carboxyl group of CaA with quinic acid increased the affinities. The affinities of ChA and FA with BSA were more sensitive to the temperature than that of CaA with BSA. Synchronous fluorescence spectroscopy and time-resolved fluorescence indicated that the Stern-Volmer plots largely deviated from linearity at high concentrations and were caused by complete quenching of the tyrosine fluorescence of BSA.

Molecular characterization of multivalent bioconjugates by size-exclusion chromatography with multiangle laser light scattering.

PubMed

Pollock, Jacob F; Ashton, Randolph S; Rode, Nikhil A; Schaffer, David V; Healy, Kevin E

2012-09-19

The degree of substitution and valency of bioconjugate reaction products are often poorly judged or require multiple time- and product-consuming chemical characterization methods. These aspects become critical when analyzing and optimizing the potency of costly polyvalent bioactive conjugates. In this study, size-exclusion chromatography with multiangle laser light scattering was paired with refractive index detection and ultraviolet spectroscopy (SEC-MALS-RI-UV) to characterize the reaction efficiency, degree of substitution, and valency of the products of conjugation of either peptides or proteins to a biopolymer scaffold, i.e., hyaluronic acid (HyA). Molecular characterization was more complete compared to estimates from a protein quantification assay, and exploitation of this method led to more accurate deduction of the molecular structures of polymer bioconjugates. Information obtained using this technique can improve macromolecular engineering design principles and help to better understand multivalent macromolecular interactions in biological systems.

Synthesis, antimalarial activity, heme binding and docking studies of N-substituted 4-aminoquinoline-pyrimidine molecular hybrids.

PubMed

Maurya, Shiv Shyam; Khan, Shabana I; Bahuguna, Aparna; Kumar, Deepak; Rawat, Diwan S

2017-03-31

A series of novel N-substituted 4-aminoquinoline-pyrimidine hybrids have been synthesized via simple and economic route and evaluated for their antimalarial activity. Most compounds showed potent antimalarial activity against both CQ-sensitive and CQ-resistant strains with high selectivity index. All the compounds were found to be non-toxic to the mammalian cell lines. The most active compound 7b was analysed for heme binding activity using UV-spectrophotometer. Compound was found to interact with heme and a complex formation between compound and heme in a 1:1 stoichiometry ratio was determined using job plots. The interaction of these hybrids was also investigated by the molecular docking studies in the binding site of wild type Pf-DHFR-TS and quadruple mutant Pf-DHFR-TS. The pharmacokinetic property analysis of best active compounds was also studied by ADMET prediction. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Molecular characterization of multivalent bioconjugates by size-exclusion chromatography (SEC) with multi-angle laser light scattering (MALS)

PubMed Central

Pollock, Jacob F.; Ashton, Randolph S.; Rode, Nikhil A.; Schaffer, David V.; Healy, Kevin E.

2013-01-01

The degree of substitution and valency of bioconjugate reaction products are often poorly judged or require multiple time- and product- consuming chemical characterization methods. These aspects become critical when analyzing and optimizing the potency of costly polyvalent bioactive conjugates. In this study, size-exclusion chromatography with multi-angle laser light scattering was paired with refractive index detection and ultraviolet spectroscopy (SEC-MALS-RI-UV) to characterize the reaction efficiency, degree of substitution, and valency of the products of conjugation of either peptides or proteins to a biopolymer scaffold, i.e., hyaluronic acid (HyA). Molecular characterization was more complete compared to estimates from a protein quantification assay, and exploitation of this method led to more accurate deduction of the molecular structures of polymer bioconjugates. Information obtained using this technique can improve macromolecular engineering design principles and better understand multivalent macromolecular interactions in biological systems. PMID:22794081

In vitro skin models and tissue engineering protocols for skin graft applications.

PubMed

Naves, Lucas B; Dhand, Chetna; Almeida, Luis; Rajamani, Lakshminarayanan; Ramakrishna, Seeram

2016-11-30

In this review, we present a brief introduction of the skin structure, a concise compilation of skin-related disorders, and a thorough discussion of different in vitro skin models, artificial skin substitutes, skin grafts, and dermal tissue engineering protocols. The advantages of the development of in vitro skin disorder models, such as UV radiation and the prototype model, melanoma model, wound healing model, psoriasis model, and full-thickness model are also discussed. Different types of skin grafts including allografts, autografts, allogeneic, and xenogeneic are described in detail with their associated applications. We also discuss different tissue engineering protocols for the design of various types of skin substitutes and their commercial outcomes. Brief highlights are given of the new generation three-dimensional printed scaffolds for tissue regeneration applications. © 2016 The Author(s). published by Portland Press Limited on behalf of the Biochemical Society.

Computational study of the absorption spectrum of defected ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Michos, F. I.; Sigalas, M. M.

2018-04-01

Energy levels and absorption spectra of defected ZnS nanoparticles (NPs) were calculated with Density Functional Theory (DFT) and Time Dependent DFT. Several types of defects were examined such as vacancies and substitutions. NPs with S vacancies were found to have their absorption spectra moved to lower energies well inside the visible spectrum with significantly high oscillator strength. Also, NPs with substitution of S atoms with Cl, Br, or I showed significant absorption. In general, this type of defect moves the absorption spectra in lower energies, thus bringing the absorption edge into the visible spectrum, while the unperturbed NPs have absorption edges in the UV region. In addition, ZnS NPs are made from more abundant and less toxic elements than the more commonly used CdSe NPs. For that reason, they may find significant applications in solar cells and other photonic applications, as well as in biosensing applications as biomarkers.

Explaining the Cyclic Voltammetry of a Poly(1,4-phenylene-ethynylene)-alt-poly(1,4-phenylene-vinylene) Copolymer upon Oxidation by using Spectroscopic Techniques.

PubMed

Enengl, Christina; Enengl, Sandra; Bouguerra, Nassima; Havlicek, Marek; Neugebauer, Helmut; Egbe, Daniel A M

2017-01-04

Poly(1,4-phenylene-ethynylene)-alt-poly(1,4-phenylene-vinylene) (PPE-PPV) copolymers have attracted quite a lot of attention in the last few years for electronic device applications owing to their enhanced fluorescence. In this work, we focus on one particular PPE-PPV copolymer with dissymmetrically substituted 1,4-phenylene-ethynylene and symmetrically substituted 1,4-phenylene-vinylene building units. Six successively performed cyclic voltammograms are presented, measured during the oxidation reactions. As the oxidation onset of the electrochemical reaction shifts to lower potentials in each cycle, this behavior is elucidated by using spectroscopic techniques ranging from UV/Vis/near-IR to mid-IR including spin-resonance techniques. Hence, these findings help to explain some of the copolymer's most advantageous properties in terms of possible oxidation products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Electrostatically Self-Assembled Thin Film Made of Zn-Substituted Tungstoborate and Rhodamine B with Photoelectrochemical Properties.

PubMed

Mao, Xu; Zhang, Jia-Ning; Gao, Li-Hua; Su, Yu; Chen, Peng-Xia; Wang, Ke-Zhi

2016-04-01

An electrostatically self-assembled multilayer thin film consisting of alternating layers of Keggin polyoxometalate of Zn-substituted tungstoborate (BW11Zn) and Rhodamine B (RhB) has successfully been prepared on a quartz and indium-tin oxide (ITO) glass substrate. The ultraviolet-visible (UV-vis) absorption spectra demonstrated that the electrostatically self-assembled film of (BW11Zn/RhB)n was uniformly deposited layer by layer, and the RhB molecules in the film formed the J-aggregation. The photoelectrochemical investigations showed that the films generated stable cathodic photocurrents that originated from RhB, and the maximal cathodic photocurrent density generated by an eight-layer film was 4.9 µA/cm2 while the film was irradiated with 100 mW/cm2 polychromatic light of 730 nm > λ > 325 nm at an applied potential of 0 V versus a saturated calomel electrode.

Silicon nanoparticle-ZnS nanophosphors for ultraviolet-based white light emitting diode

NASA Astrophysics Data System (ADS)

Stupca, Matthew; Nayfeh, Osama M.; Hoang, Tuan; Nayfeh, Munir H.; Alhreish, Bahjat; Boparai, Jack; AlDwayyan, Abdullah; AlSalhi, Mohamad

2012-10-01

Present red phosphor converters provide spectra dominated by sharp lines and suffer from availability and stability issues which are not ideal for color mixing in display or solid state lighting applications. We examine the use of mono dispersed 3 nm silicon nanoparticles, with inhomogeneously broadened red luminescence as an effective substitute for red phosphors. We tested a 3-phase hybrid nanophosphor consisting of ZnS:Ag, ZnS:Cu,Au,Al, and nanoparticles. Correlated color temperature is examined under UV and LED pumping in the range 254, 365-400 nm. The temperature is found reasonably flat for the longer wavelengths and drops for the shorter wavelengths while the color rendering index increases. The photo stability of the phosphors relative to the silicon nanoparticles is recorded. The variation in the temperature is analyzed in terms of the strength of inter-band-gap transition and continuum band to band transitions.

Synthesis and characterization of tunable coumarin- linked glasses as new class of organic/inorganic phosphors

NASA Astrophysics Data System (ADS)

Luridiana, Alberto; Pretta, Gianluca; Secci, Francesco; Frongia, Angelo; Chiriu, Daniele; Carbonaro, Carlo Maria; Corpino, Riccardo; Ricci, Pier Carlo

2014-10-01

It is well known that stilbene with a trans conformation is highly fluorescent. From the viewpoint of molecular structure, coumarins bear a carbon-carbon double bond which is fixed as trans conformation as in trans-stilbene through a lactone structure. This can help to avoid the trans-cis transformation of the double bond under ultraviolet (UV) irradiation as observed in stilbene compounds and results in strong fluorescence and high fluorescence quantum yield and photostability in most of coumarin derivatives. Herein we report some preliminary results about the synthesis and spectroscopic characterization of tunable coumarins and the development of a new linkage protocol for the obtainment of monolayer coumarin-covalently linked glasses. The resulting organic/inorganic coumarin/silica based Self-Assembled Monolayer (SMA) film is proposed as new phosphors for the substituting of critical raw materials, like rare earths, in photonics applications.

Common-path Fourier domain optical coherence tomography of irradiated human skin and ventilated isolated rabbit lungs

NASA Astrophysics Data System (ADS)

Popp, A.; Wendel, M.; Knels, L.; Knuschke, P.; Mehner, M.; Koch, T.; Boller, D.; Koch, P.; Koch, E.

2005-08-01

A compact common path Fourier domain optical coherence tomography (FD-OCT) system based on a broadband superluminescence diode is used for biomedical imaging. The epidermal thickening of human skin after exposure to ultraviolet radiation is measured to proof the feasibility of FD-OCT for future substitution of invasive biopsies in a long term study on natural UV skin protection. The FD-OCT system is also used for imaging lung parenchyma. FD-OCT images of a formalin fixated lung show the same alveolar structure as scanning electron microscopy images. In the ventilated and blood-free perfused isolated rabbit lung FD-OCT is used for real-time cross-sectional image capture of alveolar mechanics throughout tidal ventilation. The alveolar mechanics changing from alternating recruitment-derecruitment at zero positive end-expiratory pressure (PEEP) to persistent recruitment after applying a PEEP of 5 cm H2O is observed in the OCT images.

Solar UV Degradation Patterns in Photodegradable Ldpe

NASA Astrophysics Data System (ADS)

Andrady, A. L.

2016-02-01

"Degradable" polymers have been proposed as an alternative to traditional polymers as a means to potentially reduce the amount and impacts of plastic marine debris, yet the degradation of these materials in seawater is typically unknown. The light-induced degradation of a copolymer of ethylene - carbon monoxide {1%} was studied under accelerated laboratory exposure conditions. The copolymer, used as a substitute for LDPE in some applications where rapid photodegradation is desirable, loses mechanical integrity and embrittles rapidly under outdoor exposure. A laboratory weathering study of these laminates was carried out to compare the kinetics of degradation on sand to those in seawater at ambient temperature, based on the rate of change in tensile properties of the material. Virgin resin pellets of the copolymer were also exposed to laboratory weathering to detect the generation of microparticles at their surface during extensive degradation. Microparticle generation, detected by laser light scattering, as a function of the exposure duration will also be discussed.

Ferrocenyl-functionalised terpyridines and their transition-metal complexes: syntheses, structures and spectroscopic and electrochemical properties.

PubMed

Siemeling, Ulrich; Vor der Brüggen, Jens; Vorfeld, Udo; Neumann, Beate; Stammler, Anja; Stammler, Hans-George; Brockhinke, Andreas; Plessow, Regina; Zanello, Piero; Laschi, Franco; Fabrizi de Biani, Fabrizia; Fontani, Marco; Steenken, Steen; Stapper, Marion; Gurzadyan, Gagik

2003-06-16

Terpyridine ligands of the type Fc'-X-tpy (Fc'=ferrocenyl or octamethylferrocenyl, X=rigid spacer, tpy'=4'-substituted 2,2':6',2''-terpyridine) were prepared, crystallographically characterised and used for the synthesis of di- and trinuclear bis(terpyridine) complexes of RuII, FeII and ZnII. Donor-sensitiser dyads and triads based on RuII were thoroughly investigated by (spectro)electrochemistry, UV/Vis, transient absorption and luminescence spectroscopy, and an energy level scheme was derived on the basis of the data collected. Intramolecular quenching of the photoexcited RuII complexes by the redox-active Fc' groups can occur reductively and by energy transfer. Both the redox potential of the donor Fc' and the nature of the spacer X have a decisive influence on excited-state lifetimes and emission properties of the complexes. Some of the compounds show room-temperature luminescence, which is unprecedented for ferrocenyl-functionalised compounds of this kind.

Highly Efficient and Simple Route to Synthesize N-(4-Acetylphenyl)-4-chlorobenzenesulfonamide and Its Crystal Structure

NASA Astrophysics Data System (ADS)

Kobkeatthawin, T.; Chantrapromma, S.; Chidan Kumar, C. S.; Fun, H.-K.

2017-12-01

The one-pot synthesis of N-(4-acetylphenyl)-4-chlorobenzenesulfonamide under base conditions is carried out. The present method offers several advantages such as excellent yields, short reaction times and high purity. The chemical structure was elucidated using 1H-NMR, FT-IR and UV-Vis spectroscopy. The crystal structure of the substance was determined by single crystal X-ray structure analysis. The molecule is in a V-shape. The two substituted benzene rings make the dihedral angle of 84.31(9)°. In the crystal packing, the molecules are linked by N-H···O and C-H···O hydrogen bonds into double chains along the b-axis. The crystal is further stabilized by weak C-H···O, C-Cl···π and π···π interactions.

Synthesis and characterization of tunable coumarin- linked glasses as new class of organic/inorganic phosphors

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

Luridiana, Alberto; Pretta, Gianluca; Secci, Francesco

2014-10-21

It is well known that stilbene with a trans conformation is highly fluorescent. From the viewpoint of molecular structure, coumarins bear a carbon-carbon double bond which is fixed as trans conformation as in trans-stilbene through a lactone structure. This can help to avoid the trans-cis transformation of the double bond under ultraviolet (UV) irradiation as observed in stilbene compounds and results in strong fluorescence and high fluorescence quantum yield and photostability in most of coumarin derivatives. Herein we report some preliminary results about the synthesis and spectroscopic characterization of tunable coumarins and the development of a new linkage protocol formore » the obtainment of monolayer coumarin-covalently linked glasses. The resulting organic/inorganic coumarin/silica based Self-Assembled Monolayer (SMA) film is proposed as new phosphors for the substituting of critical raw materials, like rare earths, in photonics applications.« less

Correlation of Local Effects of DNA Sequence and Position of Beta-Alanine Inserts with Polyamide-DNA Complex Binding Affinities and Kinetics

PubMed Central

Wang, Shuo; Nanjunda, Rupesh; Aston, Karl; Bashkin, James K.; Wilson, W. David

2012-01-01

In order to better understand the effects of β-alanine (β) substitution and the number of heterocycles on DNA binding affinity and selectivity, the interactions of an eight-ring hairpin polyamide (PA) and two β derivatives as well as a six-heterocycle analog have been investigated with their cognate DNA sequence, 5′-TGGCTT-3′. Binding selectivity and the effects of β have been investigated with the cognate and five mutant DNAs. A set of powerful and complementary methods have been employed for both energetic and structural evaluations: UV-melting, biosensor-surface plasmon resonance, isothermal titration calorimetry, circular dichroism and a DNA ligation ladder global structure assay. The reduced number of heterocycles in the six-ring PA weakens the binding affinity; however, the smaller PA aggregates significantly less than the larger PAs, and allows us to obtain the binding thermodynamics. The PA-DNA binding enthalpy is large and negative with a large negative ΔCp, and is the primary driving component of the Gibbs free energy. The complete SPR binding results clearly show that β substitutions can substantially weaken the binding affinity of hairpin PAs in a position-dependent manner. More importantly, the changes in PA binding to the mutant DNAs further confirm the position-dependent effects on PA-DNA interaction affinity. Comparison of mutant DNA sequences also shows a different effect in recognition of T•A versus A•T base pairs. The effects of DNA mutations on binding of a single PA as well as the effects of the position of β substitution on binding tell a clear and very important story about sequence dependent binding of PAs to DNA. PMID:23167504

Thermoelectric power factor of La0.9M0.1FeO3 (M = Ca and Ba) system: Structural, band gap and electrical transport evaluations

NASA Astrophysics Data System (ADS)

Karthikeyan, N.; Kumar, R. Ramesh; Jaiganesh, G.; Sivakumar, K.

2018-01-01

The search for thermoelectric materials has been incredibly increased due to the increase in global energy demand. Hence the present work focus on preparation and characterization of thermal transport phenomena of pure and Ba/Ca substituted perovskite LaFeO3 orthoferrite system. The conventional solid state reaction technique is utilized for the preparation of LaFeO3 and La0.9M0.1FeO3 (M = Ca and Ba) compounds. Crystal structure analyses of the prepared samples are analyses using Rietveld refinement process which confirms the orthoferrite crystal structure of all the prepared compounds with induced distortion in position of atoms by the incorporation of substituent atoms. The electronic structure calculations are performed by VASP. As the LaFeO3 compound is a strongly energy correlated system, the Density Functional Theory (DFT) calculations are performed by DFT + U (Hubbard function) method. The computed band gap values are compared with the energy gap values calculated from UV-Vis spectral analysis. Electrical conductivity measurement and Arrhenius behavior for the temperature range of room temperature to 650 K are analyzed and the drift increase in conductivity with respect to temperature is due to the thermally activated mobility of charge carriers. Temperature dependent thermopower analysis is also examined using homemade seebeck coefficient measurement system. The calculation of thermoelectric power factor reveals that the Ba substituted LaFeO3 compound show highest power factor value of 3.73 μW/K2 cm at higher temperature and the superior power factor values observed in the Ba substituted compound determine the material's capability in power generating devices based on thermoelectric effect.

Coordinated aqua vs methanol substitution kinetics in fac-Re(I) tricarbonyl tropolonato complexes.

PubMed

Schutte, Marietjie; Roodt, Andreas; Visser, Hendrik G

2012-11-05

Water-soluble fac-[Re(CO)(3)(L,L'-Bid)(X)] (L,L'-Bid = tropolonato, X = H(2)O, methanol) complexes have been synthesized, and the aqua and methanol substitution reactions were investigated in water (pH range 6.3-10.0) and methanol, respectively, and compared. Thiocyanate ions were used as monodentate entering ligand. The complexes were characterized by UV-vis, IR, and NMR spectroscopy. The crystal structures of the complexes [NEt(4)] fac-[Re(Trop)(CO)(3)(H(2)O)].NO(3).H(2)O (reactant) and fac-[Re(CO)(3)(Trop)(Py)], a substitution product, are reported. Overall it was found that the aqua substitution of fac-[Re(CO)(3)(Trop)(H(2)O)] is about 10 times faster than the methanol substitution reaction for fac-[Re(CO)(3)(Trop)(MeOH)], with forward and reverse rate and stability constants [k(1) (M(-1) s(-1)), k(-1) (s(-1)), K(1), (M(-1))] for thiocyanate as monodentate entering ligand as follows: fac-[Re(CO)(3)(Trop)(H(2)O)] = 2.54 ± 0.03, 0.0077 ± 0.0005, 330 ± 22/207 ± 14 and fac-[Re(CO)(3)(Trop)(MeOH)] = 0.268 ± 0.002, 0.0044 ± 0.0002, (61 ± 3)/(52 ± 4). The activation parameters [ΔH(‡)(k1) (kJ mol(-1)), ΔS(‡)(k1) (J K(-1) mol(-1))] for the aqua and methanol complex respectively are 56.1 ± 0.7, -49 ± 2 and 64 ± 1, -43 ± 5.

Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

PubMed

Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N

2016-11-16

Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH - or • OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

Are ecologically important tree species the most useful? A case study from indigenous people in the Bolivian Amazon.

PubMed

Guèze, Maximilien; Luz, Ana Catarina; Paneque-Gálvez, Jaime; Macía, Manuel J; Orta-Martínez, Martí; Pino, Joan; Reyes-García, Victoria

2014-03-01

Researchers have argued that indigenous peoples preferably use the most apparent plant species, particularly for medicinal uses. However, the association between the ecological importance of a species and its usefulness remains unclear. In this paper we quantify such association for six use categories (firewood, construction, materials, food, medicines and other uses). We collected data on the uses of 58 tree species, as reported by 93 informants in 22 villages in the Tsimane' territory (Bolivian Amazon). We calculated the ecological importance of the same species by deriving their importance value index (IVI) in 48 0.1-ha old-growth forest plots. Matching both data sets, we found a positive relation between the IVI of a species and its overall use value (UV) as well as with its UV for construction and materials. We found a negative relation between IVI and UV for species that were reportedly used for medicine and food uses, and no clear pattern for the other categories. We hypothesize that species used for construction or crafting purposes because of their physical properties are more easily substitutable than species used for medicinal or edible purposes because of their chemical properties.

Are ecologically important tree species the most useful? A case study from indigenous people in the Bolivian Amazon

PubMed Central

Guèze, Maximilien; Luz, Ana Catarina; Paneque-Gálvez, Jaime; Macía, Manuel J.; Orta-Martínez, Martí; Pino, Joan; Reyes-García, Victoria

2015-01-01

Researchers have argued that indigenous peoples preferably use the most apparent plant species, particularly for medicinal uses. However, the association between the ecological importance of a species and its usefulness remains unclear. In this paper we quantify such association for six use categories (firewood, construction, materials, food, medicines and other uses). We collected data on the uses of 58 tree species, as reported by 93 informants in 22 villages in the Tsimane’ territory (Bolivian Amazon). We calculated the ecological importance of the same species by deriving their importance value index (IVI) in 48 0.1-ha old-growth forest plots. Matching both data sets, we found a positive relation between the IVI of a species and its overall use value (UV) as well as with its UV for construction and materials. We found a negative relation between IVI and UV for species that were reportedly used for medicine and food uses, and no clear pattern for the other categories. We hypothesize that species used for construction or crafting purposes because of their physical properties are more easily substitutable than species used for medicinal or edible purposes because of their chemical properties. PMID:26097243

The structural and optical properties of type III human collagen biosynthetic corneal substitutes

PubMed Central

Hayes, Sally; Lewis, Phillip; Islam, M. Mirazul; Doutch, James; Sorensen, Thomas; White, Tomas; Griffith, May; Meek, Keith M.

2015-01-01

The structural and optical properties of clinically biocompatible, cell-free hydrogels comprised of synthetically cross-linked and moulded recombinant human collagen type III (RHCIII) with and without the incorporation of 2-methacryloyloxyethyl phosphorylcholine (MPC) were assessed using transmission electron microscopy (TEM), X-ray scattering, spectroscopy and refractometry. These findings were examined alongside similarly obtained data from 21 human donor corneas. TEM demonstrated the presence of loosely bundled aggregates of fine collagen filaments within both RHCIII and RHCIII-MPC implants, which X-ray scattering showed to lack D-banding and be preferentially aligned in a uniaxial orientation throughout. This arrangement differs from the predominantly biaxial alignment of collagen fibrils that exists in the human cornea. By virtue of their high water content (90%), very fine collagen filaments (2–9 nm) and lack of cells, the collagen hydrogels were found to transmit almost all incident light in the visible spectrum. They also transmitted a large proportion of UV light compared to the cornea which acts as an effective UV filter. Patients implanted with these hydrogels should be cautious about UV exposure prior to regrowth of the epithelium and in-growth of corneal cells into the implants. PMID:26159106

UV-Vis spectroscopy and density functional study of solvent effect on the charge transfer band of the n → σ* complexes of 2-Methylpyridine and 2-Chloropyridine with molecular iodine

NASA Astrophysics Data System (ADS)

Gogoi, Pallavi; Mohan, Uttam; Borpuzari, Manash Protim; Boruah, Abhijit; Baruah, Surjya Kumar

2017-03-01

UV-Vis spectroscopy has established that Pyridine substitutes form n→σ* charge transfer (CT) complexes with molecular Iodine. This study is a combined approach of purely experimental UV-Vis spectroscopy, Multiple linear regression theory and Computational chemistry to analyze the effect of solvent upon the charge transfer band of 2-Methylpyridine-I2 and 2-Chloropyridine-I2 complexes. Regression analysis verifies the dependence of the CT band upon different solvent parameters. Dielectric constant and refractive index are considered among the bulk solvent parameters and Hansen, Kamlet and Catalan parameters are taken into consideration at the molecular level. Density Functional Theory results explain well the blue shift of the CT bands in polar medium as an outcome of stronger donor acceptor interaction. A logarithmic relation between the bond length of the bridging atoms of the donor and the acceptor with the dielectric constant of the medium is established. Tauc plot and TDDFT study indicates a non-vertical electronic transition in the complexes. Buckingham and Lippert Mataga equations are applied to check the Polarizability effect on the CT band.

Photocatalytic Activity of Vanadium-Substituted ETS-10

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

Nash,M.; Rykov, S.; Lobo, R.

2007-01-01

Various amounts of vanadium have been isomorphously substituted for titanium in ETS-10, creating samples with V/(V+Ti) ratios of 0.13, 0.33, 0.43, and 1.00 and characterized experimentally using Raman, near-edge X-ray absorption fine structure (NEXAFS), X-ray powder diffraction, N{sub 2} adsorption, scanning electron microscopy (SEM), UV/vis spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Raman spectra reveal a disordered chain structure that contains different V-O bonds along with the presence of a V-O-Ti peak. The UV/vis spectra of the vanadium samples have three new absorption features in the visible region at 450, 594, and 850 nm, suggesting both V{sup 4+}more » and V{sup 5+} are present in the samples. NEXAFS results confirm the presence of both V{sup 5+} and V{sup 4+} in the vanadium samples, with a fraction of V{sup 4+} within the range of 0.2-0.4. The addition of vanadium lowers the band gap energy of ETS-10 from 4.32 eV to a minimum of 3.58 eV for the 0.43ETVS-10 sample. Studies of the photocatalytic polymerization of ethylene show that the 594 nm transition has no photocatalytic activity. The visible transition around 450 nm in the vanadium-incorporated samples is photocatalytically active, and the lower-concentration vanadium samples have higher photocatalytic activity than that of ETS-10 and AM-6, the all-vanadium analogue of ETS-10.« less

Assessment of benzophenone-4 reactivity with free chlorine by liquid chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Negreira, N; Rodríguez, I; Rodil, R; Cela, R

2012-09-19

The stability of the UV filter benzophenone-4 (BP-4) in free chlorine-containing water was investigated, for the first time, by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS). High mass accuracy and resolution capabilities of this hybrid mass spectrometer were used for the reliable assignation of empirical formulae and chemical structures of BP-4 derivatives. Time-course profiles of the parent compound and its by-products were simultaneously recorded by direct injection of sample aliquots, after quenching the excess of chlorine, in the LC-QqTOF-MS system. At neutral pHs, in excess of chlorine, BP-4 showed a limited stability fitting a pseudo-first-order degradation kinetics. A noticeable reduction in the half-lives of BP-4 was observed when increasing the sample pH between 6 and 8 units and also in presence of bromide traces. The reaction pathway of this UV filter involved a first electrophilic substitution of hydrogen per chlorine (or bromide) in the phenolic ring, followed by oxidation of the carbonyl moiety to an ester group, which induced a further electrophilic substitution in the same aromatic ring. Above reactions were also noticed when mixing a BP-4 containing personal care product with chlorinated tap water and in chlorinated swimming pool and sewage water, previously spiked with a BP-4 standard. Copyright © 2012 Elsevier B.V. All rights reserved.

Luminescence and thermal stability tuning in (Ba,Mn)3(Gd,Y)Na(PO4)5F:Eu2+ phosphors via cation-substitution

NASA Astrophysics Data System (ADS)

Mei, Juan; Lv, Lemin; Gao, Junsong; Wei, Yi; Feng, Yuxin; Yan, Chunjie; Li, Guogang

2018-04-01

In this work, [Y3+-Gd3+] and [Mn2+-Ba2+] substitutions were designed in Ba3GdNa(PO4)5F:Eu2+ system, which were marked as BG1-xYxNPF:Eu2+ and B1-yMyGNPF:Eu2+, respectively. It is found that their luminescence properties and thermal stability could be obviously tuned. For BG1-xYxNPF:Eu2+ series, under 365 nm UV light, the emission spectra exhibited a continuous red-shift from 458 nm (x = 0) to 485 nm (x = 1) with the corresponding luminescence varying from blue light to cyan light. For B1-yMyGNPF:Eu2+ series, it was observed the coexistence of blue-green and enhanced red emission of Eu2+ and the appearance of Eu3+ emission when Mn2+ partly substituted Ba2+, resulting in a final white emission. In addition, the thermal stabilities of B1-yMyGNPF:Eu2+ were obviously improved with Mn2+ doping. The corresponding luminescence and thermal stability tuning mechanisms were investigated.

Lifetimes and reactivities of some 1,2-didehydroazepines commonly used in photoaffinity labeling experiments in aqueous solutions.

PubMed

Rizk, Mary S; Shi, Xiaofeng; Platz, Matthew S

2006-01-17

The reactive 1,2-didehydroazepine (cyclic ketenimine) intermediates produced upon photolysis of phenyl azide, 3-hydroxyphenyl azide, 3-methoxyphenyl azide, and 3-nitrophenyl azide in water and in HEPES buffer were studied by laser flash photolysis techniques with UV-vis detection of the transient intermediates. The lifetimes of the 1,2-didehydroazepines were obtained along with the absolute rate constants of their reactions with typical amino acids, nucleosides, and other simple reagents present in a biochemical milieu. The nitro substituent greatly accelerates the bimolecular reactions of the cyclic ketenimines, and the 3-methoxy group greatly decelerates the absolute reactivity of 1,2-didehydroazepines. The intermediate produced by photolysis of 3-hydroxyphenyl azide is much more reactive than the intermediate produced by photolysis of 3-methoxyphenyl azide. We propose that the hydroxyl-substituted 1,2-didehydoazepines rapidly (<10 micros) tautomerize in water to form azepinones and much more rapidly than the corresponding 3-methoxy-substituted cyclic ketenimines undergo hydrolysis. Azepinones react more rapidly with nucleophiles than do methoxy-substituted 1,2-didehydroazepines and are the active species present upon the photolysis of 3-hydroxyphenyl azide in aqueous solution.

UV irradiation improves the bond strength of resin cement to fiber posts.

PubMed

Zhong, Bo; Zhang, Yong; Zhou, Jianfeng; Chen, Li; Li, Deli; Tan, Jianguo

2011-01-01

The purpose is to evaluate the effect of UV irradiation on the bond strength between epoxy-based glass fiber posts and resin cement. Twelve epoxy-based glass fiber posts were randomly divided into three groups. Group 1 (Cont.): No surface treatment. Group 2 (Low-UV): UV irradiation was conducted from a distance of 10 cm for 10 min. Group 3 (High-UV): UV irradiation was conducted from a distance of 1 cm for 3 min. A resin cement (CLEARFIL SA LUTING) was used for the post cementation to form resin slabs which contained fiber posts in the center. Microtensile bond strengths were tested and the mean bond strengths (MPa) were 18.81 for Cont. group, 23.65 for Low-UV group, 34.75 for High-UV group. UV irradiation had a significant effect on the bond strength (p<0.05). UV irradiation demonstrates its capability to improve the bond strength between epoxy-based glass fiber posts and resin cement.

Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations.

PubMed

Karthikeyan, N; Prince, J Joseph; Ramalingam, S; Periandy, S

2015-03-15

In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The (13)C and (1)H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Level of UV-B radiation influences the effects of glyphosate-based herbicide on the spotted salamander.

PubMed

Levis, Nicholas A; Johnson, Jarrett R

2015-07-01

Glyphosate-based herbicides are the number one pesticide in the United States and are used commonly around the world. Understanding the affects of glyphosate-based herbicides on non-target wildlife, for example amphibians, is critical for evaluation of regulations pertaining to the use of such herbicides. Additionally, it is important to understand how variation in biotic and abiotic environmental conditions, such as UV-B light regime, could potentially affect how glyphosate-based herbicides interact with non-target species. This study used artificial pond mesocosms to identify the effects of generic glyphosate-based herbicide (GLY-4 Plus) on mortality, cellular immune response, body size, and morphological plasticity of larvae of the spotted salamander (Ambystoma maculatum) under conditions that reflect moderate (UV(M)) and low (UV(L)) UV-B light regimes. Survival within a given UV-B level was unaffected by herbicide presence or absence. However, when herbicide was present, survival varied between UV-B levels with higher survival in UV(M) conditions. Herbicide presence in the UV(M) treatments also decreased body size and reduced cellular immune response. In the UV(L) treatments, the presence of herbicide increased body size and affected tail morphology. Finally, in the absence of herbicide, body size and cellular immune response were higher in UV(M) treatments compared to UV(L) treatments. Thus, the effects of herbicide on salamander fitness were dependent on UV-B level. As anthropogenic habitat modifications continue to alter landscapes that contain amphibian breeding ponds, salamanders may increasingly find themselves in locations with reduced canopy cover and increased levels of UV light. Our findings suggest that the probability of surviving exposure to the glyphosate-based herbicide used in this study may be elevated in more open canopy ponds, but the effects on other components of fitness may be varied and unexpected.

Mechanical properties and cytotoxicity of experimental soft lining materials based on urethane acrylate oligomers.

PubMed

Kanie, Takahito; Tomita, Koichi; Tokuda, Masayuki; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

2009-07-01

The purpose of this investigation was to determine whether experimental light-curing soft lining materials (ESLMs) based on commercially available urethane acrylate oligomers (UA-160TM, UV-3200B, UV-3500BA, and UV-3700B) are suitable for clinical use by measuring their viscosity, compressive modulus, Shore A hardness, tensile strength, adhesive strength, and cytotoxicity. The viscosities of the four ESLMs at 25 degrees C were 10.5 Pa.s, UV-3500BA; 144.0 Pa.s, UA-160TM; 328.8 Pa.s, UV-3700B; and 1079.7 Pa.s, UV-3200B. Polymerized UV-3700B was very soft, whereas the softness of the other ESLMs was similar to that of conventional soft lining materials. No significant difference in adhesive strength was observed between UV-3500BA and UV-3700B at 1 day and those at 12 months. Cytotoxicity was measured by a MTT-based assay using HeLa S3 and Ca9-22 cells. UV-3200B and UV-3700B oligomers and all four polymerized ESLMs showed cell viability over 95.2% (p < 0.05).

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics, transformation products, and toxicity evolvement.

PubMed

Dong, Bizhang; Hu, Jiye

2016-10-01

The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 (-)), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 (-), Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L(-1) Fe (III) and 500 mg L(-1) TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.

Pathogen reduction by ultraviolet C light effectively inactivates human white blood cells in platelet products.

PubMed

Pohler, Petra; Müller, Meike; Winkler, Carla; Schaudien, Dirk; Sewald, Katherina; Müller, Thomas H; Seltsam, Axel

2015-02-01

Residual white blood cells (WBCs) in cellular blood components induce a variety of adverse immune events, including nonhemolytic febrile transfusion reactions, alloimmunization to HLA antigens, and transfusion-associated graft-versus-host disease (TA-GVHD). Pathogen reduction (PR) methods such as the ultraviolet C (UVC) light-based THERAFLEX UV-Platelets system were developed to reduce the risk of transfusion-transmitted infection. As UVC light targets nucleic acids, it interferes with the replication of both pathogens and WBCs. This preclinical study aimed to evaluate the ability of UVC light to inactivate contaminating WBCs in platelet concentrates (PCs). The in vitro and in vivo function of WBCs from UVC-treated PCs was compared to that of WBCs from gamma-irradiated and untreated PCs by measuring cell viability, proliferation, cytokine secretion, antigen presentation in vitro, and xenogeneic GVHD responses in a humanized mouse model. UVC light was at least as effective as gamma irradiation in preventing GVHD in the mouse model. It was more effective in suppressing T-cell proliferation (>5-log reduction in the limiting dilution assay), cytokine secretion, and antigen presentation than gamma irradiation. The THERAFLEX UV-Platelets (MacoPharma) PR system can substitute gamma irradiation for TA-GVHD prophylaxis in platelet (PLT) transfusion. Moreover, UVC treatment achieves suppression of antigen presentation and inhibition of cytokine accumulation during storage of PCs, which has potential benefits for transfusion recipients. © 2014 AABB.

A molecular mechanism of azoxystrobin resistance in Penicillium digitatum UV mutants and a PCR-based assay for detection of azoxystrobin-resistant strains in packing- or store-house isolates.

PubMed

Zhang, Zhifang; Zhu, Zengrong; Ma, Zhonghua; Li, Hongye

2009-05-31

Sixty-five isolates of Pencillium digitatum (Pers.:Fr) Sacc., a causative agent of green mold of postharvest citrus, were collected from various locations in Zhejiang province in 2000, 2005 and 2006, and assayed for their sensitivity to the quinone outside inhibitor (QoI) fungicide azoxystrobin. The results showed that azoxystrobin is highly effective against P. digitatum, in vitro, and that the effective concentrations resulting in reduction of conidial germination and mycelial growth by 50% (EC(50)) averaged 0.0426 microg/ml and 0.0250 microg/ml, respectively. Twenty-eight azoxystrobin-resistant mutants were obtained by UV mutagenesis and subsequent selection on medium amended with azoxystrobin (12 microg/ml) and salicylhydroxamic acid. All obtained mutants were highly resistant to azoxystrobin and their resistance was genetically stable. Analysis of the cytochrome b gene structure of P. digitatum (Pdcyt b) showed the absence of type I intron in the first hot spot region of mutation. These results indicate that P. digitatum is likely to evolve high levels of resistance to azoxystrobin after its application. Analysis of partial sequences of Pdcyt b from both the azoxystrobin-sensitive parental isolate and the 28 azoxystrobin-resistant mutants revealed that a point mutation, which leads to the substitution at code 143 of alanine for glycine (G143A), is responsible for the observed azoxystrobin resistance in the laboratory mutants. Based on this point mutation, two allele-specific PCR primers were designed and optimized for allele-specific PCR detection of azoxystrobin-resistant isolates of P. digitatum.

Pathogen reduction through additive-free short-wave UV light irradiation retains the optimal efficacy of human platelet lysate for the expansion of human bone marrow mesenchymal stem cells.

PubMed

Viau, Sabrina; Chabrand, Lucie; Eap, Sandy; Lorant, Judith; Rouger, Karl; Goudaliez, Francis; Sumian, Chryslain; Delorme, Bruno

2017-01-01

We recently developed and characterized a standardized and clinical grade human Platelet Lysate (hPL) that constitutes an advantageous substitute for fetal bovine serum (FBS) for human mesenchymal stem cell (hMSC) expansion required in cell therapy procedures, avoiding xenogenic risks (virological and immunological) and ethical issues. Because of the progressive use of pathogen-reduced (PR) labile blood components, and the requirement of ensuring the viral safety of raw materials for cell therapy products, we evaluated the impact of the novel procedure known as THERAFLEX UV-Platelets for pathogen reduction on hPL quality (growth factors content) and efficacy (as a medium supplement for hMSC expansion). This technology is based on short-wave ultraviolet light (UV-C) that induces non-reversible damages in DNA and RNA of pathogens while preserving protein structures and functions, and has the main advantage of not needing the addition of any photosensitizing additives (that might secondarily interfere with hMSCs). We applied the THERAFLEX UV-Platelets procedure on fresh platelet concentrates (PCs) suspended in platelet additive solution and prepared hPL from these treated PCs. We compared the quality and efficacy of PR-hPL with the corresponding non-PR ones. We found no impact on the content of five cytokines tested (EGF, bFGF, PDGF-AB, VEGF and IGF-1) but a significant decrease in TGF-ß1 (-21%, n = 11, p<0.01). We performed large-scale culture of hMSCs from bone marrow (BM) during three passages and showed that hPL or PR-hPL at 8% triggered comparable BM-hMSC proliferation as FBS at 10% plus bFGF. Moreover, after proliferation of hMSCs in an hPL- or PR-hPL-containing medium, their profile of membrane marker expression, their clonogenic potential and immunosuppressive properties were maintained, in comparison with BM-hMSCs cultured under FBS conditions. The potential to differentiate towards the adipogenic and osteogenic lineages of hMSCs cultured in parallel in the three conditions also remained identical. We demonstrated the feasibility of using UV-C-treated platelets to subsequently obtain pathogen-reduced hPL, while preserving its optimal quality and efficacy for hMSC expansion in cell therapy applications.

Pathogen reduction through additive-free short-wave UV light irradiation retains the optimal efficacy of human platelet lysate for the expansion of human bone marrow mesenchymal stem cells

PubMed Central

Viau, Sabrina; Chabrand, Lucie; Eap, Sandy; Lorant, Judith; Rouger, Karl; Goudaliez, Francis; Sumian, Chryslain; Delorme, Bruno

2017-01-01

Background We recently developed and characterized a standardized and clinical grade human Platelet Lysate (hPL) that constitutes an advantageous substitute for fetal bovine serum (FBS) for human mesenchymal stem cell (hMSC) expansion required in cell therapy procedures, avoiding xenogenic risks (virological and immunological) and ethical issues. Because of the progressive use of pathogen-reduced (PR) labile blood components, and the requirement of ensuring the viral safety of raw materials for cell therapy products, we evaluated the impact of the novel procedure known as THERAFLEX UV-Platelets for pathogen reduction on hPL quality (growth factors content) and efficacy (as a medium supplement for hMSC expansion). This technology is based on short-wave ultraviolet light (UV-C) that induces non-reversible damages in DNA and RNA of pathogens while preserving protein structures and functions, and has the main advantage of not needing the addition of any photosensitizing additives (that might secondarily interfere with hMSCs). Methodology / Principal findings We applied the THERAFLEX UV-Platelets procedure on fresh platelet concentrates (PCs) suspended in platelet additive solution and prepared hPL from these treated PCs. We compared the quality and efficacy of PR-hPL with the corresponding non-PR ones. We found no impact on the content of five cytokines tested (EGF, bFGF, PDGF-AB, VEGF and IGF-1) but a significant decrease in TGF-ß1 (-21%, n = 11, p<0.01). We performed large-scale culture of hMSCs from bone marrow (BM) during three passages and showed that hPL or PR-hPL at 8% triggered comparable BM-hMSC proliferation as FBS at 10% plus bFGF. Moreover, after proliferation of hMSCs in an hPL- or PR-hPL-containing medium, their profile of membrane marker expression, their clonogenic potential and immunosuppressive properties were maintained, in comparison with BM-hMSCs cultured under FBS conditions. The potential to differentiate towards the adipogenic and osteogenic lineages of hMSCs cultured in parallel in the three conditions also remained identical. Conclusion / Significance We demonstrated the feasibility of using UV-C-treated platelets to subsequently obtain pathogen-reduced hPL, while preserving its optimal quality and efficacy for hMSC expansion in cell therapy applications. PMID:28763452

Dihydronaphthalenone Carboxylates - Spectral Characteristics and Structure

NASA Astrophysics Data System (ADS)

Bakalova, Sn.; Georgieva, A.; Nikolov, P.; Stanoeva, E.

1997-05-01

The absorption and luminescence characteristics of a group of newly synthesized methyl esters of 2-alkyl (p-substituted-aryl) -aminomethylene-3,4-dihydro-1(2 H)-naphthalenone-4-carboxylic acids have been investigated. The studied compounds may exist in three tautomeric forms. On the basis of comparison of their electronic spectra to those of similar substances, the observed substituent effect on the position of the UV-VIS absorption bands, the IR spectra and the results of PPP-SCF-CI quantum-chemical calculations it is concluded that the keto tautomer predominates in solution.

Photophysical, electrochemical, thermal and aggregation properties of new metal phthalocyanines

NASA Astrophysics Data System (ADS)

Jeong, Jaemyeng; Kumar, Rangaraju Satish; Mergu, Naveen; Son, Young-A.

2017-11-01

In this study, the synthesis of di(ethylene glycol) naphthalene substituted metal-phthalocyanines was reported. These novel phthalocyanines were characterized by elemental and spectroscopic analysis, including 1H NMR, FT-IR, UV-Vis spectral and MALDI-TOF mass data. The aggregation behavior of these phthalocyanines was examined in chloroform at different concentrations, and we confirmed that the phthalocyanines were non-aggregated. Further thermal stability, electrochemical, theoretical studies and metal sensing properties also investigated. In addition, we successfully prepared phthalocyanine (6d) blended polyurethane electrospun (ES) nanofibers.

Surface studies of low molecular weight photolysis products from UV-ozone oxidised polystyrene

NASA Astrophysics Data System (ADS)

Davidson, M. R.; Mitchell, S. A.; Bradley, R. H.

2005-05-01

The production of low molecular weight oxidised material during UV-ozone treatment of polystyrene has been studied by XPS, GC-MS, FTIR and UV/visible spectroscopy. XPS analysis of the oxidised polystyrene surfaces before and after washing with water or methanol indicates that the removal of oxidation products and the surface that remains after washing is strongly dependent on the choice of solvent. Methanol washing removes a greater proportion of the more highly oxidised carbonyl and carboxyl groups resulting in a surface with a lower oxygen content than that remaining after water washing. Extended exposure to UV-ozone treatment reveals a two-stage oxidation process with mono-substituted benzene rings such as benzaldehyde, acetophenone and benzoic acid being produced at exposure times less than 15 min. Compounds, more typical of those formed via dehydration reactions of existing oxidised species, are produced at longer exposure times. UV-visible spectroscopy and Fourier transform infrared spectroscopy also confirm the presence of carboxylic acid, aromatic ketones and esters. Measurements of water contact angle on a 10 min treated surface reveals that methanol washing produces a more hydrophilic surface than water washing, the resulting water contact angles being 47° and 62° respectively. Ageing of methanol washed surfaces for 24 h leads to a recovery of the water contact angle back to 62° which suggests some form of post-washing surface relaxation process. Since XPS analyses show no increase in the oxygen concentration of the methanol washed surfaces after a 24 h ageing period, the increase in contact angle found with ageing is attributed to the reorientation of very near-surface functional groups i.e. within the XPS sampling depth.

Theoretical and Experimental Spectroscopic Analysis of Cyano-Substituted Styrylpyridine Compounds

PubMed Central

Castro, Maria Eugenia; Percino, Maria Judith; Chapela, Victor M.; Ceron, Margarita; Soriano-Moro, Guillermo; Lopez-Cruz, Jorge; Melendez, Francisco J.

2013-01-01

A combined theoretical and experimental study on the structure, infrared, UV-Vis and 1H NMR data of trans-2-(m-cyanostyryl)pyridine, trans-2-[3-methyl-(m-cyanostyryl)] pyridine and trans-4-(m-cyanostyryl)pyridine is presented. The synthesis was carried out with an efficient Knoevenagel condensation using green chemistry conditions. Theoretical geometry optimizations and their IR spectra were carried out using the Density Functional Theory (DFT) in both gas and solution phases. For theoretical UV-Vis and 1H NMR spectra, the Time-Dependent DFT (TD-DFT) and the Gauge-Including Atomic Orbital (GIAO) methods were used, respectively. The theoretical characterization matched the experimental measurements, showing a good correlation. The effect of cyano- and methyl-substituents, as well as of the N-atom position in the pyridine ring on the UV-Vis, IR and NMR spectra, was evaluated. The UV-Vis results showed no significant effect due to electron-withdrawing cyano- and electron-donating methyl-substituents. The N-atom position, however, caused a slight change in the maximum absorption wavelengths. The IR normal modes were assigned for the cyano- and methyl-groups. 1H NMR spectra showed the typical doublet signals due to protons in the trans position of a double bond. The theoretical characterization was visibly useful to assign accurately the signals in IR and 1H NMR spectra, as well as to identify the most probable conformation that could be present in the formation of the styrylpyridine-like compounds. PMID:23429190

The GP(Y/F) Domain of TF1 Integrase Multimerizes when Present in a Fragment, and Substitutions in This Domain Reduce Enzymatic Activity of the Full-length Protein*S⃞

PubMed Central

Ebina, Hirotaka; Chatterjee, Atreyi Ghatak; Judson, Robert L.; Levin, Henry L.

2008-01-01

Integrases (INs) of retroviruses and long terminal repeat retrotransposons possess a C-terminal domain with DNA binding activity. Other than this binding activity, little is known about how the C-terminal domain contributes to integration. A stretch of conserved amino acids called the GP(Y/F) domain has been identified within the C-terminal IN domains of two distantly related families, the γ-retroviruses and the metavirus retrotransposons. To enhance understanding of the C-terminal domain, we examined the function of the GP(Y/F) domain in the IN of Tf1, a long terminal repeat retrotransposon of Schizosaccharomyces pombe. The activities of recombinant IN were measured with an assay that modeled the reverse of integration called disintegration. Although deletion of the entire C-terminal domain disrupted disintegration activity, an alanine substitution (P365A) in a conserved amino acid of the GP(Y/F) domain did not significantly reduce disintegration. When assayed for the ability to join two molecules of DNA in a reaction that modeled forward integration, the P365A substitution disrupted activity. UV cross-linking experiments detected DNA binding activity in the C-terminal domain and found that this activity was not reduced by substitutions in two conserved amino acids of the GP(Y/F) domain, G364A and P365A. Gel filtration and cross-linking of a 71-amino acid fragment containing the GP(Y/F) domain revealed a surprising ability to form dimers, trimers, and tetramers that was disrupted by the G364A and P365A substitutions. These results suggest that the GP(Y/F) residues may play roles in promoting multimerization and intermolecular strand joining. PMID:18397885

The GP(Y/F) domain of TF1 integrase multimerizes when present in a fragment, and substitutions in this domain reduce enzymatic activity of the full-length protein.

PubMed

Ebina, Hirotaka; Chatterjee, Atreyi Ghatak; Judson, Robert L; Levin, Henry L

2008-06-06

Integrases (INs) of retroviruses and long terminal repeat retrotransposons possess a C-terminal domain with DNA binding activity. Other than this binding activity, little is known about how the C-terminal domain contributes to integration. A stretch of conserved amino acids called the GP(Y/F) domain has been identified within the C-terminal IN domains of two distantly related families, the gamma-retroviruses and the metavirus retrotransposons. To enhance understanding of the C-terminal domain, we examined the function of the GP(Y/F) domain in the IN of Tf1, a long terminal repeat retrotransposon of Schizosaccharomyces pombe. The activities of recombinant IN were measured with an assay that modeled the reverse of integration called disintegration. Although deletion of the entire C-terminal domain disrupted disintegration activity, an alanine substitution (P365A) in a conserved amino acid of the GP(Y/F) domain did not significantly reduce disintegration. When assayed for the ability to join two molecules of DNA in a reaction that modeled forward integration, the P365A substitution disrupted activity. UV cross-linking experiments detected DNA binding activity in the C-terminal domain and found that this activity was not reduced by substitutions in two conserved amino acids of the GP(Y/F) domain, G364A and P365A. Gel filtration and cross-linking of a 71-amino acid fragment containing the GP(Y/F) domain revealed a surprising ability to form dimers, trimers, and tetramers that was disrupted by the G364A and P365A substitutions. These results suggest that the GP(Y/F) residues may play roles in promoting multimerization and intermolecular strand joining.

Attomole-level protein fingerprinting based on intrinsic peptide fluorescence.

PubMed

Okerberg, E; Shear, J B

2001-04-01

Protein identification has relied heavily on proteolytic analysis, but current techniques are often slow and generally consume large quantities of valuable protein sample. We report the development of a rapid, ultralow volume protein analysis strategy based on tryptic digestion within the tip of a 1.5-microm capillary channel followed by separation of the proteolytic fragments using capillary electrophoresis (CE). Two-photon excitation is used to probe the intrinsic fluorescence of peptide fragments through "deep-UV" excitation of aromatic amino acid residues at the outlet of the CE channel. Detection limits using this technique are 0.7, 2.4, and 23 amol for the aromatic amino acids tryptophan, tyrosine, and phenylalanine, respectively. In these studies, we demonstrate the capacity to differentiate bovine and yeast cytochrome c variants using less than 15 amol of protein through tryptic fingerprinting. Moreover, the detection of a single amino acid substitution between bovine and canine cytochrome c illustrates the sensitivity of this approach to minor differences in protein sequence. The 2-pL sample volume required for this on-column tryptic digestion is, to our knowledge, the smallest yet reported for a proteolytic assay.

Spectrum of cisplatin-induced mutations in Escherichia coli

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

Burnouf, D.; Duane, M.; Fuchs, R.P.

1987-06-01

Using a forward-mutation assay based on the inactivation of the tetracycline-resistance gene located on plasmid pBR322, we have determined the mutation spectrum induced in Escherichia coli by cisplatin (cis-diamminedichloroplatinum(II)), a widely used antitumor drug. Cisplatin is known to form mainly intrastrand diadducts at ApG and GpG sites. We found that cisplatin efficiently induces mutations in an SOS-dependent way (i.e., dependent upon UV irradiation of the host bacteria). More than 90% of the mutations are single-base-pair substitutions occurring at the potential sites of cisplatin adducts (ApG and GpG). Taking into account the relative proportions of ApG and GpG adducts, we foundmore » that the ApG adducts are at least 5 times more mutagenic than the GpG adducts. Moreover, a strong mutation specificity was seen at the 5' side of the ApG adducts (A X T----T X A transversions). The observation that most mutations occur at the 5' end of the adduct at both ApG and GpG sites is discussed in relation to recent structural data.« less

Photovoltaic Devices Prepared through a Trihydroxy Substitution Strategy on an Unsymmetrical Squaraine Dye.

PubMed

Wu, Jianglin; Si, Changfeng; Chen, Yao; Yang, Lin; Hu, Bin; Chen, Guo; Lu, Zhiyun; Huang, Yan

2018-03-02

A series of unsymmetrical arene-1,3-squaraine (USQ) derivatives with two, three, or four hydroxy (-OH) substituents, namely, USQ-2-OH, USQ-3-OH, or USQ-4-OH, respectively, were designed and synthesized, and the effect of the number of hydroxy groups on the optoelectronic properties of USQs were investigated. Despite the three compounds having similar UV/Vis absorption and HOMO energy levels, solution-processed bulk-heterojunction (BHJ) small-molecule organic solar cells with USQ-3-OH as electron-donor materials exhibit the highest power conversion efficiency of 6.07 %, which could be mainly attributed to the higher hole mobility and smaller phase separation. It is also noteworthy that the short-circuit current (J sc ) of the USQ-3-OH-based device is as high as 14.95 mA cm -2 , which is the highest J sc values reported for squaraine-based BHJ solar cells to date. The results also indicate that more -OH substituents on squaraine dyes do not necessarily lead to better photovoltaic performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic, Electrochemical and DFT Studies of Phosphorescent Homoleptic Cyclometalated Iridium(III) Complexes Based on Substituted 4-Fluorophenylvinyl- and 4-Methoxyphenylvinylquinolines

PubMed Central

Adeloye, Adewale O.; Adekunle, Abolanle S.; Ramasami, Ponnadurai

2017-01-01

This study reports the synthesis and comparative investigation of the substituent effects of a new series of highly luminescent homoleptic tris-cyclometalated iridium(III) complexes of the type [Ir(N˄C)3]. These are based on two ligand type derivatives comprising of 4-fluorophenylvinylquinolines and 4-methoxyphenylvinylquinolines with electron-donating and/or electron-withdrawing groups as aryl substituents at 2-position. The structures of the ligands and their complexes were characterized by means of FT-IR, UV-Vis and NMR spectrometry complemented with photoluminescence and cyclic voltammetry. The photophysical properties of 2-aryl-4-(4-fluorophenylvinyl)quinoline and its corresponding complex were also studied using the density functional theory method. The photoluminescent properties of the ligands and the corresponding complexes showed high fluorescent intensities and quantum yields in solvents of different polarities. The photoluminescence spectra of the complexes in solid film, showed common transmission curves at longer wavelengths maximum (λem = 697 nm) possibly originating from the interference of scattered light of higher-order transmission of monochromators. PMID:28934145

Flocculation characteristics of polyacrylamide grafted cellulose from Phyllostachys heterocycla: An efficient and eco-friendly flocculant.

PubMed

Liu, Hongyi; Yang, Xiaogang; Zhang, Yong; Zhu, Hangcheng; Yao, Juming

2014-08-01

This work presents a synthesis process and flocculation characteristics of an eco-friendly flocculant based on bamboo pulp cellulose (BPC) from Phyllostachys heterocycla. Ployacrylamide (PAM) was grafted onto the BPC by free-radical graft copolymerization in homogeneous aqueous solution. The optimal synthesis conditions of the bamboo pulp cellulose-graft-ployacrylamide flocculant (BPC-g-PAM) and its performance on wastewater treatments were investigated. A UV-based method was used to rapidly determine the degree of substitution (DS) of BPC. The results showed that, under the optimal synthesis conditions, the obtained BPC-g-PAM held a grafting ratio of 43.8% and DS of 1.31. Turbidity removal of the product reached 98.0% accompanying with the significant flocculation and sedimentation in target suspensions. The flocculation mechanism was explored by means of zeta potential method. For negatively charged contaminants, like kaolin clay particles, the BPC-g-PAM could remove the contaminants efficiently via bridging and charge neutralization in acidic or neutral environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Spectroscopic, Electrochemical and DFT Studies of Phosphorescent Homoleptic Cyclometalated Iridium(III) Complexes Based on Substituted 4-Fluorophenylvinyl- and 4-Methoxyphenylvinylquinolines.

PubMed

Adeloye, Adewale O; Mphahlele, Malose J; Adekunle, Abolanle S; Rhyman, Lydia; Ramasami, Ponnadurai

2017-09-21

This study reports the synthesis and comparative investigation of the substituent effects of a new series of highly luminescent homoleptic tris-cyclometalated iridium(III) complexes of the type [Ir(N ˄ C)₃]. These are based on two ligand type derivatives comprising of 4-fluorophenylvinylquinolines and 4-methoxyphenylvinylquinolines with electron-donating and/or electron-withdrawing groups as aryl substituents at 2-position. The structures of the ligands and their complexes were characterized by means of FT-IR, UV-Vis and NMR spectrometry complemented with photoluminescence and cyclic voltammetry. The photophysical properties of 2-aryl-4-(4-fluorophenylvinyl)quinoline and its corresponding complex were also studied using the density functional theory method. The photoluminescent properties of the ligands and the corresponding complexes showed high fluorescent intensities and quantum yields in solvents of different polarities. The photoluminescence spectra of the complexes in solid film, showed common transmission curves at longer wavelengths maximum (λ em = 697 nm) possibly originating from the interference of scattered light of higher-order transmission of monochromators.

Sub-50 fs excited state dynamics of 6-chloroguanine upon deep ultraviolet excitation.

PubMed

Mondal, Sayan; Puranik, Mrinalini

2016-05-18

The photophysical properties of natural nucleobases and their respective nucleotides are ascribed to the sub-picosecond lifetime of their first singlet states in the UV-B region (260-350 nm). Electronic transitions of the ππ* type, which are stronger than those in the UV-B region, lie at the red edge of the UV-C range (100-260 nm) in all isolated nucleobases. The lowest energetic excited states in the UV-B region of nucleobases have been investigated using a plethora of experimental and theoretical methods in gas and solution phases. The sub-picosecond lifetime of these molecules is not a general attribute of all nucleobases but specific to the five primary nucleobases and a few xanthine and methylated derivatives. To determine the overall UV photostability, we aim to understand the effect of more energetic photons lying in the UV-C region on nucleobases. To determine the UV-C initiated photophysics of a nucleobase system, we chose a halogen substituted purine, 6-chloroguanine (6-ClG), that we had investigated previously using resonance Raman spectroscopy. We have performed quantitative measurements of the resonance Raman cross-section across the Bb absorption band (210-230 nm) and constructed the Raman excitation profiles. We modeled the excitation profiles using Lee and Heller's time-dependent theory of resonance Raman intensities to extract the initial excited state dynamics of 6-ClG within 30-50 fs after photoexcitation. We found that imidazole and pyrimidine rings of 6-ClG undergo expansion and contraction, respectively, following photoexcitation to the Bb state. The amount of distortions of the excited state structure from that of the ground state structure is reflected by the total internal reorganization energy that is determined at 112 cm(-1). The contribution of the inertial component of the solvent response towards the total reorganization energy was obtained at 1220 cm(-1). In addition, our simulation also yields an instantaneous response of the first solvation shell within an ultrafast timescale of less than 30 fs following photoexcitation.

Phototransformation of the insecticide fipronil: identification of novel photoproducts and evidence for an alternative pathway of photodegradation.

PubMed

Raveton, Muriel; Aajoud, Asmae; Willison, John C; Aouadi, Heddia; Tissut, Michel; Ravanel, Patrick

2006-07-01

Fipronil is a recently discovered insecticide of the phenylpyrazole series. It has a highly selective biochemical mode of action, which has led to its use in a large number of important agronomical, household, and veterinary applications. Previous studies have shown that, during exposure to light, fipronil is converted into a desulfurated derivative (desulfinyl-fipronil), which has slightly reduced insecticidal activity. In this study, the photodegradation of fipronil was studied in solution at low light intensities (sunlight or UV lamp). In addition to desulfinyl-fipronil, a large number of minor photoproducts were observed, including diversely substituted phenylpyrazole derivatives and aniline derivatives that had lost the pyrazole ring. Desulfinylfipronil itself was shown to be relatively stable under both UV light and sunlight, with only limited changes occurring in the substitution of the aromatic ring. Since this compound accumulated to levels corresponding to only 30-55% of the amount of fipronil degraded, it was concluded that one or more alternative pathways of photodegradation must be operating. On the basis of the structurally identified photoproducts, it is proposed that fipronil photodegradation occurs via at least two distinct pathways, one of which involves desulfuration at the 4-position of the pyrazole ring giving the desulfinyl derivative and the other of which involves a different modification of the 4-substituent, leading to cleavage of the pyrazole ring and the formation of aniline derivatives. The latter compounds do not accumulate to high levels and may, therefore, be degraded further. The ecological significance of these results is discussed, particularly with regard to the insecticidal activity of the photoproducts.

Light, Molecules, Action: Broadband UV-visible transient absorption studies of excited state dynamics in photoactive molecules

NASA Astrophysics Data System (ADS)

Sension, Roseanne

2015-03-01

Broadband UV-visible transient absorption spectroscopy provides a powerful tool for the investigation of the dynamics of electronically excited molecules in the condensed phase. It is now possible to obtain transient spectra on a routine basis spanning the range from <300 nm to >800 nm with femtosecond time resolution. We have used this method to study the excited state dynamics and internal conversion of a range of molecular systems with potential application as optically powered molecular devices. The cyclohexadiene ring-opening reaction is the basis of a class of important optical switches and of the biological synthesis of previtamin D3. The ring-opening reaction is ultrafast, occurring on a picosecond to subpicosecond times scale depending on the substituents around the ring. These have a significant influence on the dynamics and electronic structure of the electronically excited molecule. The results of a series of transient absorption studies as a function of chromophore substitution and environment will be presented. The cis-trans isomerization of polyene molecules, especially substituted stilbenes, provides another important class of functional molecular transformations. Again the excited state dynamics can be ultrafast with photochemistry controlled by details of the curve crossings and conical intersections. Finally the photochemistry of the even more complex set of cobalamin chromophores with a photoalabile C-Co bond has been proposed as a tool for spatio-temporal control of molecule delivery including drug delivery. Broadband transient absorption spectroscopy has been used to investigate the ultrafast electronic dynamics of a range of cobalamin compounds with comparison to detailed theoretical calculations. The results of these studies will be presented.

Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

NASA Astrophysics Data System (ADS)

Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

2014-01-01

Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

Spectroscopic Study of the Interaction between Horse Heart Myoglobin and Zirconium(IV)-Substituted Polyoxometalates as Artificial Proteases.

PubMed

Ly, Hong Giang T; Parac-Vogt, Tatjana N

2017-09-20

A recent study [Angew. Chem. Int. Ed. 2015, 54, 7391-7394] has shown that horse heart myoglobin (HHM) is selectively hydrolyzed by a range of zirconium(IV)-substituted polyoxometalates (POMs) under mild conditions. In this study, the molecular interactions between the Zr-POM catalysts and HHM are investigated by using a range of complementary techniques, including circular dichroism (CD), UV/Vis spectroscopy, tryptophan fluorescence spectroscopy, and 1 H and 31 P NMR spectroscopy. A tryptophan fluorescence quenching study reveals that, among all examined Zr-POMs, the most reactive POM, 2:2 Zr IV -Keggin, exhibits the strongest interaction with HHM. 31 P NMR spectroscopy studies show that this POM dissociates in solution, resulting in the formation of a monomeric 1:1 Zr IV -Keggin structure, which is likely to be a catalytically active species. In the presence of Zr IV -POMs, HHM does not undergo complete denaturation, as evidenced by CD, UV/Vis, tryptophan fluorescence, and 1 H NMR spectroscopy. CD spectroscopy shows a gradual decrease in the α-helical content of HHM upon addition of Zr IV -POMs. The largest effect is observed in the presence of a large Zr IV -Wells-Dawson structure, whereas small Zr IV -Lindqvist POM has the least influence on the decrease in the α-helical content of HHM. In all cases, the Soret band at λ=409 nm is maintained in the presence of all examined Zr-POMs, which indicates that no conformational changes in the protein occur near the heme group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative study of the flavonoids of some Verbena species cultivated in Egypt by using high-performance liquid chromatography coupled with ultraviolet spectroscopy and atmospheric pressure chemical ionization mass spectrometry.

PubMed

El-Hela, Atef A; Al-Amier, Hussein A; Ibrahim, Taghreed A

2010-10-08

Verbena rigida L., Verbena tenera Spreng. and Verbena venosa L. were investigated for their flavonoid content. Analysis was carried out by high-performance liquid chromatography coupled to diode array UV detection (LC-UV), using different techniques, also using post-column addition of shift reagents, afforded precise structural information about the position of the free hydroxyl groups in the flavonoid nucleus. LC-MS using atmospheric pressure chemical ionization (APCI) in the positive mode provided the molecular weight, the number of hydroxyl groups, the number of sugars and an idea about the substitution pattern of the flavonoid. On-line UV and MS data demonstrated the presence of orientin, vitexin, isovitexin, luteolin, luteolin 7-O-glucoside, apigenin 7-O-glucoside in addition to luteolin, chryseriol and apigenin aglycones in the three Verbena species with different concentrations. Quantitative determination of flavonoid content revealed the presence of 69.84 mg/g dry sample, 88.26 mg/g dry sample and 85.82 mg/g dry sample total flavonoid compounds in V. rigida L., V. tenera Spreng. and V. venosa L., respectively. The method developed for identification is useful for further chromatographic fingerprinting of plant flavonoids. Copyright © 2010 Elsevier B.V. All rights reserved.

The sunless study: a beach randomized trial of a skin cancer prevention intervention promoting sunless tanning.

PubMed

Pagoto, Sherry L; Schneider, Kristin L; Oleski, Jessica; Bodenlos, Jamie S; Ma, Yunsheng

2010-09-01

To examine the impact of a skin cancer prevention intervention that promoted sunless tanning as a substitute for sunbathing. Randomized controlled trial. Public beaches in Massachusetts. Women (N = 250) were recruited to participate in the study during their visit to a public beach. Intervention The intervention included motivational messages to use sunless tanning as an alternative to UV tanning, instructions for proper use of sunless tanning products, attractive images of women with sunless tans, a free trial of a sunless tanning product, skin cancer education, and UV imaging. The control participants completed surveys. The primary outcome was sunbathing 2 months and 1 year after the intervention. Secondary outcomes included sunburns, sun protection use, and sunless tanning. At 2 months, intervention participants reduced their sunbathing significantly more than did controls and reported significantly fewer sunburns and greater use of protective clothing. At 1 year, intervention participants reported significant decreases in sunbathing and increases in sunless tanning relative to control participants but no differences in the other outcomes. This intervention, which promoted sunless tanning as an alternative to UV tanning, had a short-term effect on sunbathing, sunburns, and use of protective clothing and a longer-term effect on sunbathing and sunless tanning. clinicaltrials.gov Identifier: NCT00403377.

Structural and photocatalytic studies of hydrothermally synthesized Mn2+-TiO2 nanoparticles under UV and visible light irradiation

NASA Astrophysics Data System (ADS)

Kamble, Ravi; Sabale, Sandip; Chikode, Prashant; Puri, Vijaya; Mahajan, Smita

2016-11-01

Pure TiO2 and Mn2+-TiO2 nanoparticles have been prepared by simple hydrothermal method with different Mn2+ concentrations. Obtained samples were analysed to determine it’s structural, optical, morphological and compositional properties using x-ray diffraction, UV-DRS, Raman, photoluminescence, XPS, TEM and EDS analysis. The EDS micrograph confirms the existence of Mn2+ atoms in TiO2 matrix with 0.86, 1.60 and 1.90 wt%. The crystallite size as well as band gap decreases with increase in Mn2+ concentration. The average particle size obtained from TEM was found 8-11 nm which is in good agreement with XRD results. Raman bands at 640, 518 and 398 cm-1 further confirmed pure phase anatase in all samples. XPS shows the proper substitutions of few sites of Ti4+ ions by Mn2+ ions in the TiO2 host lattice. The intensity of PL spectra for Mn2+-TiO2 shows a gradual decrease in the peak intensity with increasing Mn2+ concentration in TiO2, it implies lower electron-hole recombination rate as Mn2+ ions increases. The obtained samples were further studied for its photocatalytic activities using malachite green dye under UV light and visible light.

A sunblock based on bioadhesive nanoparticles

NASA Astrophysics Data System (ADS)

Deng, Yang; Ediriwickrema, Asiri; Yang, Fan; Lewis, Julia; Girardi, Michael; Saltzman, W. Mark

2015-12-01

The majority of commercial sunblock preparations use organic or inorganic ultraviolet (UV) filters. Despite protecting against cutaneous phototoxicity, direct cellular exposure to UV filters has raised a variety of health concerns. Here, we show that the encapsulation of padimate O (PO)--a model UV filter--in bioadhesive nanoparticles (BNPs) prevents epidermal cellular exposure to UV filters while enhancing UV protection. BNPs are readily suspended in water, facilitate adherence to the stratum corneum without subsequent intra-epidermal or follicular penetration, and their interaction with skin is water resistant yet the particles can be removed via active towel drying. Although the sunblock based on BNPs contained less than 5 wt% of the UV-filter concentration found in commercial standards, the anti-UV effect was comparable when tested in two murine models. Moreover, the BNP-based sunblock significantly reduced double-stranded DNA breaks when compared with a commercial sunscreen formulation.

TEMIS UV product validation using NILU-UV ground-based measurements in Thessaloniki, Greece

NASA Astrophysics Data System (ADS)

Zempila, Melina-Maria; van Geffen, Jos H. G. M.; Taylor, Michael; Fountoulakis, Ilias; Koukouli, Maria-Elissavet; van Weele, Michiel; van der A, Ronald J.; Bais, Alkiviadis; Meleti, Charikleia; Balis, Dimitrios

2017-06-01

This study aims to cross-validate ground-based and satellite-based models of three photobiological UV effective dose products: the Commission Internationale de l'Éclairage (CIE) erythemal UV, the production of vitamin D in the skin, and DNA damage, using high-temporal-resolution surface-based measurements of solar UV spectral irradiances from a synergy of instruments and models. The satellite-based Tropospheric Emission Monitoring Internet Service (TEMIS; version 1.4) UV daily dose data products were evaluated over the period 2009 to 2014 with ground-based data from a Norsk Institutt for Luftforskning (NILU)-UV multifilter radiometer located at the northern midlatitude super-site of the Laboratory of Atmospheric Physics, Aristotle University of Thessaloniki (LAP/AUTh), in Greece. For the NILU-UV effective dose rates retrieval algorithm, a neural network (NN) was trained to learn the nonlinear functional relation between NILU-UV irradiances and collocated Brewer-based photobiological effective dose products. Then the algorithm was subjected to sensitivity analysis and validation. The correlation of the NN estimates with target outputs was high (r = 0. 988 to 0.990) and with a very low bias (0.000 to 0.011 in absolute units) proving the robustness of the NN algorithm. For further evaluation of the NILU NN-derived products, retrievals of the vitamin D and DNA-damage effective doses from a collocated Yankee Environmental Systems (YES) UVB-1 pyranometer were used. For cloud-free days, differences in the derived UV doses are better than 2 % for all UV dose products, revealing the reference quality of the ground-based UV doses at Thessaloniki from the NILU-UV NN retrievals. The TEMIS UV doses used in this study are derived from ozone measurements by the SCIAMACHY/Envisat and GOME2/MetOp-A satellite instruments, over the European domain in combination with SEVIRI/Meteosat-based diurnal cycle of the cloud cover fraction per 0. 5° × 0. 5° (lat × long) grid cells. TEMIS UV doses were found to be ˜ 12.5 % higher than the NILU NN estimates but, despite the presence of a visually apparent seasonal pattern, the R2 values were found to be robustly high and equal to 0.92-0.93 for 1588 all-sky coincidences. These results significantly improve when limiting the dataset to cloud-free days with differences of 0.57 % for the erythemal doses, 1.22 % for the vitamin D doses, and 1.18 % for the DNA-damage doses, with standard deviations of the order of 11-13 %. The improvement of the comparative statistics under cloud-free cases further testifies to the importance of the appropriate consideration of the contribution of clouds in the UV radiation reaching the Earth's surface. For the urban area of Thessaloniki, with highly variable aerosol, the weakness of the implicit aerosol information introduced to the TEMIS UV dose algorithm was revealed by comparison of the datasets to aerosol optical depths at 340 nm as reported by a collocated CIMEL sun photometer, operating in Thessaloniki at LAP/AUTh as part of the NASA Aerosol Robotic Network.

Synthesis of p-type nickel oxide nanosheets on n-type titanium dioxide nanorod arrays for p-n heterojunction-based UV photosensor

NASA Astrophysics Data System (ADS)

Yusoff, M. M.; Mamat, M. H.; Malek, M. F.; Abdullah, M. A. R.; Ismail, A. S.; Saidi, S. A.; Mohamed, R.; Suriani, A. B.; Khusaimi, Z.; Rusop, M.

2018-05-01

Titanium dioxide (TiO2) nanorod arrays (TNAs) were synthesized and deposited on fluorine tin oxide (FTO)-coated glass substrate using a novel and facile immersion method in a glass container. The synthesis and deposition of p-type nickel oxide (NiO) nanosheets (NS) on the n-type TNAs was investigated in the p-n heterojunction photodiode (PD) for the application of ultraviolet (UV) photosensor. The fabricated TNAs/NiO NS based UV photosensor exhibited a highly increased photocurrent of 4.3 µA under UV radiation (365 nm, 750 µW/cm2) at 1.0 V reverse bias. In this study, the fabricated TNAs/NiO NS p-n heterojunction based photodiode showed potential applications for UV photosensor based on the stable photo-generated current attained under UV radiation.

Validation Thin Layer Chromatography for the Determination of Acetaminophen in Tablets and Comparison with a Pharmacopeial Method

PubMed Central

Pyka, Alina; Budzisz, Marika; Dołowy, Małgorzata

2013-01-01

Adsorption thin layer chromatography (NP-TLC) with densitometry has been established for the identification and the quantification of acetaminophen in three leading commercial products of pharmaceutical tablets coded as brand: P1 (Product no. 1), P2 (Product no. 2), and P3 (Product no. 3). Applied chromatographic conditions have separated acetaminophen from its related substances, namely, 4-aminophenol and and 4′-chloroacetanilide. UV densitometry was performed in absorbance mode at 248 nm. The presented method was validated by specificity, range, linearity, accuracy, precision, detection limit, quantitative limit, and robustness. The TLC-densitometric method was also compared with a pharmacopeial UV-spectrophotometric method for the assay of acetaminophen, and the results confirmed statistically that the NP-TLC-densitometric method can be used as a substitute method. It could be said that the validated NP-TLC-densitometric method is suitable for the routine analysis of acetaminophen in quantity control laboratories. PMID:24063006

Spectral-Polarization Properties and Light Resistance of Polyvinyl-Alcohol Films Colored With Disazo Dyes

NASA Astrophysics Data System (ADS)

Fillipovich, L. N.; Ariko, N. G.; Agabekov, V. E.; Malashko, P. M.

2005-09-01

Polarizers containing disazo dyes from the group of azobenzene-azonaphthalene have been developed. It has been established that their polarizing ability is determined by the mutual disposition of the azo group and electron-donor substituents in the naphthalene ring. On diazo coupling of γ acid into the α position relative to the oxy group, the M1 and M3 dyes are formed, the polarizing ability of which in uniaxially oriented polyvinyl-alcohol films is higher than in the M2 dye produced as a result of diazo coupling into the α position relative to the amino group. On irradiation by UV light, the dyes are subjected to photodestruction, which, in the case of M2, proceeds through trans-cis-isomerization. The rate of photodestruction depends on the aggregation of the dye molecules, and it increases in the presence of a free-radical initiator. The UV absorber (substituted benzotriazole) and the uniaxial orientation of the film retard this process.

GENETICS OF HUMAN CELL LINES

PubMed Central

Djordjevic, B.; Szybalski, Waclaw

1960-01-01

The human cell line D98S can be cultivated indefinitely in the presence of up to 3 x 10–5 M 5-bromodeoxyuridine (BUDR), without loss of cell viability. During this time, BUDR is incorporated into both strands of the DNA molecules, replacing up to 45 per cent of the thymidine and thereby rendering the cells highly sensitive to UV light and to x-rays. Cells grown for a limited period of time in the presence of 5-iododeoxyuridine (IUDR) become UV-sensitized, while prolonged cultivation with IUDR results in the loss of cell viability. The properties of the BUDR label permitted the demonstration that: (a) human DNA replicates in a "semiconservative" manner; (b) the degree of radiosensitization of BUDR-treated cells depends on whether the DNA has been substituted in one strand only ("unifilarly") or in both strands ("bifilarly"); (c) functional human DNA is produced during partial inhibition of protein synthesis. The potential applicability of this new rational principle of radiosensitization to the radiotherapy of neoplastic diseases is discussed. PMID:13723177

Effect of Eu3+ doping on the structural, morphological and luminescence properties ZnO nanostructures

NASA Astrophysics Data System (ADS)

Vinoditha, U.; Balakrishna, K. M.; Sarojini, B. K.; Narayana, B.; Kumara, K.

2018-05-01

Pure and Eu3+ ions (1, 3, 5 atomic wt%) doped ZnO nanostructures are synthesized by a surfactant assisted hydrothermal method. The effect of doping concentrations on structural, morphological and optical properties of ZnO nanostructures is studied. The XRD analysis shows good crystallinity and the phase purity of the ZnO nanostructures. A shift in the standard Zn-O stretching mode after Eu3+ doping is observed in the FTIR spectra. The images of FESEM demonstrate the morphological variations from hexagonal nanorods to nanoflowers on varying the dopant concentrations. Substitution of Eu3+ ions into Zn2+ sites is confirmed by EDX analysis. The dominance of particle shape over the UV-Visible absorption properties of the prepared samples is noticed. The photoluminescence (PL) emission of undoped and doped ZnO nanostructures show dominant near band edge emission (NBE) in the UV region and minor defect induced deep level emissions in the visible region.

Characterization and quantification of the chemical compositions of Scutellariae Barbatae herba and differentiation from its substitute by combining UHPLC-PDA-QTOF-MS/MS with UHPLC-MS/MS.

PubMed

Zhang, Zhifeng; He, Lili; Lu, Luyang; Liu, Yuan; Dong, Gengting; Miao, Jianhua; Luo, Pei

2015-05-10

The aim of this study was to investigate the possibility of using the non-official species Scutellaria indica L. as the substitute for the official species Scutellaria barbata D. Don. A sensitive, precise and accurate method was developed to identify their chemical compositions from the crude extracts using UHPLC-PDA-QTOF-MS/MS. 36 peaks were detected and 28 peaks have been tentatively and structurally characterized by comparing their retention times, UV spectra and HR-MS data with those of the reference substances and/or the data of the literatures. Additionally, 5 flavonoids have been quantified by multiple reaction monitoring (MRM) in the negative ionization mode. The results demonstrated that there were 23 common peaks between these two species. However, the other 13 peaks from S. barbata could not be detected in S. indica. Furthermore, the content of 5 flavonoids is significantly different. Scutellarein cannot be detected in S. indica, which was considered as the characteristic component for distinguishing the two species. Our data, therefore, clearly demonstrate that S. indica may not be used as the substitute for S. barbata and further investigation is needed to determine through investigation of their therapeutic efficacy. Copyright © 2015. Published by Elsevier B.V.

Inhibition kinetics and molecular simulation of p-substituted cinnamic acid derivatives on tyrosinase.

PubMed

Cui, Yi; Hu, Yong-Hua; Yu, Feng; Zheng, Jing; Chen, Lin-Shan; Chen, Qing-Xi; Wang, Qin

2017-02-01

This study was to investigate the inhibition effects of para-substituted cinnamic acid derivatives (4-chlorocinnamic acid, 4-ethoxycinnamic acid and 4-nitrocinnamic acid) on tyrosinase catalyzing the substrates, with the purpose of elucidating the inhibition mechanism of the tested derivatives on tyrosinase by the UV-vis spectrum, fluorescence spectroscopy, copper interacting and molecular docking, respectively. The native-PAGE results showed that 4-chlorocinnamic acid (4-CCA), 4-ethoxycinnamic acid (4-ECA) and 4-nitrocinnamic acid (4-NCA) had inhibitory effects on tyrosinase. Spectrophotometric analysis used to determine the inhibition capabilities of these compounds on tyrosinase catalyzing L-tyrosine (L-Tyr) and L-3,4-Dihydroxyphenylalanine (L-DOPA) as well. The IC 50 values and inhibition constants were further determined. Moreover, quenching mechanisms of tested compounds to tyrosinase belonged to static type and a red shift on fluorescence emission peak occurred when 4-NCA added. Copper interacting and molecular docking demonstrated that 4-CCA could not bind directly to the copper, but it could interact with residues in the active center of tyrosinase. Meanwhile, 4-ECA and 4-NCA could chelate a copper ion of tyrosinase. Anti-tyrosinase activities of para-substituted cinnamic acid derivatives would lay scientific foundation for their utilization in designing of novel tyrosinase inhibitors. Copyright © 2016 Elsevier B.V. All rights reserved.

Double Tryptophan Exciton Probe to Gauge Proximal Side Chains in Proteins- Augmentation at Low Temperature

PubMed Central

Gasymov, Oktay K.; Abduragimov, Adil R.; Glasgow, Ben J.

2015-01-01

The circular dichroic (CD) exciton couplet between tryptophans and/or tyrosines offers the potential to probe distances within 10Å in proteins. The exciton effect has been used with native chromophores in critical positions in a few proteins. Here, site-directed mutagenesis created double tryptophan probes for key sites of a protein (tear lipocalin). For tear lipocalin the crystal and solution structures are concordant in both apo- and holo-forms. Double tryptophan substitutions were performed at sites that could probe conformation and were likely within 10 Å. Far-UV CD spectra of double Trp mutants were performed with controls that had non-interacting substituted tryptophans. Low temperature (77K) was tested for augmentation of the exciton signal. Exciton coupling appeared with tryptophan substitutions at positions within loop A-B (28 and 31, 33), between loop A-B (28) and strand G (103 and 105), as well as between the strands B (35) and C (56). The CD exciton couplet signals were amplified 3–5 fold at 77K. The results were concordant with close distances in crystal and solution structures. The exciton couplets had functional significance and correctly assigned the holo-conformation. The methodology creates an effective probe to identify proximal amino acids in a variety of motifs. PMID:25693116

Synthesis and characterization of tetra phenoxy-substituted halogen-rich metallophthalocyanine derivatives: A study on their LCD color filter requirements

NASA Astrophysics Data System (ADS)

Muthukumar, Palanisamy; Kim, Hak-Soo; Jeong, Jong Woo; Son, Young-A.

2016-09-01

This study addresses the synthesis and characterization of new tetra phenoxy-substituted halogen-rich metallophthalocyanine derivatives (MPcs) 4-7 (M = Co, Ni, Cu and Zn). The synthesized new compounds were characterized using UV-Vis, FT-IR, MALDI-TOF, 1H NMR and elemental analyses. In addition, the basic requirements such as aggregation behavior, thermal stability, transmittance and solubility in propylene glycol monomethyl ether acetate (PGMEA) of MPcs 4-7 were investigated for their usage as a green color filter in Liquid Crystal Displays (LCDs). All of the MPcs showed thermal stability and sufficient solubility in PGMEA. However, the addition of binder into PGMEA solution of MPcs 5 and 6 leads to precipitation. Among the four MPcs, zinc phthalocyanine (7) showed higher transmittance. The higher transmittance of zinc phthalocyanine (7) along with its thermal stability and sufficient solubility in PGMEA are promising for its application as a green color filter in LCDs.

Investigation of the photophysical and photochemical properties of peripherally tetra-substituted water-soluble zwitterionic and cationic zinc(ii) phthalocyanines.

PubMed

Çolak, Senem; Durmuş, Mahmut; Yıldız, Salih Zeki

2016-06-21

In this study, 4-{4-[N-((3-dimethylamino)propyl)amide]phenoxy}phthalonitrile () and its zinc(ii) phthalocyanine derivative () were synthesized for the first time. 4-(N-((3-Dimethylamino)propyl)amide)phenoxy substituted zinc(ii) phthalocyanine () was converted to its water-soluble sulfobetaine (), betaine () and N-oxide () containing zwitterionic and quaternized cationic () derivatives. All newly synthesized compounds () were characterized by the combination of UV-vis, FT-IR, (1)H NMR, mass spectroscopy techniques and elemental analysis. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen quantum yields) properties were investigated in DMSO for all the synthesized zinc(ii) phthalocyanines () and in both DMSO and aqueous solutions for zwitterionic and cationic phthalocyanines () for the specification of their capability as photosensitizers in photodynamic therapy (PDT). The binding behavior of water soluble phthalocyanines () to the bovine serum albumin protein was also examined for the determination of their transportation ability in the blood stream.

Synthesis, characterization and tin/copper-nitrogen substitutional effect on photocatalytic activity of honeycomb ordered P2-Na2Ni2TeO6

NASA Astrophysics Data System (ADS)

Kadari, Ramaswamy; Velchuri, Radha; Sreenu, K.; Ravi, Gundeboina; Munirathnam, Nagegownivari R.; Vithal, Muga

2016-11-01

We have successfully prepared visible light active tin/copper-nitrogen co-doped honeycomb ordered P2-Na2Ni2TeO6 photocatalysts by solid state/ion exchange methods. Powder XRD, TG analysis, SEM, surface area, O-N-H analysis, ICP-OES, FT-IR and UV-DRS measurements are employed to characterize all the samples. All the doped compositions adopted hexagonal lattice with space group P63/mcm. The photocatalytic activity of all the samples was studied against the degradation of methyl violet (MV) and methylene blue (MB) under visible light irradiation. The variation of the photocatalytic activity due to the substitution of cation, anion and co-doping in Na2Ni2TeO6 is investigated. Co-doped samples have exhibited higher activity compared to rest of the materials. The role of reactive intermediate species in the photocatalytic degradation of dyes is also studied using appropriate scavengers.

Synthesis and pKa determination of new enantiopure dimethyl-substituted acridino-crown ethers containing a carboxyl group: Useful candidates for enantiomeric recognition studies.

PubMed

Németh, Tamás; Dargó, Gergő; Petró, József Levente; Petrik, Zsófia; Lévai, Sándor; Krámos, Balázs; Béni, Zoltán; Nagy, József; Balogh, György Tibor; Huszthy, Péter; Tóth, Tünde

2017-09-01

New enantiopure dimethyl-substituted acridino-18-crown-6 and acridino-21-crown-7 ethers containing a carboxyl group at position 9 of the acridine ring [(S,S)-8, (S,S)-9, (R,R)-10] were synthesized. The pK a values of the new crown ethers [(S,S)-8, (S,S)-9, (R,R)-10] and of an earlier reported macrocycle [(R,R)-2] were determined by UV-pH titrations. Crown ether (S,S)-8 was attached to silica gel by covalent bonds and the enantiomeric separation ability of the newly prepared chiral stationary phase [(S,S)-CSP-12] was studied by high-performance liquid chromatography (HPLC). Homochiral preference was observed and the best separation was achieved for the enantiomers of 1-NEA. Ligands (S,S)-9 and (R,R)-10 are precursors of enantioselective sensor and selector molecules for the enantiomers of protonated primary amines, amino acids, and their derivatives. © 2017 Wiley Periodicals, Inc.

Molecular complexes of L-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: Spectral and theoretical investigations

NASA Astrophysics Data System (ADS)

Ganesh, K.; El-Mossalamy, E. H.; Satheshkumar, A.; Balraj, C.; Elango, K. P.

2013-12-01

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ1-4). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH = 7). The interaction of MQ1-4 with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations.

Structural, optical, mechanical and dielectric studies of pure and doped L-Prolinium trichloroacetate single crystals.

PubMed

Renuka, N; Ramesh Babu, R; Vijayan, N; Vasanthakumar, Geetha; Krishna, Anuj; Ramamurthi, K

2015-02-25

In the present work, pure and metal substituted L-Prolinium trichloroacetate (LPTCA) single crystals were grown by slow evaporation method. The grown crystals were subjected to single crystal X-ray diffraction (XRD), powder X-ray diffraction, FTIR, UV-Visible-NIR, hardness, photoluminescence and dielectric studies. The dopant concentration in the crystals was measured by inductively coupled plasma (ICP) analysis. Single crystal X-ray diffraction studies of the pure and metal substituted LPTCA revealed that the grown crystals belong to the trigonal system. Ni(2+) and Co(2+) doping slightly altered the lattice parameters of LPTCA without affecting the basic structure of the crystal. FTIR spectral analysis confirms the presence of various functional groups in the grown crystals. The mechanical behavior of pure and doped crystals was analyzed by Vickers's microhardness test. The optical transmittance, dielectric and photoluminescence properties of the pure and doped crystals were analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

Production of cured meat color in nitrite-free Harbin red sausage by Lactobacillus fermentum fermentation.

PubMed

Zhang, Xue; Kong, Baohua; Xiong, Youling L

2007-12-01

Lactobacillus fermentum was substituted for nitrite to produce cured pink color in a Chinese-style sausage. Treatments included inoculations (10(4), 10(6), and 10(8)CFU/g meat) followed by fermentation at 30°C for 8h and then at 4°C for 16h. Control sausage (with sodium nitrite, 60mg/kg meat) was cured at 4°C for 24h without L. fermentum. The UV-Vis spectra of pigment extract from L. fermentum-treated sausage were identical to that of nitrosylmyoglobin (NO-Mb) formed in nitrite-treated control. The NO-Mb concentration and the colorimetric a(∗) value of sausage treated with 10(8)CFU/g meat of L. fermentum essentially replicated those in nitrite-cured meat. Free amino acid content in sausage treated with L. fermentum was greater and the pH slightly lower compared with the nitrite-cured control sample. This study showed that L. fermentum has the potential to substitute for nitrite in the sausage production.

Effect of pigment concentration on fastness and color values of thermal and UV curable pigment printing

NASA Astrophysics Data System (ADS)

Baysal, Gulcin; Kalav, Berdan; Karagüzel Kayaoğlu, Burçak

2017-10-01

In the current study, it is aimed to determine the effect of pigment concentration on fastness and colour values of thermal and ultraviolet (UV) curable pigment printing on synthetic leather. For this purpose, thermal curable solvent-based and UV curable water-based formulations were prepared with different pigment concentrations (3, 5 and 7%) separately and applied by screen printing technique using a screen printing machine. Samples printed with solvent-based formulations were thermally cured and samples printed with water-based formulations were cured using a UV curing machine equipped with gallium and mercury (Ga/Hg) lamps at room temperature. The crock fastness values of samples printed with solvent-based formulations showed that increase in pigment concentration was not effective on both dry and wet crock fastness values. On the other hand, in samples printed with UV curable water-based formulations, dry crock fastness was improved and evaluated as very good for all pigment concentrations. However, increasing the pigment concentration affected the wet crock fastness values adversely and lower values were observed. As the energy level increased for each irradiation source, the fastness values were improved. In comparison with samples printed with solvent-based formulations, samples printed with UV curable water-based formulations yielded higher K/S values at all pigment concentrations. The results suggested that, higher K/S values can be obtained in samples printed with UV curable water-based formulations at a lower pigment concentration compared to samples printed with solvent-based formulations.

Society already achieves economic benefits from generic substitution but fails to do the same for therapeutic substitution.

PubMed

Gumbs, Pearl D; Verschuren, W M Monique; Souverein, Patrick C; Mantel-Teeuwisse, Aukje K; de Wit, G Ardine; de Boer, Anthonius; Klungel, Olaf H

2007-11-01

To assess the potential annual savings due to generic and therapeutic substitution of statin therapy for the general Dutch population, taking the patients medical history into account. We conducted a population-based costing study using the PHARMO Record Linkage System (RLS). PHARMO RLS contains drug dispensing records from a representative sample of pharmacies located in more than 50 regions in the Netherlands. We selected all statin users in the database since 2003. The cost-savings of generic substitution of statin therapy for all simvastatin and pravastatin users, and of therapeutic substitution of statin therapy for other statin users were calculated. Substituting current users and new users of statins were considered separately. Therapeutic substitution was based on the medical history of the individual patient. Patients were only substituted if there was an appropriate substitute available. The appropriateness of substitution was based on drug-drug interactions between statins and possible comedication and the availability of an equipotent alternative. Substituting (generic and therapeutic) statin therapy for all current users would lead to potential annual savings of approximately 87 million euros. Substituting (generic and therapeutic) all starters on statin therapy would lead to potential annual savings of around 51 million euros. In the case of generic substitution only, the potential annual savings for all current simvastatin and pravastatin users would be 2.4 million euros and for the new users about 1.8 million euros. From an economic point of view, society could gain a lot from substituting statin therapy, especially from therapeutic substitution.

Activation of rhenium(I) toward substitution in fac-[Re(N,O'-Bid)(CO)3(HOCH3)] by Schiff-base bidentate ligands (N,O'-Bid).

PubMed

Brink, Alice; Visser, Hendrik G; Roodt, Andreas

2013-08-05

A series of fac-[Re(N,O'-Bid)(CO)3(L)] (N,O'-Bid = monoanionic bidentate Schiff-base ligands with N,O donor atoms; L = neutral monodentate ligand) has been synthesized, and the methanol substitution reactions have been investigated. The complexes were characterized by NMR, IR, and UV-vis spectroscopy. X-ray crystal structures of the compounds fac-[Re(Sal-mTol)(CO)3(HOCH3)], fac-[Re(Sal-pTol)(CO)3(HOCH3)], fac-[Re(Sal-Ph)(CO)3(HOCH3)], and fac-[Re(Sal-Ph)(CO)3(Py)] (Sal-mTol = 2-(m-tolyliminomethyl)phenolato; Sal-pTol = 2-(p-tolyliminomethyl)phenolato; Sal-Ph = 2-(phenyliminomethyl)phenolato; Py = pyridine) are reported. Significant activation for the methanol substitution is induced by the use of the N,O bidentate ligand as manifested by the second order rate constants, with limiting kinetics being observed for the first time. Rate constants (25 °C) (k1 or k3) and activation parameters (ΔHk‡, kJ mol(-1); ΔSk‡, J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(Sal-mTol)(CO)3(HOCH3)] 3-chloropyridine: (k1) 2.33 ± 0.01 M(-1) s(-1); 85.1 ± 0.6, 48 ± 2; fac-[Re(Sal-mTol)(CO)3(HOCH3)] pyridine: (k1) 1.29 ± 0.02 M(-1) s(-1); 92 ± 2, 66 ± 7; fac-[Re(Sal-mTol)(CO)3(HOCH3)] 4-picoline: (k1) 1.27 ± 0.05 M(-1) s(-1); 88 ± 2, 53 ± 6; (k3) 3.9 ± 0.03 s(-1); 78 ± 8, 30 ± 27; (kf) 1.7 ± 0.02 M(-1) s(-1); 86 ± 2, 49 ± 6; fac-[Re(Sal-mTol)(CO)3(HOCH3)] DMAP (k3) 1.15 ± 0.02 s(-1); 88 ± 2, 52 ± 7. An interchange dissociative mechanism is proposed.

Validation of an Innovative Satellite-Based UV Dosimeter

NASA Astrophysics Data System (ADS)

Morelli, Marco; Masini, Andrea; Simeone, Emilio; Khazova, Marina

2016-08-01

We present an innovative satellite-based UV (ultraviolet) radiation dosimeter with a mobile app interface that has been validated by exploiting both ground-based measurements and an in-vivo assessment of the erythemal effects on some volunteers having a controlled exposure to solar radiation.Both validations showed that the satellite-based UV dosimeter has a good accuracy and reliability needed for health-related applications.The app with this satellite-based UV dosimeter also includes other related functionalities such as the provision of safe sun exposure time updated in real-time and end exposure visual/sound alert. This app will be launched on the global market by siHealth Ltd in May 2016 under the name of "HappySun" and available both for Android and for iOS devices (more info on http://www.happysun.co.uk).Extensive R&D activities are on-going for further improvement of the satellite-based UV dosimeter's accuracy.

A new approach to correct for absorbing aerosols in OMI UV

NASA Astrophysics Data System (ADS)

Arola, A.; Kazadzis, S.; Lindfors, A.; Krotkov, N.; Kujanpää, J.; Tamminen, J.; Bais, A.; di Sarra, A.; Villaplana, J. M.; Brogniez, C.; Siani, A. M.; Janouch, M.; Weihs, P.; Webb, A.; Koskela, T.; Kouremeti, N.; Meloni, D.; Buchard, V.; Auriol, F.; Ialongo, I.; Staneck, M.; Simic, S.; Smedley, A.; Kinne, S.

2009-11-01

Several validation studies of surface UV irradiance based on the Ozone Monitoring Instrument (OMI) satellite data have shown a high correlation with ground-based measurements but a positive bias in many locations. The main part of the bias can be attributed to the boundary layer aerosol absorption that is not accounted for in the current satellite UV algorithms. To correct for this shortfall, a post-correction procedure was applied, based on global climatological fields of aerosol absorption optical depth. These fields were obtained by using global aerosol optical depth and aerosol single scattering albedo data assembled by combining global aerosol model data and ground-based aerosol measurements from AERONET. The resulting improvements in the satellite-based surface UV irradiance were evaluated by comparing satellite and ground-based spectral irradiances at various European UV monitoring sites. The results generally showed a significantly reduced bias by 5-20%, a lower variability, and an unchanged, high correlation coefficient.

Implementation of UV-based advanced oxidation processes in algal medium recycling.

PubMed

Wang, Wenxuan; Sha, Jun; Lu, Zhiying; Shao, Senlin; Sun, Peizhe; Hu, Qiang; Zhang, Xuezhi

2018-09-01

Algae show great potential as sustainable feedstock for numerous bioproducts. However, large volume of water consumption during algal biomass production makes that the culture media recycling is a necessity due to economic and environmental concern. To avoid the negative effect of enriched organic matters in the harvested culture media, pre-treatment prior to medium replenishment and reuse is required. In this study, degradation of algenitic organic matters (AOM) in the culture media by UV-based photolysis processes (i.e., direct UV, UV/peroxydisulfate (PDS), UV/H 2 O 2 , and UV/NH 2 Cl) was explored. The results showed that UV, UV/PDS, UV/H 2 O 2 and UV/NH 2 Cl caused a decrease of SUVA for 29.9%, 35.4%, 40.45%, and 22.6%, respectively, though the organic matter was almost not mineralized. Fluorescence excitation-emission matrix combined with parallel factor analysis indicated that UV/PDS and UV/H 2 O 2 degraded 47.26%-56.31% of the fulvic-like and humic-like fractions in AOM. Powder activated carbon absorption and growth evaluation for the AOPs-treated media indicated that UV/PDS and UV/H 2 O 2 processes not only could remove the growth inhibitors in the media, but were also beneficial to the algae growth. These results suggested that UV/PDS and UV/H 2 O 2 could effectively degrade the hydrophobic components in AOM and converted the growth inhibition fraction of AOM in the recycled media into nutrient source for algal growth. Different from the general application of UV-based AOP in the wastewater treatment, this study provided an innovative idea about how to pre-treat AOM in the media recycling: utilization rather than removal, which was a more sustainable and environment-friendly technology. Copyright © 2018 Elsevier B.V. All rights reserved.

Changes in biologically active ultraviolet radiation reaching the Earth's surface.

PubMed

Madronich, S; McKenzie, R L; Björn, L O; Caldwell, M M

1998-10-01

Stratospheric ozone levels are near their lowest point since measurements began, so current ultraviolet-B (UV-B) radiation levels are thought to be close to their maximum. Total stratospheric content of ozone-depleting substances is expected to reach a maximum before the year 2000. All other things being equal, the current ozone losses and related UV-B increases should be close to their maximum. Increases in surface erythemal (sunburning) UV radiation relative to the values in the 1970s are estimated to be: about 7% at Northern Hemisphere mid-latitudes in winter/spring; about 4% at Northern Hemisphere mid-latitudes in summer/fall; about 6% at Southern Hemisphere mid-latitudes on a year-round basis; about 130% in the Antarctic in spring; and about 22% in the Arctic in spring. Reductions in atmospheric ozone are expected to result in higher amounts of UV-B radiation reaching the Earth's surface. The expected correlation between increases in surface UV-B radiation and decreases in overhead ozone has been further demonstrated and quantified by ground-based instruments under a wide range of conditions. Improved measurements of UV-B radiation are now providing better geographical and temporal coverage. Surface UV-B radiation levels are highly variable because of cloud cover, and also because of local effects including pollutants and surface reflections. These factors usually decrease atmospheric transmission and therefore the surface irradiances at UV-B as well as other wavelengths. Occasional cloud-induced increases have also been reported. With a few exceptions, the direct detection of UV-B trends at low- and mid-latitudes remains problematic due to this high natural variability, the relatively small ozone changes, and the practical difficulties of maintaining long-term stability in networks of UV-measuring instruments. Few reliable UV-B radiation measurements are available from pre-ozone-depletion days. Satellite-based observations of atmospheric ozone and clouds are being used, together with models of atmospheric transmission, to provide global coverage and long-term estimates of surface UV-B radiation. Estimates of long-term (1979-1992) trends in zonally averaged UV irradiances that include cloud effects are nearly identical to those for clear-sky estimates, providing evidence that clouds have not influenced the UV-B trends. However, the limitations of satellite-derived UV estimates should be recognized. To assess uncertainties inherent in this approach, additional validations involving comparisons with ground-based observations are required. Direct comparisons of ground-based UV-B radiation measurements between a few mid-latitude sites in the Northern and Southern Hemispheres have shown larger differences than those estimated using satellite data. Ground-based measurements show that summertime erythemal UV irradiances in the Southern Hemisphere exceed those at comparable latitudes of the Northern Hemisphere by up to 40%, whereas corresponding satellite-based estimates yield only 10-15% differences. Atmospheric pollution may be a factor in this discrepancy between ground-based measurements and satellite-derived estimates. UV-B measurements at more sites are required to determine whether the larger observed differences are globally representative. High levels of UV-B radiation continue to be observed in Antarctica during the recurrent spring-time ozone hole. For example, during ozone-hole episodes, measured biologically damaging radiation at Palmer Station, Antarctica (64 degrees S) has been found to approach and occasionally even exceed maximum summer values at San Diego, CA, USA (32 degrees N). Long-term predictions of future UV-B levels are difficult and uncertain. Nevertheless, current best estimates suggest that a slow recovery to pre-ozone depletion levels may be expected during the next half-century. (ABSTRACT TRUNCATED)

Phenanthridine-Containing Pincer-like Amido Complexes of Nickel, Palladium, and Platinum.

PubMed

Mandapati, Pavan; Giesbrecht, Patrick K; Davis, Rebecca L; Herbert, David E

2017-03-20

Proligands based on bis(8-quinolinyl)amine (L1) were prepared containing one (L2) and two (L3) benzo-fused N-heterocyclic phenanthridinyl (3,4-benzoquinolinyl) units. Taken as a series, L1-L3 provides a ligand template for exploring systematic π-extension in the context of tridentate pincer-like amido complexes of group 10 metals (1-M, 2-M, and 3-M; M = Ni, Pd, Pt). Inclusion of phenanthridinyl units was enabled by development of a cross-coupling/condensation route to 6-unsubstituted, 4-substituted phenanthridines (4-Br, 4-NO 2 , 4-NH 2 ) suitable for elaboration into the target ligand frameworks. Complexes 1-M, 2-M, and 3-M are redox-active; electrochemistry and UV-vis absorption spectroscopy were used to investigate the impact of π-extension on the electronic properties of the metal complexes. Unlike what is typically observed for benzannulated ligand-metal complexes, extending the π-system in metal complexes 1-M to 2-M to 3-M led to only a moderate red shift in the relative highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap as estimated by electrochemistry and similarly subtle changes to the onset of the lowest-energy absorption observed by UV-vis spectroscopy. Time-dependent density functional theory calculations revealed that benzannulation significantly impacts the atomic contributions to the LUMO and LUMO+1 orbitals, altering the orbital contributions to the lowest-energy transition but leaving the energy of this transition essentially unchanged.

Changing blue fluorescent protein to green fluorescent protein using chemical RNA editing as a novel strategy in genetic restoration.

PubMed

Vu, Luyen T; Nguyen, Thanh T K; Alam, Shafiul; Sakamoto, Takashi; Fujimoto, Kenzo; Suzuki, Hitoshi; Tsukahara, Toshifumi

2015-11-01

Using the transition from cytosine of BFP (blue fluorescent protein) gene to uridine of GFP (green fluorescent protein) gene at position 199 as a model, we successfully controlled photochemical RNA editing to effect site-directed deamination of cytidine (C) to uridine (U). Oligodeoxynucleotides (ODNs) containing 5'-carboxyvinyl-2'-deoxyuridine ((CV) U) were used for reversible photoligation, and single-stranded 100-nt BFP DNA and in vitro-transcribed full-length BFP mRNA were the targets. Photo-cross-linking with the responsive ODNs was performed using UV (366 nm) irradiation, which was followed by heat treatment, and the cross-linked nucleotide was cleaved through photosplitting (UV, 312 nm). The products were analyzed using restriction fragment length polymorphism (RFLP) and fluorescence measurements. Western blotting and fluorescence-analysis results revealed that in vitro-translated proteins were synthesized from mRNAs after site-directed RNA editing. We detected substantial amounts of the target-base-substituted fragment using RFLP and observed highly reproducible spectra of the transition-GFP signal using fluorescence spectroscopy, which indicated protein stability. ODNc restored approximately 10% of the C-to-U transition. Thus, we successfully used non-enzymatic site-directed deamination for genetic restoration in vitro. In the near future, in vivo studies that include cultured cells and model animals will be conducted to treat genetic disorders. © 2015 John Wiley & Sons A/S.

Synthesis of 2-Azulenyltetrathiafulvalenes by Palladium-Catalyzed Direct Arylation of 2-Chloroazulenes with Tetrathiafulvalene and Their Optical and Electrochemical Properties.

PubMed

Shoji, Taku; Araki, Takanori; Sugiyama, Shuhei; Ohta, Akira; Sekiguchi, Ryuta; Ito, Shunji; Okujima, Tetsuo; Toyota, Kozo

2017-02-03

Tetrathiafulvalene (TTF) derivatives with 2-azulenyl substituents 5-11 were prepared by the palladium-catalyzed direct arylation reaction of 2-chloroazulenes with TTF in good yield. Photophysical properties of these compounds were investigated by UV-vis spectroscopy and theoretical calculations. Redox behavior of the novel azulene-substituted TTFs was examined by using cyclic voltammetry and differential pulse voltammetry, which revealed their multistep electrochemical oxidation and/or reduction properties. Moreover, these TTF derivatives showed significant spectral change in the visible region under the redox conditions.

Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

DOE R&D Accomplishments Database

Continetti, R. E.; Balko, B. A.; Lee, Y. T.

1989-02-01

A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

A New F131V Mutation in Chlamydomonas Phytoene Desaturase Locates a Cluster of Norflurazon Resistance Mutations near the FAD-Binding Site in 3D Protein Models

PubMed Central

Suarez, Julio V.; Banks, Stephen; Thomas, Paul G.; Day, Anil

2014-01-01

The green alga Chlamydomonas reinhardtii provides a tractable genetic model to study herbicide mode of action using forward genetics. The herbicide norflurazon inhibits phytoene desaturase, which is required for carotenoid synthesis. Locating amino acid substitutions in mutant phytoene desaturases conferring norflurazon resistance provides a genetic approach to map the herbicide binding site. We isolated a UV-induced mutant able to grow in very high concentrations of norflurazon (150 µM). The phytoene desaturase gene in the mutant strain contained the first resistance mutation to be localised to the dinucleotide-binding Rossmann-likedomain. A highly conserved phenylalanine amino acid at position 131 of the 564 amino acid precursor protein was changed to a valine in the mutant protein. F131, and two other amino acids whose substitution confers norflurazon resistance in homologous phytoene desaturase proteins, map to distant regions in the primary sequence of the C. reinhardtii protein (V472, L505) but in tertiary models these residues cluster together to a region close to the predicted FAD binding site. The mutant gene allowed direct 5 µM norflurazon based selection of transformants, which were tolerant to other bleaching herbicides including fluridone, flurtamone, and diflufenican but were more sensitive to beflubutamid than wild type cells. Norflurazon resistance and beflubutamid sensitivity allow either positive or negative selection against transformants expressing the mutant phytoene desaturase gene. PMID:24936791

ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

PubMed

Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

2013-11-07

The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

Synthesis, spectroscopic characterization, DFT study and antimicrobial activity of novel alkylaminopyrazole derivatives

NASA Astrophysics Data System (ADS)

Zalaru, Christina; Dumitrascu, Florea; Draghici, Constantin; Tarcomnicu, Isabela; Tatia, Rodica; Moldovan, Lucia; Chifiriuc, Mariana-Carmen; Lazar, Veronica; Marinescu, Maria; Nitulescu, Mihai George; Ferbinteanu, Marilena

2018-03-01

A new series of substituted N,N-bis-[(1H-pyrazol-1-yl)methyl]-aminohexadecane Mannich bases were synthesized, characterized by IR, 1H NMR 13C NMR, UV-Vis, MS and elemental analysis, and tested for their biological activity. All the synthesized compounds were tested for in vitro antimicrobial activity against a panel of selected bacterial and fungal strains using erythromycin and clotrimazole as standards. Most of the synthesized compounds demonstrated very good activity at minimum inhibitory concentrations (MICs). Compound 3b with an halogen atom into the pharmacophore structure exhibited the most significant activity against Bacillus subtilis (MIC = 0.007 μgmLL-1) versus erythromycin as standard. In vitro cytotoxicity of the new compounds was studied using MTT assay. The analysis of the test cells showed that the newly synthesized alkylaminopyrazoles derivatives were biocompatible until a concentration of 5 μgmL-1; two compounds presented a high degree of biocompatibility on the studied concentration range.

Design and synthesis of a new organic receptor and evaluation of colorimetric anion sensing ability in organo-aqueous medium

NASA Astrophysics Data System (ADS)

Srikala, P.; Tarafder, Kartick; Trivedi, Darshak R.

2017-01-01

A new organic receptor has been designed and synthesized by the combination of aromatic dialdehyde with nitro-substituted aminophenol resulting in a Schiff base compound. The receptor exhibited a colorimetric response for F- and AcO- ion with a distinct color change from pale yellow to red and pink respectively in dry DMSO solvent and yellow to pale greenish yellow in DMSO:H2O (9:1, v/v). UV-Vis titration studies displayed a significant shift in absorption maxima in comparison with the free receptor. The shift could be attributed to the hydrogen bonding interactions between the active anions and the hydroxyl functionality aided by the electron withdrawing nitro substituent on the receptor. 1H NMR titration and density functionality studies have been performed to understand the nature of interaction of receptor and anions. The lower detection limit of 1.12 ppm was obtained in organic media for F- ion confirming the real time application of the receptor.

The synthesis and characterization of azocalix[4]arene based chemosensors and investigation of their properties

NASA Astrophysics Data System (ADS)

Elçin, Serkan; Çılgı, Gülbanu Koyundereli; Bayrakdar, Alpaslan; Deligöz, Hasalettin

2015-05-01

In the present study, azocalix[4]arenes were prepared by linking 4-methoxy, 4-methyl, 4-ethyl, 4-chloro, 4-bromo and 4-nitroaniline to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arene tetraester derivatives, (4a-f), have been prepared with the incorporation of ethyl ester units to azocalix[4]arene. Characterization of the synthesized azocalix[4]arenes was carried using elemental analyses, UV-vis, FT-IR and 1H NMR spectroscopic techniques. The effect of varying pH levels and solvent types on the absorption ability of azocalix[n]arenes substituted with electron-donating and electron-withdrawing groups was examined. Thermal decomposition of azocalix[4]arene derivatives (4a-f) was investigated by means of thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) analyses. In conclusion of the examination of the extraction we found a selectivity characteristic of these compounds toward Ag+, Hg+ and Hg2+ cations.

Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

PubMed

Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

2013-02-01

The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl₃/OXY and 0.212 CHCl₃/DiOXY. Copyright © 2012 Elsevier Ltd. All rights reserved.

Polymeric material prepared from Schiff base based on O-carboxymethyl chitosan and its Cu(II) and Pd(II) complexes

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2016-07-01

In this study, a new eco-friendly Schiff base based on O-carboxymethyl chitosan ([OCMCS-7a]) and its copper(II) and palladium(II) complexes were synthesized. Characterizations of [OCMCS-7a] and its metal complexes were conducted using FTIR, 1H NMR, 13C NMR, TG/DTG, XRD, SEM-EDAX, ICP, UV-VIS, GC-MS, elemental analysis, magnetic moment and molar conductivity measurements. The degree of substitution (DS) of [OCMCS-7a] was determined by elemental analysis to be 0.44. It was shown by the solubility test that [OCMCS-7a] was completely soluble in water. Surface images of chitosan, [OCMCS-7a] and its Cu(II) and Pd(II) complexes were investigated using the SEM-EDAX technique. Their thermal behaviors and crystallinities of the synthesized complexes were determined by TG/DTG and X-ray powder diffraction techniques, respectively. The metal contents of the obtained complexes were determined using an ICP-OES instrument. From the analyses, it was noted that the thermal stabilities and crystallinities of [OCMCS-7a] and its complexes decreased compared to chitosan. As a consequence of surface screening, it was also noted that the surface structure of the chitosan was smoother than that of the obtained compounds.

Online educative activities for solar ultraviolet radiation based on measurements of cloud amount and solar exposures.

PubMed

Parisi, A V; Downs, N; Turner, J; Amar, A

2016-09-01

A set of online activities for children and the community that are based on an integrated real-time solar UV and cloud measurement system are described. These activities use the functionality of the internet to provide an educative tool for school children and the public on the influence of cloud and the angle of the sun above the horizon on the global erythemal UV or sunburning UV, the diffuse erythemal UV, the global UVA (320-400nm) and the vitamin D effective UV. Additionally, the units of UV exposure and UV irradiance are investigated, along with the meaning and calculation of the UV index (UVI). This research will help ensure that children and the general public are better informed about sun safety by improving their personal understanding of the daily and the atmospheric factors that influence solar UV radiation and the solar UV exposures of the various wavebands in the natural environment. The activities may correct common misconceptions of children and the public about UV irradiances and exposure, utilising the widespread reach of the internet to increase the public's awareness of the factors influencing UV irradiances and exposures in order to provide clear information for minimizing UV exposure, while maintaining healthy, outdoor lifestyles. Copyright © 2016 Elsevier B.V. All rights reserved.

Calibration and Limitations of the Mg II Line-based Black Hole Masses

NASA Astrophysics Data System (ADS)

Woo, Jong-Hak; Le, Huynh Anh N.; Karouzos, Marios; Park, Dawoo; Park, Daeseong; Malkan, Matthew A.; Treu, Tommaso; Bennert, Vardha N.

2018-06-01

We present single-epoch black hole mass ({M}BH}) calibrations based on the rest-frame ultraviolet (UV) and optical measurements of Mg II 2798 Å and Hβ 4861 Å lines and the active galactic nucleus (AGN) continuum, using a sample of 52 moderate-luminosity AGNs at z ∼ 0.4 and z ∼ 0.6 with high-quality Keck spectra. We combine this sample with a large number of luminous AGNs from the Sloan Digital Sky Survey to increase the dynamic range for a better comparison of UV and optical velocity and luminosity measurements. With respect to the reference {M}BH} based on the line dispersion of Hβ and continuum luminosity at 5100 Å, we calibrate the UV and optical mass estimators by determining the best-fit values of the coefficients in the mass equation. By investigating whether the UV estimators show a systematic trend with Eddington ratio, FWHM of Hβ, Fe II strength, or UV/optical slope, we find no significant bias except for the slope. By fitting the systematic difference of Mg II-based and Hβ-based masses with the L 3000/L 5100 ratio, we provide a correction term as a function of the spectral index as ΔC = 0.24 (1 + α λ ) + 0.17, which can be added to the Mg II-based mass estimators if the spectral slope can be well determined. The derived UV mass estimators typically show >∼0.2 dex intrinsic scatter with respect to the Hβ-based {M}BH}, suggesting that the UV-based mass has an additional uncertainty of ∼0.2 dex, even if high-quality rest-frame UV spectra are available.

Modulated grayscale UV pattern for uniform photopolymerization based on a digital micromirror device system

NASA Astrophysics Data System (ADS)

Yoon, Jinsik; Kim, Kibeom; Park, Wook

2017-07-01

We present an essential method for generating microparticles uniformly in a single ultraviolet (UV) light exposure area for optofluidic maskless lithography. In the optofluidic maskless lithography process, the productivity of monodisperse microparticles depends on the size of the UV exposure area. An effective fabrication area is determined by the size of the UV intensity profile map, satisfying the required uniformity of UV intensity. To increase the productivity of monodisperse microparticles in optofluidic maskless lithography, we expanded the effective UV exposure area by modulating the intensity of the desired UV light pattern based on the premeasured UV intensity profile map. We verified the improvement of the uniformity of the microparticles generated by the proposed modulation technique, providing histogram analyses of the conjugated fluorescent intensities and the sizes of the microparticles. Additionally, we demonstrated the generation of DNA uniformly encapsulated in microparticles.

Deep-UV Based Acousto-Optic Tunable Filter for Spectral Sensing Applications

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S.

2006-01-01

In this paper, recent progress made in the development of quartz and KDP crystal based acousto-optic tunable filters (AOTF) are presented. These AOTFs are developed for operation over deep-UV to near-UV wavelengths of 190 nm to 400 nm. Preliminary output performance measurements of quartz AOTF and design specifications of KDP AOTF are presented. At 355 nm, the quartz AOTF device offered approx.15% diffraction efficiency with a passband full-width-half-maximum (FWHM) of less than 0.0625 nm. Further characterization of quartz AOTF devices at deep-UV wavelengths is progressing. The hermetic packaging of KDP AOTF is nearing completion. The solid-state optical sources being used for excitation include nonlinear optics based high-energy tunable UV transmitters that operate around 320 nm and 308 nm wavelengths, and a tunable deep-UV laser operating over 193 nm to 210 nm. These AOTF devices have been developed as turn-key devices for primarily for space-based chemical and biological sensing applications using laser induced Fluorescence and resonance Raman techniques.

Far-UV-induced dimeric photoproducts in short oligonucleotides: sequence effects.

PubMed

Douki, T; Zalizniak, T; Cadet, J

1997-08-01

Cyclobutane pyrimidine dimers and pyrimidine(6-4)pyrimidone adducts represent the two major classes of far-UV-induced DNA photoproducts. Because of the lack of appropriate detection methods for each individual photoproduct, little is known about the effect of the sequence on their formation. In the present work, the photoproduct distribution obtained upon exposure of a series of dinucleoside monophosphates to 254 nm light was determined. In the latter model compounds, the presence of a cytosine, located at either the 5'- or the 3'-side of a thymine moiety, led to the preferential formation of (6-4) adducts, whereas the cis-syn cyclobutane dimer was the main thymine-thymine photoproduct. In contrast, the yield of dimeric photoproducts, and particularly of (6-4) photoadducts, was very low upon irradiation of the cytosine-cytosine dinucleoside monophosphate. However, substitution of cytosine by uracil led to an increase in the yield of (6-4) photoproduct. It was also shown that the presence of a phosphate group at the 5'- end of a thymine-thymine dinucleoside monophosphate does not modify the photoproduct distribution. As an extension of the studies on dinucleoside monophosphates, the trinucleotide TpdCpT was used as a more relevant DNA model. The yields of formation of the thymine-cytosine and cytosine-thymine (6-4) photoproducts were in a 5:1 ratio, very close to the value obtained upon photolysis of the related dinucleoside monophosphates. The characterization of the two TpdCpT (6-4) adducts was based on 1H NMR, UV and mass spectroscopy analyses. Additional evidence for the structures was inferred from the analysis of the enzymatic digestion products of the (6-4) adducts of TpdCpT with phosphodiesterases. The latter enzymes were shown to induce the quantitative release of the photoproduct as a modified dinucleoside monophosphate in a highly sequence-specific manner.

UV-cured adhesives for carbon fiber composite applications

NASA Astrophysics Data System (ADS)

Lu, Hsiao-Chun

Carbon fiber composite materials are increasingly used in automobile, marine, and aerospace industries due to their unique properties, including high strength, high stiffness and low weight. However, due to their brittle characteristic, these structures are prone to physical damage, such as a bird strike or impact damage. Once the structure is damaged, it is important to have fast and reliable temporary repair until the permanent repair or replacement can take place. In this dissertation, UV-based adhesives were used to provide a bonding strength for temporary repair. Adhesively bonded patch repair is an efficient and effective method for temporary repair. In this study, precured patches (hard patches) and dry fabric patches with laminating resins (soft patches) were performed. UV-based epoxy adhesives were applied to both patch repair systems. For precured patch repair, the bonding strengths were investigated under different surface treatments for bonding area and different adhesives thicknesses. The shear stresses of different UV exposure times and curing times were tested. Besides, the large patch repair was investigated as well. For soft patch repair, the hand wet lay-up was applied due to high viscosity of UV resins. A modified single lap shear testing (ASTM D5868) was applied to determine the shear stress. The large patches used fiber glass instead of carbon fiber to prove the possibility of repair with UV epoxy resin by hand wet lay-up process. The hand lay-up procedure was applied and assisted by vacuum pressure to eliminate the air bubbles and consolidate the patches. To enhance the bonding strength and effective soft patch repair, vacuum assisted resin transferring molding (VaRTM) is the better option. However, only low viscosity resins can be operated by VaRTM. Hence, new UV-based adhesives were formulated. The new UV-based adhesives included photoinitiator (PI), epoxy and different solvents. Solvents were used to compound the photoinitiator into epoxy monomer. Acetone, tetrahydrofuran (THF) and chloroform were used as well as their anhydrous solvents. The UV exposure times and curing times of new UV-based resins were tested. FT-IR, DSC and DMA were used to investigate structure, glass transition temperatures(Tg) and properties of polymer. In summary, the UV-based adhesive was applied to adhesively bonded hard patch and soft patch repair. In addition, new UV-based resins were formulated for the VaRTM process. The in-field repair can be effective and efficient by using UV adhesives.

Satellite estimation of surface spectral ultraviolet irradiance using OMI data in East Asia

NASA Astrophysics Data System (ADS)

Lee, H.; Kim, J.; Jeong, U.

2017-12-01

Due to a strong influence to the human health and ecosystem environment, continuous monitoring of the surface ultraviolet (UV) irradiance is important nowadays. The amount of UVA (320-400 nm) and UVB (290-320 nm) radiation at the Earth surface depends on the extent of Rayleigh scattering by atmospheric gas molecules, the radiative absorption by ozone, radiative scattering by clouds, and both absorption and scattering by airborne aerosols. Thus advanced consideration of these factors is the essential part to establish the process of UV irradiance estimation. Also UV index (UVI) is a simple parameter to show the strength of surface UV irradiance, therefore UVI has been widely utilized for the purpose of UV monitoring. In this study, we estimate surface UV irradiance at East Asia using realistic input based on OMI Total Ozone and reflectivity, and then validate this estimated comparing to UV irradiance from World Ozone and Ultraviolet Radiation Data Centre (WOUDC) data. In this work, we also try to develop our own retrieval algorithm for better estimation of surface irradiance. We use the Vector Linearized Discrete Ordinate Radiative Transfer (VLIDORT) model version 2.6 for our UV irradiance calculation. The input to the VLIDORT radiative transfer calculations are the total ozone column (TOMS V7 climatology), the surface albedo (Herman and Celarier, 1997) and the cloud optical depth. Based on these, the UV irradiance is calculated based on look-up table (LUT) approach. To correct absorbing aerosol, UV irradiance algorithm added climatological aerosol information (Arola et al., 2009). The further study, we analyze the comprehensive uncertainty analysis based on LUT and all input parameters.

37 CFR 2.35 - Adding, deleting, or substituting bases.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 37 Patents, Trademarks, and Copyrights 1 2013-07-01 2013-07-01 false Adding, deleting, or substituting bases. 2.35 Section 2.35 Patents, Trademarks, and Copyrights UNITED STATES PATENT AND TRADEMARK..., deleting, or substituting bases. (a) In an application under section 66(a) of the Act, an applicant may not...

37 CFR 2.35 - Adding, deleting, or substituting bases.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 37 Patents, Trademarks, and Copyrights 1 2011-07-01 2011-07-01 false Adding, deleting, or substituting bases. 2.35 Section 2.35 Patents, Trademarks, and Copyrights UNITED STATES PATENT AND TRADEMARK..., deleting, or substituting bases. (a) In an application under section 66(a) of the Act, an applicant may not...

37 CFR 2.35 - Adding, deleting, or substituting bases.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 37 Patents, Trademarks, and Copyrights 1 2012-07-01 2012-07-01 false Adding, deleting, or substituting bases. 2.35 Section 2.35 Patents, Trademarks, and Copyrights UNITED STATES PATENT AND TRADEMARK..., deleting, or substituting bases. (a) In an application under section 66(a) of the Act, an applicant may not...

37 CFR 2.35 - Adding, deleting, or substituting bases.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 37 Patents, Trademarks, and Copyrights 1 2010-07-01 2010-07-01 false Adding, deleting, or substituting bases. 2.35 Section 2.35 Patents, Trademarks, and Copyrights UNITED STATES PATENT AND TRADEMARK..., deleting, or substituting bases. (a) In an application under section 66(a) of the Act, an applicant may not...

Quantitation of base substitutions in eukaryotic 5S rRNA: selection for the maintenance of RNA secondary structure.

PubMed

Curtiss, W C; Vournakis, J N

1984-01-01

Eukaryotic 5S rRNA sequences from 34 diverse species were compared by the following method: (1) The sequences were aligned; (2) the positions of substitutions were located by comparison of all possible pairs of sequences; (3) the substitution sites were mapped to an assumed general base pairing model; and (4) the R-Y model of base stacking was used to study stacking pattern relationships in the structure. An analysis of the sequence and structure variability in each region of the molecule is presented. It was found that the degree of base substitution varies over a wide range, from absolute conservation to occurrence of over 90% of the possible observable substitutions. The substitutions are located primarily in stem regions of the 5S rRNA secondary structure. More than 88% of the substitutions in helical regions maintain base pairing. The disruptive substitutions are primarily located at the edges of helical regions, resulting in shortening of the helical regions and lengthening of the adjacent nonpaired regions. Base stacking patterns determined by the R-Y model are mapped onto the general secondary structure. Intrastrand and interstrand stacking could stabilize alternative coaxial structures and limit the conformational flexibility of nonpaired regions. Two short contiguous regions are 100% conserved in all species. This may reflect evolutionary constraints imposed at the DNA level by the requirement for binding of a 5S gene transcription initiation factor during gene expression.

Towards a high performing UV-A sensor based on Silicon Carbide and hydrogenated Silicon Nitride absorbing layers

NASA Astrophysics Data System (ADS)

Mazzillo, M.; Sciuto, A.; Mannino, G.; Renna, L.; Costa, N.; Badalà, P.

2016-10-01

Exposure to ultraviolet (UV) radiation is a major risk factor for most skin cancers. The sun is our primary natural source of UV radiation. The strength of the sun's ultraviolet radiation is expressed as Solar UV Index (UVI). UV-A (320-400 nm) and UV-B (290-320 nm) rays mostly contribute to UVI. UV-B is typically the most destructive form of UV radiation because it has enough energy to cause photochemical damage to cellular DNA. Also overexposure to UV-A rays, although these are less energetic than UV-B photons, has been associated with toughening of the skin, suppression of the immune system, and cataract formation. The use of preventive measures to decrease sunlight UV radiation absorption is fundamental to reduce acute and irreversible health diseases to skin, eyes and immune system. In this perspective UV sensors able to monitor in a monolithic and compact chip the UV Index and relative UV-A and UV-B components of solar spectrum can play a relevant role for prevention, especially in view of the integration of these detectors in close at hand portable devices. Here we present the preliminary results obtained on our UV-A sensor technology based on the use of hydrogenated Silicon Nitride (SiN:H) thin passivating layers deposited on the surface of thin continuous metal film Ni2Si/4H-SiC Schottky detectors, already used for UV-Index monitoring. The first UV-A detector prototypes exhibit a very low leakage current density of about 0.2 pA/mm2 and a peak responsivity value of 0.027 A/W at 330 nm, both measured at 0V bias.

Introducing Aliphatic Substitution with a Discovery Experiment Using Competing Electrophiles

ERIC Educational Resources Information Center

Curran, Timothy P.; Mostovoy, Amelia J.; Curran, Margaret E.; Berger, Clara

2016-01-01

A facile, discovery-based experiment is described that introduces aliphatic substitution in an introductory undergraduate organic chemistry curriculum. Unlike other discovery-based experiments that examine substitution using two competing nucleophiles with a single electrophile, this experiment compares two isomeric, competing electrophiles…

Cobalt ferrite based magnetostrictive materials for magnetic stress sensor and actuator applications

NASA Technical Reports Server (NTRS)

Jiles, David C. (Inventor); Paulsen, Jason A. (Inventor); Snyder, John E. (Inventor); Lo, Chester C. H. (Inventor); Ring, Andrew P. (Inventor); Bormann, Keith A. (Inventor)

2008-01-01

Magnetostrictive material based on cobalt ferrite is described. The cobalt ferrite is substituted with transition metals (such manganese (Mn), chromium (Cr), zinc (Zn) and copper (Cu) or mixtures thereof) by substituting the transition metals for iron or cobalt to form substituted cobalt ferrite that provides mechanical properties that make the substituted cobalt ferrite material effective for use as sensors and actuators. The substitution of transition metals lowers the Curie temperature of the material (as compared to cobalt ferrite) while maintaining a suitable magnetostriction for stress sensing applications.

Fluorescent J-aggregates of core-substituted perylene bisimides: studies on structure-property relationship, nucleation-elongation mechanism, and sergeants-and-soldiers principle.

PubMed

Kaiser, Theo E; Stepanenko, Vladimir; Würthner, Frank

2009-05-20

A series of highly soluble and fluorescent, at core tetraaryloxy-substituted and in imide positions hydrogen atom containing perylene bisimide (PBI) dyes 1a-e with varying peripheral side chains have been synthesized and thoroughly characterized. The self-assembly of these PBIs has been studied in detail by UV/vis, linear dichroism (LD) and circular dichroism (CD) spectroscopy, and scanning probe microscopy (AFM, STM). These studies revealed that the present PBIs self-assemble into extended double string cables, which consist of two hydrogen-bonded supramolecular polymeric chains of densely packed and strongly excitonically coupled PBI chromophores, providing highly fluorescent J-aggregates. The aggregation strength ("melting" temperature) and the fluorescence properties of these J-aggregates are dependent on the number and chain length of the peripheral alkoxy substituents, thus revealing a structure-property relationship. In contrast to previously reported assemblies of PBIs, for which the aggregation process is described by the isodesmic (or equal K) model, a cooperative nucleation-elongation mechanism applies for the aggregation of the present assemblies as revealed by concentration-dependent UV/vis absorption studies with the chiral PBI 1e, providing equilibrium constants for dimerization (= nucleation) of K(2) = 13 +/- 11 L mol(-1) and for elongation of K = 2.3 +/- 0.1 x 10(6) L mol(-1) in methylcyclohexane (MCH). LD spectroscopic measurements have been performed to analyze the orientation of the monomers within the aggregates. The nonlinearity of chiral amplification in PBI aggregates directed by sergeants-and-soldiers principle has been elucidated by coaggregation experiments of different PBI dyes using CD spectroscopy. The dimensions as well as the molecular arrangement of the monomeric units in assemblies have been explored by atomic force microscopy (AFM) and scanning tunneling microscopy (STM).

Structure-property relationship of 3-(4-substituted benzyl)-1,3-diazaspiro[4.4]nonane-2,4-diones as new potentional anticonvulsant agents. An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Lazić, Anita M.; Božić, Bojan Đ.; Vitnik, Vesna D.; Vitnik, Željko J.; Rogan, Jelena R.; Radovanović, Lidija D.; Valentić, Nataša V.; Ušćumlić, Gordana S.

2017-01-01

The structure-property relationship of newly synthesized 3-(4-substituted benzyl)-1,3-diazaspiro [4.4]nonane-2,4-diones was studied by experimental and calculated methods. The prepared compounds were characterized by UV-Vis, FT-IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. The crystal structure was elucidated by single-crystal X-ray diffraction. The 3-benzyl-1,3-diazaspiro[4.4]nonane-2,4-dione crystallizes in triclinic P-1 space group, with two crystallographically independent molecules in the asymmetric unit. Cyclopentane ring adopts an envelope conformation. A three-dimensional crystal packing is governed by hydrogen N-H⋯O bonds, numerous C-H⋯O/N and C-H … π interactions between neighboring molecules. Density functional theory (DFT) calculations with B3LYP and M06-2X methods using 6-311++G(d,p) basis set were performed to provide structural and spectroscopic information. Comparisons between experimental and calculated UV-Vis spectral properties suggest that the monomeric form of the investigated spirohydantoins is dominant in all used solvents. The effects of substituents on the absorption spectra of spirohydantoins are interpreted by correlation of absorption frequencies with Hammett equation. The lipophilicities of the investigated molecules were estimated by calculation of their log P values. Some of the spirohydantoins synthesized in this work, exhibit the lipophilicities comparable to the standard medicine anticonvulsant drug Phenytoin. The results obtained in this investigation afford guidelines for the preparation of new derivatives of spirohydantoin as potential anticonvulsant agents and for better understanding the structure-activity relationship.

Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

PubMed

Srithep, Sirinthip; Phattarapattamawong, Songkeart

2017-06-01

The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fiscal Year 2011 Director’s Strategic Initiative Final Report Heterogeneous Device Architectures Incorporating Nitride Semiconductors for Enhanced Functionality of Optoelectronic Devices

DTIC Science & Technology

2014-03-01

electromagnetic radiation across the spectrum from the ultraviolet ( UV ) to terahertz, heterogeneous integration of these materials with others having different...weak absorption that limit the QE of homogenous SiC-based photodetectors in the deep UV and near UV regions, respectively. Furthermore, we have...Polarization-Enhanced III-Nitride-SiC Avalanche Photodiodes Semiconductor-based ultraviolet ( UV ) avalanche photodetectors (APDs) have significant promise

Mesoporous silica aerogel as a drug carrier for the enhancement of the sunscreen ability of benzophenone-3.

PubMed

Li, C C; Chen, Y T; Lin, Y T; Sie, S F; Chen-Yang, Y W

2014-03-01

In the present study, about 45 and 34 wt% of benzophenone-3 (BP-3), an organic UV filter, was adsorbed on a high surface area mesoporous silica (MS) drug carrier to prepare BP-3-bearing MS (MSBP) sunscreen materials MSBP-1 and MSBP-2, respectively. The effect of the adsorption of BP-3 by MS on the UV protection ability of MSBP was demonstrated and a synergistic UV protection effect was observed in the as-prepared MSBP UV filters. Compared with free BP-3, adsorbed BP-3 had greatly reduced crystallinity and the dispersion of MSBP was significantly improved in the sunscreen. The in vitro sun protection factor (SPF) and in vitro UV-A values of the MSBP-2-based sunscreen was about 17.3% and 17.0% higher than that of free BP-3-based sunscreen, respectively, indicating that the ability of the sunscreen to protect against UV-B and UV-A improved because of the BP-3 content of the MS matrix. In addition, the decrease in SPF and UV-A values over time was significantly less in the MSBP-based sunscreens than in free BP-3-based sunscreen. Results of this study reveal that MS is a promising organic sunscreen carrier as well as a potential carrier for other topical drugs. Copyright © 2013 Elsevier B.V. All rights reserved.

Is ultraviolet exposure acquired at work the most important risk factor for cutaneous squamous cell carcinoma? Results of the population-based case-control study FB-181.

PubMed

Schmitt, J; Haufe, E; Trautmann, F; Schulze, H-J; Elsner, P; Drexler, H; Bauer, A; Letzel, S; John, S M; Fartasch, M; Brüning, T; Seidler, A; Dugas-Breit, S; Gina, M; Weistenhöfer, W; Bachmann, K; Bruhn, I; Lang, B M; Bonness, S; Allam, J P; Grobe, W; Stange, T; Westerhausen, S; Knuschke, P; Wittlich, M; Diepgen, T L

2018-02-01

Squamous cell carcinoma (SCC) is one of the most frequent types of cancer constituting a significant public health burden. Prevention strategies focus on limiting ultraviolet (UV) exposure during leisure time. However, the relative impact of occupational and nonoccupational UV exposure for SCC occurrence is unclear. To investigate the association between occupational and nonoccupational UV exposure for SCC in a multicentre population-based case-control study hypothesizing that high occupational UV exposure increases the risk of SCC. Consecutive patients with incident SCC (n = 632) were recruited from a German national dermatology network. Population-based controls (n = 996) without history of skin cancer were recruited from corresponding residents' registration offices and propensity score matched to cases. Lifetime UV exposure, sociodemographic and clinical characteristics were assessed by trained physicians. Occupational and nonoccupational UV exposure doses were estimated by masked investigators using established reference values. Odds ratios (ORs) and corresponding 95% confidence intervals (CIs) were assessed using conditional logistic regression adjusting for relevant confounders. Total solar UV exposure was significantly associated with increased SCC. The OR for high (> 90th percentile) vs. low (< 40th percentile) and high vs, moderate (40-59th percentile) occupational UV exposure was 1·95 (95% CI 1·19-3·18) and 2·44 (95% CI 1·47-4·06) for SCC. Adjusting for occupational UV exposure, nonoccupational UV exposure was not significantly related to SCC incidence. Dose-response relationships were observed for occupational but not for nonoccupational solar UV exposure. Solar occupational UV exposure is a major determinant of incident SCC. Our findings indicate that prevention strategies should be further expanded to the occupational setting. © 2017 British Association of Dermatologists.

In vitro photostability and photoprotection studies of a novel 'multi-active' UV-absorber.

PubMed

Venditti, E; Spadoni, T; Tiano, L; Astolfi, P; Greci, L; Littarru, G P; Damiani, E

2008-08-01

This paper reports on the synthesis and properties of a new UV-absorber (OC-NO) based on the most popular UV filter worldwide, ethylhexyl methoxycinnamate (OMC) in which the methoxy group has been replaced with a pyrrolidine nitroxide bearing antioxidant activity. This sunscreen active has therefore both UV-absorbing and antioxidant properties which could ideally address both the UV-B and UV-A skin photo-damage. For broad-spectrum coverage, the combinations of OC-NO with two commonly used UV-A absorbers (BMDBM and DHHB) were also studied. The results obtained reveal that OC-NO: (a) is as photostable as OMC after UV-A exposure; (b) acts as free radical scavenger as demonstrated by EPR and chemical studies; (c) reduces UV-A and UV-A+BMDBM induced lipid peroxidation in liposomes and cells, measured as reduced TBARS levels and increased C11-BODIPY red fluorescence, respectively; (d) has comparable antioxidant activity to that of vitamin E and BHT commonly used in skin care formulations; (e) is non-cytotoxic to human skin fibroblasts as assessed with the MTT assay when exposed to increasing doses of UV-A; and (f) OC-NO+DHHB is a promising, photostable broad spectrum UV-filter combination that concomitantly reduces UV-induced free radical damage. These results suggest that nitroxide/antioxidant-based UV-absorbers may pave the way for the utilization of 'multi-active' ingredients in sunscreens thereby reducing the number of ingredients in these formulations.

Origin of photoluminescence in β -G a2O3

NASA Astrophysics Data System (ADS)

Ho, Quoc Duy; Frauenheim, Thomas; Deák, Peter

2018-03-01

β -G a2O3 , a candidate material for power electronics and UV optoelectronics, shows strong room-temperature photoluminescence (PL). In addition to the three well-known bands of as-grown samples in the UV, blue, and green, also red PL was observed upon nitrogen doping. This raises the possibility of applying β -G a2O3 nanostructures as white phosphors. Using an optimized, Koopmans-compliant hybrid functional, we show that most intrinsic point defects, as well as substitutional nitrogen, act as deep acceptors, and each of the observed PL bands can be explained by electron recombination with a hole trapped in one of them. We suggest this mechanism to be general in wide-band-gap semiconductors which can only be doped n -type. Calculations on the nitrogen acceptor reproduce the observed red luminescence accurately. Earlier we have shown that not only the energy, but the polarization properties of the UV band can be explained by self-trapped hole states. Here we find that the blue band has its origin mainly in singly negative Ga-O divacancies, and the green band is caused dominantly by interstitial O atoms (with minor contribution of Ga vacancies to both). These assignments can explain the experimentally observed dependence of the PL bands on free-electron concentration and stoichiometry. The information provided here paves the way for the conscious tuning of light emission from β -G a2O3 .

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine (Pinus sylvestris) wood. Part II. Hydrophilic compounds.

PubMed

Nuopponen, M; Willför, S; Jääskeläinen, A-S; Vuorinen, T

2004-11-01

Hydrophilic extracts of Scots pine (Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm(-1). Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm(-1). The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm(-1). The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm(-1)) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine ( Pinus sylvestris) wood . Part II. Hydrophilic compounds

NASA Astrophysics Data System (ADS)

Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Vuorinen, T.

2004-11-01

Hydrophilic extracts of Scots pine ( Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm -1. Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm -1. The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm -1. The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm -1) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

UV-screening chitosan nanocontainers: increasing the photostability of encapsulated materials and controlled release

NASA Astrophysics Data System (ADS)

Anumansirikul, Nattaporm; Wittayasuporn, Mayura; Klinubol, Patcharawalai; Tachaprutinun, A.; Wanichwecharungruang, Supason P.

2008-05-01

Methyl ether terminated poly(ethylene glycol)-4-methoxycinnamoylphthaloylchitosan (PCPLC), a UV absorptive polymer, and methyl ether terminated poly(ethylene glycol)-phthaloylchitosan (PPLC) were synthesized, characterized and self-assembled into stable water-dispersible spherical nanoparticles. The encapsulation of a model compound, 2-ethylhexyl-4-methoxycinnamate (EHMC), was carried out to give particles with 67% (w/w) EHMC loading. The E to Z photoisomerization of EHMC encapsulated inside both particles was monitored and compared to non-encapsulated EHMC. Minimal E to Z photoisomerization was observed when EHMC was encapsulated in PCPLC particles prepared from a polymer with a maximum degree of 4-methoxycinnamoyl substitution. The results indicated that the grafted UVB absorptive chromophore, 4-methoxycinnamoyl moieties, situated at the shell of PCPLC nanoparticles acted as a UV-filtering barrier, protecting the encapsulated EHMC from the UVB radiation, thus minimizing its photoisomerization. In vitro experiments revealed the pH-dependent controlled release of EHMC from PCPLC and PPLC particles. Ex vivo experiments, using a Franz diffusion cell with baby mouse skin, indicated that neither PPLC nor PCPLC particles could penetrate the skin into the receptor medium after a 24 h topical application. When applied on the baby mouse skin, both EHMC-encapsulated PPLC and EHMC-encapsulated PCPLC showed comparable controlled releases of the EHMC. The released EHMC could transdermally penetrate the baby mouse skin.

Occupational UV-Exposure is a Major Risk Factor for Basal Cell Carcinoma: Results of the Population-Based Case-Control Study FB-181.

PubMed

Schmitt, Jochen; Haufe, Eva; Trautmann, Freya; Schulze, Hans-Joachim; Elsner, Peter; Drexler, Hans; Bauer, Andrea; Letzel, Stephan; John, Swen Malte; Fartasch, Manigé; Brüning, Thomas; Seidler, Andreas; Dugas-Breit, Susanne; Gina, Michal; Weistenhöfer, Wobbeke; Bachmann, Klaus; Bruhn, Ilka; Lang, Berenice Mareen; Bonness, Sonja; Allam, Jean Pierre; Grobe, William; Stange, Thoralf; Westerhausen, Stephan; Knuschke, Peter; Wittlich, Marc; Diepgen, Thomas Ludwig

2018-01-01

The aim of this study was to investigate the role of occupational and nonoccupational ultraviolet (UV)-exposure concerning the development of basal cell carcinoma (BCC). We undertook a population-based multicenter case-control study. Patients with first incident BCC (n = 836) were propensity score matched by age and sex to controls without skin cancer (n = 836). Sociodemographic characteristics, clinical characteristics, and lifetime UV-exposure were assessed by trained investigators. The differential estimation of occupational and nonoccupational UV-exposure dosages was based on validated instruments and established reference values. Associations were assessed using multivariable-adjusted conditional logistic regression models. Individuals with high levels of occupational UV-exposure were at significantly increased BCC-risk compared with individuals with low [odds ratio (OR) 1.84; 95% confidence interval (95% CI) 1.19 to 2.83 and moderate (OR 1.97; 95% CI 1.20 to 3.22) occupational UV-exposure. Nonoccupational UV-exposure was not independently associated with BCC. Skin cancer prevention strategies should be expanded to the occupational setting.

Optimisation of UV irradiation as a binding site conserving method for crosslinking collagen-based scaffolds.

PubMed

Davidenko, Natalia; Bax, Daniel V; Schuster, Carlos F; Farndale, Richard W; Hamaia, Samir W; Best, Serena M; Cameron, Ruth E

2016-01-01

Short wavelength (λ = 254 nm) UV irradiation was evaluated over a range of intensities (0.06 to 0.96 J/cm(2)) as a means of cross-linking collagen- and gelatin-based scaffolds, to tailor their material characteristics whilst retaining biological functionality. Zero-link carbodiimide treatments are commonly applied to collagen-based materials, forming cross-links from carboxylate anions (for example the acidic E of GFOGER) that are an essential part of integrin binding sites on collagen. Cross-linking these amino acids therefore disrupts the bioactivity of collagen. In contrast, UV irradiation forms bonds from less important aromatic tyrosine and phenylalanine residues. We therefore hypothesised that UV cross-linking would not compromise collagen cell reactivity. Here, highly porous (~99 %) isotropic, collagen-based scaffolds were produced via ice-templating. A series of scaffolds (pore diameters ranging from 130-260 μm) with ascending stability in water was made from gelatin, two different sources of collagen I, or blends of these materials. Glucose, known to aid UV crosslinking of collagen, was added to some lower-stability formulations. These scaffolds were exposed to different doses of UV irradiation, and the scaffold morphology, dissolution stability in water, resistance to compression and cell reactivity was assessed. Stabilisation in aqueous media varied with both the nature of the collagen-based material employed and the UV intensity. Scaffolds made from the most stable materials showed the greatest stability after irradiation, although the levels of cross-linking in all cases were relatively low. Scaffolds made from pure collagen from the two different sources showed different optimum levels of irradiation, suggesting altered balance between stabilisation from cross-linking and destabilisation from denaturation. The introduction of glucose into the scaffold enhanced the efficacy of UV cross-linking. Finally, as hypothesized, cell attachment, spreading and proliferation on collagen materials were unaffected by UV cross-linking. UV irradiation may therefore be used to provide relatively low level cross-linking of collagen without loss of biological functionality.

Research on APD-based non-line-of-sight UV communication system

NASA Astrophysics Data System (ADS)

Wang, Rongyang; Wang, Ling; Li, Chao; Zhang, Wenjing; Yuan, Yonggang; Xu, Jintong; Zhang, Yan; Li, Xiangyang

2010-10-01

In this paper, specific issues in designing an avalanche photodiode (APD)-based non-line-of-sight (NLOS) ultraviolet (UV) communication system are investigated. A proper wavelength of the UV LEDs and a system configuration should be considered carefully to assure the feasibility of this system. Using the single scattering model, the received optical power at the sensitive area of the APD can be calculated. According to the calculation, it revealed that the scattered ultraviolet signal level was very low; therefore, a post signal processing circuit was necessary. The authors put forward the key components of the circuit based on the compromise between signal bandwidth and gain. The performance of this circuit was evaluated by means of software simulation, and continued work was involved to improve its signal noise ratio (SNR). The transmitter used in this system was 365 nm UV LED array. Strictly speaking, this was not the practical outdoor UV communication system. Since the scattering coefficient of 365 nm UV only drops a little compared with solar blind UV, the research-grade UV communication could be carried out in a darkroom without a great influence. By combining an APD with a compound parabolic concentrator (CPC) optical system, the effective collection area and field of view (FOV) of the detector could be adjusted. Several issues were also raised to improve the performance of UV communication system, including using more powerful UV LEDs and choosing suitable modulation schemes.

The influence of specific neighboring bases on substitution bias in noncoding regions of the plant chloroplast genome.

PubMed

Morton, B R; Oberholzer, V M; Clegg, M T

1997-09-01

Substitutions occurring in noncoding sequences of the plant chloroplast genome violate the independence of sites that is assumed by substitution models in molecular evolution. The probability that a substitution at a site is a transversion, as opposed to a transition, increases significantly with increasing A + T content of the two adjacent nucleotides. In the present study, this dependency of substitutions on local context is examined further in a number of noncoding regions from the chloroplast genome of members of the grass family (Poaceae). Two features were examined; the influence of specific neighboring bases, as opposed to the general A + T content, on transversion proportion and an influence on substitutions by nucleotides other than the two immediately adjacent to the site of substitution. In both cases, a significant effect was found. In the case of specific nucleotides, transversion proportion is significantly higher at sites with a pyrimidine immediately 5' on either strand. Substitutions at sites of the type YNR, where N is the site of substitution, have the highest rate of transversion. This specific effect is secondary to the A + T content effect such that, in terms of proportion of substitutions that are transversions, the nucleotides are ranked T > A > C > G as to their effect when they are immediately 5' to the site of substitution. In the case of nucleotides other than the immediate neighbors, a significant influence on substitution dynamics is observed in the case where the two neighboring bases are both A and/or T. Thus, substitutions are primarily, but not exclusively, influenced by the composition of the two nucleotides that are immediately adjacent. These results indicate that the pattern of molecular evolution of the plant chloroplast genome is extremely complex as a result of a variety of inter-site dependencies.

Light-extraction enhancement of GaN-based 395  nm flip-chip light-emitting diodes by an Al-doped ITO transparent conductive electrode.

PubMed

Xu, Jin; Zhang, Wei; Peng, Meng; Dai, Jiangnan; Chen, Changqing

2018-06-01

The distinct ultraviolet (UV) light absorption of indium tin oxide (ITO) limits the performance of GaN-based near-UV light-emitting diodes (LEDs). Herein, we report an Al-doped ITO with enhanced UV transmittance and low sheet resistance as the transparent conductive electrode for GaN-based 395 nm flip-chip near-UV LEDs. The thickness dependence of optical and electrical properties of Al-doped ITO films is investigated. The optimal Al-doped ITO film exhibited a transmittance of 93.2% at 395 nm and an average sheet resistance of 30.1  Ω/sq. Meanwhile, at an injection current of 300 mA, the forward voltage decreased from 3.14 to 3.11 V, and the light output power increased by 13% for the 395 nm near-UV flip-chip LEDs with the optimal Al-doped ITO over those with pure ITO. This Letter provides a simple and repeatable approach to further improve the light extraction efficiency of GaN-based near-UV LEDs.

Soil burial biodegradation studies of palm oil-based UV-curable films

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

Tajau, Rida, E-mail: rida@nuclearmalaysia.gov.my; Salleh, Mek Zah, E-mail: mekzah@nuclearmalaysia.gov.my; Salleh, Nik Ghazali Nik, E-mail: nik-ghazali@nuclearmalaysia.gov.my

The palm oil-based ultraviolet (uv)-curable films were subjected to an outdoor soil burial test to investigate the biodegradation under natural environment. The films were burial in the soil experiment plot at the Nuclear Malaysia’s Dengkil complex. The uv-curable films were synthesized from the epoxidized palm oil acrylated (EPOLA) resin and the polyurethane palm oil (POBUA) resin, respectively. Biodegradation tests are more specific to burial film in soil experiments for 12 months under natural conditions. The biodegradability of palm oil resin based uv-curable films were investigated and compared with the petrochemical resin based film. The films properties were compared with respectmore » to properties of the thermal characteristic, the crystallinity, the morphology and the weight loss which are analyzed using the thermogravimetric analysis (TGA), the differential scanning calorimetry (DSC), the scanning electron microscope (SEM), an optical microscope and the weight loss of film calculation. These findings suggested that the palm oil-based uv-curable films show quite satisfactory biodegradation levels.« less

Soil burial biodegradation studies of palm oil-based UV-curable films

NASA Astrophysics Data System (ADS)

Tajau, Rida; Salleh, Mek Zah; Salleh, Nik Ghazali Nik; Abdurahman, Mohamad Norahiman; Salih, Ashraf Mohammed; Fathy, Siti Farhana; Azman, Anis Asmi; Hamidi, Nur Amira

2016-01-01

The palm oil-based ultraviolet (uv)-curable films were subjected to an outdoor soil burial test to investigate the biodegradation under natural environment. The films were burial in the soil experiment plot at the Nuclear Malaysia's Dengkil complex. The uv-curable films were synthesized from the epoxidized palm oil acrylated (EPOLA) resin and the polyurethane palm oil (POBUA) resin, respectively. Biodegradation tests are more specific to burial film in soil experiments for 12 months under natural conditions. The biodegradability of palm oil resin based uv-curable films were investigated and compared with the petrochemical resin based film. The films properties were compared with respect to properties of the thermal characteristic, the crystallinity, the morphology and the weight loss which are analyzed using the thermogravimetric analysis (TGA), the differential scanning calorimetry (DSC), the scanning electron microscope (SEM), an optical microscope and the weight loss of film calculation. These findings suggested that the palm oil-based uv-curable films show quite satisfactory biodegradation levels.

Kinetic and spectroscopic characterization of tungsten-substituted DMSO reductase from Rhodobacter sphaeroides.

PubMed

Pacheco, Josué; Niks, Dimitri; Hille, Russ

2018-03-01

We have examined the kinetic and spectroscopic properties of a tungsten-substituted form of DMSO reductase from Rhodobacter sphaeroides, an enzyme that normally possesses molybdenum. Partial reduction with sodium dithionite yields a well-resolved W(V) EPR signal of the so-called "high-g split" type that exhibits markedly greater g-anisotropy than the corresponding Mo(V) signal of the native form of the enzyme, with the g values shifted to higher magnetic field by as much as Δg ave  = 0.056. Deuteration of the enzyme confirms that the coupled proton is solvent-exchangeable, allowing us to accurately simulate the tungsten hyperfine coupling. Global curve-fitting analysis of UV/vis absorption spectra observed in the course of the reaction of the tungsten-substituted enzyme with sodium dithionite affords a well-defined absorption spectrum for the W(V) species. Surprisingly, the absorption spectrum for this species exhibits significantly larger molar extinction coefficients than either the reduced or the oxidized spectrum. This spectrum, in conjunction with those for fully oxidized W(VI) and fully reduced W(IV) enzyme, has been used to deconvolute the absorption spectra seen in the course of turnover, in the which enzyme is reacted with sodium dithionite and DMSO, demonstrating that the W(V) is an authentic catalytic intermediate that accumulates to approximately 50% of the total enzyme in the steady state.

Synthesis, characterization and photophysical-theoretical analysis of compounds A-π-D. 1. Effect of alkyl-phenyl substituted amines in photophysical properties

NASA Astrophysics Data System (ADS)

Ortega, E.; Montecinos, R.; Cattin, L.; Díaz, F. R.; del Valle, M. A.; Bernède, J. C.

2017-08-01

The study of new dipolar A-π-D molecules, which have an acceptor (A) and donor (D) charge joined by a conjugate bridge, have been an attention focus in the recent years due their different properties. In the current work, a molecular system has been modified in order to compare the effect on properties, such as quantum yield. Thus, two series were generated (alkyl- and alkoxy-substituted) to determine if molecules with tertiary asymmetric amines change their optical properties and whether quantum yield is affected. The different products have been characterized by several techniques such as UV-Vis spectrophotometry, elemental analysis, NMR, FT-IR, mass spectroscopy and fluorescence spectroscopy. Furthermore, their behavior in eight organic solvents, dichloromethane, tetrahydrofuran, ethyl acetate, 1,4-dioxane, acetone, acetonitrile, dimethylformamide and dimethylsulfoxide were experimentally and theoretically studied. The quantum yields were higher for the alkyl-substituted series. Theoretically, the dihedral angles formed between the tertiary amine and carbonyl group moieties have a correlation with quantum yield values, helping to explain why they are higher in non-polar solvents. Consequently, the maximum quantum yield was obtained with (E)-2-cyano-3-(5-((E)-2-(9,9-diethyl-7-(methyl(phenyl)amino)-9H-fluoren-2-yl) vinyl)thiophen-2-yl)acrylic acid (M8-1) in 1,4-dioxane, reaching 98.8%.

Optical, Thermal, and Mechanical Characterization of Ga2 Se3 -Added GLS Glass.

PubMed

Ravagli, Andrea; Craig, Christopher; Alzaidy, Ghada A; Bastock, Paul; Hewak, Daniel W

2017-07-01

Gallium lanthanum sulfide glass (GLS) has been widely studied in the last 40 years for middle-infrared applications. In this work, the results of the substitution of selenium for sulphur in GLS glass are described. The samples are prepared via melt-quench method in an argon-purged atmosphere. A wide range of compositional substitutions are studied to define the glass-forming region of the modified material. The complete substitution of Ga 2 S 3 by Ga 2 Se 3 is achieved by involving new higher quenching rate techniques compared to those containing only sulfides. The samples exhibiting glassy characteristics are further characterized. In particular, the optical and thermal properties of the sample are investigated in order to understand the role of selenium in the formation of the glass. The addition of selenium to GLS glass generally results in a lower glass transition temperature and an extended transmission window. Particularly, the IR edge is found to be extended from about 9 µm for GLS glass to about 15 µm for Se-added GLS glass defined by the 50% transmission point. Furthermore, the addition of selenium does not affect the UV edge dramatically. The role of selenium is hypothesized in the glass formation to explain these changes. © 2017 University of Southampton. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization and serum albumin binding studies of vitamin K3 derivatives.

PubMed

Suganthi, Murugesan; Elango, Kuppanagounder P

2017-01-01

Synthesis, characterization and bovine serum albumin (BSA) binding properties of three derivatives of vitamin K3 have been described. Results of UV-Vis and fluorescence spectra indicate complexation between BSA and the ligands with conformational changes in protein, which is strongly supported by synchronous and three dimensional fluorescence studies. Addition of the ligands quenches the fluorescence of BSA which is accompanied by reduction in quantum yield (Ф) from 0.1010 to 0.0775-0.0986 range. Thermodynamic investigations reveal that hydrophobic interaction is the major binding force in the spontaneous binding of these ligands with BSA. The binding constants obtained depend on the substituent present in the quinone ring, which correlates linearly with the Taft's field substituent constant (σ F ). The results show that compound with strong electron withdrawing nitro-group forms relatively stronger complex with BSA than amino and thioglycolate substituted ones. Circular dichroism studies show that the α-helical content of the protein, upon complexation with the ligands, decreases in the case of amino and nitro substituted vitamin K3 while increases in thioglycolate substituted compound. Molecular docking studies indicated that the vitamin K3 derivatives are surrounded by hydrophobic residues of the BSA molecule, which is in good agreement with the results of fluorescence spectral and thermodynamic studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Iohexol degradation in wastewater and urine by UV-based Advanced Oxidation Processes (AOPs): Process modeling and by-products identification.

PubMed

Giannakis, Stefanos; Jovic, Milica; Gasilova, Natalia; Pastor Gelabert, Miquel; Schindelholz, Simon; Furbringer, Jean-Marie; Girault, Hubert; Pulgarin, César

2017-06-15

In this work, an Iodinated Contrast Medium (ICM), Iohexol, was subjected to treatment by 3 Advanced Oxidation Processes (AOPs) (UV, UV/H 2 O 2 , UV/H 2 O 2 /Fe 2+ ). Water, wastewater and urine were spiked with Iohexol, in order to investigate the treatment efficiency of AOPs. A tri-level approach has been deployed to assess the UV-based AOPs efficacy. The treatment was heavily influenced by the UV transmittance and the organics content of the matrix, as dilution and acidification improved the degradation but iron/H 2 O 2 increase only moderately. Furthermore, optimization of the treatment conditions, as well as modeling of the degradation was performed, by step-wise constructed quadratic or product models, and determination of the optimal operational regions was achieved through desirability functions. Finally, global chemical parameters (COD, TOC and UV-Vis absorbance) were followed in parallel with specific analyses to elucidate the degradation process of Iohexol by UV-based AOPs. Through HPLC/MS analysis the degradation pathway and the effects the operational parameters were monitored, thus attributing the pathways the respective modifications. The addition of iron in the UV/H 2 O 2 process inflicted additional pathways beneficial for both Iohexol and organics removal from the matrix. Copyright © 2016 Elsevier Ltd. All rights reserved.

TOMS UV Algorithm: Problems and Enhancements. 2

NASA Technical Reports Server (NTRS)

Krotkov, Nickolay; Herman, Jay; Bhartia, P. K.; Seftor, Colin; Arola, Antti; Kaurola, Jussi; Kroskinen, Lasse; Kalliskota, S.; Taalas, Petteri; Geogdzhaev, I.

2002-01-01

Satellite instruments provide global maps of surface ultraviolet (UV) irradiance by combining backscattered radiance measurements with radiative transfer models. The models are limited by uncertainties in input parameters of the atmosphere and the surface. We evaluate the effects of possible enhancements of the current Total Ozone Mapping Spectrometer (TOMS) surface UV irradiance algorithm focusing on effects of diurnal variation of cloudiness and improved treatment of snow/ice. The emphasis is on comparison between the results of the current (version 1) TOMS UV algorithm and each of the changes proposed. We evaluate different approaches for improved treatment of pixel average cloud attenuation, with and without snow/ice on the ground. In addition to treating clouds based only on the measurements at the local time of the TOMS observations, the results from other satellites and weather assimilation models can be used to estimate attenuation of the incident UV irradiance throughout the day. A new method is proposed to obtain a more realistic treatment of snow covered terrain. The method is based on a statistical relation between UV reflectivity and snow depth. The new method reduced the bias between the TOMS UV estimations and ground-based UV measurements for snow periods. The improved (version 2) algorithm will be applied to re-process the existing TOMS UV data record (since 1978) and to the future satellite sensors (e.g., Quik/TOMS, GOME, OMI on EOS/Aura and Triana/EPIC).

Switching on fluorescence for selective visual recognition of naringenin and morin with a metal-organic coordination polymer of Zn(bix) [bix = 1,4-bis(imidazol-1-ylmethyl)benzene

NASA Astrophysics Data System (ADS)

Zhao, Xi Juan; Wang, Hui Juan; Liang, Li Jiao; Li, Yuan Fang

2013-02-01

Flavonoids such as naringenin and morin are ubiquitous in a wide range of foods isolated from plants, and have diverse effects on plants even on human health. Here, we establish a selective visual method for recognition of aringenin and morin based on the "switched on" fluorescence induced by a metal-organic coordination polymer of Zn(bix) [bix = 1,4-bis(imidazol-1-ylmethyl)benzene]. Owing to the coordination interaction of aringenin and morin with Zn(II) from the polymeric structure of Zn(bix), the conformational free rotation of naringenin and morin is restricted leading to relatively rigid structures. And as a consequence, the fluorescence is switched on. While luteolin and quercetin, holding a very similar structure with naringenin and morin, have no such fluorescence enhancement most likely owing to the 3'-hydroxy substitution in the B ring. Under 365 nm UV lamp light, we can visually recognize and discriminate naringenin and morin from them each other and luteolin as well as quercetin based on the colors of their emission. With this recognition system, the detection of naringenin and morin in human urine was made with satisfactory results.

Efficient removal of endosulfan from aqueous solution by UV-C/peroxides: a comparative study.

PubMed

Shah, Noor S; He, Xuexiang; Khan, Hasan M; Khan, Javed Ali; O'Shea, Kevin E; Boccelli, Dominic L; Dionysiou, Dionysios D

2013-12-15

This study explored the efficiency of UV-C-based advanced oxidation processes (AOPs), i.e., UV/S2O8(2-), UV/HSO5(-), and UV/H2O2 for the degradation of endosulfan, an organochlorine insecticide and an emerging water pollutant. A significant removal, 91%, 86%, and 64%, of endosulfan, at an initial concentration of 2.45 μM and UV fluence of 480 mJ/cm(2), was achieved by UV/S2O8(2-), UV/HSO5(-), and UV/H2O2 processes, respectively, at a [peroxide]0/[endosulfan]0 molar ratio of 20. The efficiency of these processes was, however, inhibited in the presence of radical scavengers, such as alcohols (e.g., tertiary butyl alcohol and isopropyl alcohol) and natural organic matter (NOM). The inhibition was also influenced by common inorganic anions in the order of nitrite > bicarbonate > chloride > nitrate ≈ sulfate. The observed pseudo-first-order rate constant decreased while the degradation rate increased with increasing initial concentration of the target contaminant. The degradation mechanism of endosulfan by the AOPs was evaluated revealing the main by-product as endosulfan ether. Results of this study suggest that UV-C-based AOPs are potential methods for the removal of pesticides, such as endosulfan and its by-products, from contaminated water. Copyright © 2013 Elsevier B.V. All rights reserved.

Sulfamethazine degradation in water by the VUV/UV process: Kinetics, mechanism and antibacterial activity determination based on a mini-fluidic VUV/UV photoreaction system.

PubMed

Li, Mengkai; Wang, Chen; Yau, Miaoling; Bolton, James R; Qiang, Zhimin

2017-01-01

A mini-fluidic VUV/UV photoreaction system (MVPS) was developed in our previous study, and it was demonstrated as a powerful tool for studies on pollutant degradation by the VUV/UV process. In this study, we investigated the VUV/UV photodegradation of sulfamethazine (SMN), one of the most frequently detected antibiotics in the environment. The determination methods of photochemical kinetic parameters (e.g., photon fluence-based rate constant and quantum yield) were developed based on the MVPS. The photon fluence-based reaction rate constants for SMN degradation by UV alone and VUV/UV processes were determined as 0.07 × 10 3 and 4.11 × 10 3  m 2  einstein -1 , respectively, while their quantum yields were calculated as 0.019 and 0.369, respectively. The second-order reaction rate constant between hydroxyl radical (HO • ) and SMN was determined to be 8.9 × 10 9  M -1  s -1 in VUV/UV irradiation experiments, which were conducted without addition of any other chemical. The pH effect on the SMN degradation by the VUV/UV process arose principally from SMN and HO speciation. In addition, six byproducts were identified and the potential degradation pathways of SMN including hydroxylation and SO 2 elimination were proposed. The antibacterial activity of the SMN solution, assessed by the growth inhibition tests of Escherichia coli, decreased by about 80% after VUV/UV treatment up to a photon fluence of 3.58 × 10 -3  einstein m -2 . This study has developed methods for the determination of photochemical kinetic parameters using the newly developed MVPS and has demonstrated that the VUV/UV process is an effective technology to remove sulfonamide antibiotics in water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases

PubMed Central

Barbatti, Mario; Aquino, Adélia J. A.; Szymczak, Jaroslaw J.; Nachtigallová, Dana; Hobza, Pavel; Lischka, Hans

2010-01-01

A comprehensive effort in photodynamical ab initio simulations of the ultrafast deactivation pathways for all five nucleobases adenine, guanine, cytosine, thymine, and uracil is reported. These simulations are based on a complete nonadiabatic surface-hopping approach using extended multiconfigurational wave functions. Even though all five nucleobases share the basic internal conversion mechanisms, the calculations show a distinct grouping into purine and pyrimidine bases as concerns the complexity of the photodynamics. The purine bases adenine and guanine represent the most simple photodeactivation mechanism with the dynamics leading along a diabatic ππ* path directly and without barrier to the conical intersection seam with the ground state. In the case of the pyrimidine bases, the dynamics starts off in much flatter regions of the ππ* energy surface due to coupling of several states. This fact prohibits a clear formation of a single reaction path. Thus, the photodynamics of the pyrimidine bases is much richer and includes also nπ* states with varying importance, depending on the actual nucleobase considered. Trapping in local minima may occur and, therefore, the deactivation time to the ground state is also much longer in these cases. Implications of these findings are discussed (i) for identifying structural possibilities where singlet/triplet transitions can occur because of sufficient retention time during the singlet dynamics and (ii) concerning the flexibility of finding other deactivation pathways in substituted pyrimidines serving as candidates for alternative nucleobases. PMID:21115845

Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

PubMed

Sharma, Jyoti; Mishra, I M; Kumar, Vineet

2015-06-01

This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Design, fabrication, and measurement of two silicon-based ultraviolet and blue-extended photodiodes

NASA Astrophysics Data System (ADS)

Chen, Changping; Wang, Han; Jiang, Zhenyu; Jin, Xiangliang; Luo, Jun

2014-12-01

Two silicon-based ultraviolet (UV) and blue-extended photodiodes are presented, which were fabricated for light detection in the ultraviolet/blue spectral range. Stripe-shaped and octagon-ring-shaped structures were designed to verify parameters of the UV-responsivity, UV-selectivity, breakdown voltage, and response time. The ultra-shallow lateral pn junction had been successfully realized in a standard 0.5-μm complementary metal oxide semiconductor (CMOS) process to enlarge the pn junction area, enhance the absorption of UV light, and improve the responsivity and quantum efficiency. The test results illustrated that the stripe-shaped structure has the lower breakdown voltage, higher UV-responsicity, and higher UV-selectivity. But the octagon-ring-shaped structure has the lower dark current. The response time of both structures was almost the same.

UV LED charge control of an electrically isolated proof mass in a Gravitational Reference Sensor configuration at 255 nm

NASA Astrophysics Data System (ADS)

Balakrishnan, Karthik; Sun, Ke-Xun

2012-07-01

Precise control over the potential of an electrically isolated proof mass is necessary for the operation of devices such as a Gravitational Reference Sensor (GRS) and satellite missions such as LISA. We show that AlGaN UV LEDs operating at 255 nm are an effective substitute for Mercury vapor lamps used in previous missions because of their ability to withstand space qualification levels of vibration and thermal cycling. After 27 thermal and thermal vacuum cycles and 9 minutes of 14.07 g RMS vibration, there is less than 3% change in current draw, less than 15% change in optical power, and no change in spectral peak or FWHM (full width at half maximum). We also demonstrate UV LED stimulated photoemission from a wide variety of thin film carbide proof mass coating candidates (SiC, Mo2C, TaC, TiC, ZrC) that were applied using electron beam evaporation on an Aluminum 6061-T6 substrate. All tested carbide films have measured quantum efficiencies of 3.8-6.8*10^-7 and reflectivities of 0.11-0.15, which compare favorably with the properties of previously used gold films. We demonstrate the ability to control proof mass potential on an 89 mm diameter spherical proof mass over a 20 mm gap in a GRS-like configuration. Proof mass potential was measured via a non-contact DC probe, which would allow control without introducing dynamic forcing of the spacecraft. Finally we provide a look ahead to an upcoming technology demonstration mission of UV LEDs and future applications toward charge control of electrically isolated proof masses.

p48 Activates a UV-Damaged-DNA Binding Factor and Is Defective in Xeroderma Pigmentosum Group E Cells That Lack Binding Activity

PubMed Central

Hwang, Byung Joon; Toering, Stephanie; Francke, Uta; Chu, Gilbert

1998-01-01

A subset of xeroderma pigmentosum (XP) group E cells lack a factor that binds to DNA damaged by UV radiation. This factor can be purified to homogeneity as p125, a 125-kDa polypeptide. However, when cDNA encoding p125 is translated in vitro, only a small fraction binds to UV-damaged DNA, suggesting that a second factor is required for the activation of p125. We discovered that most hamster cell lines expressed inactive p125, which was activated in somatic cell hybrids containing human chromosome region 11p11.2-11cen. This region excluded p125 but included p48, which encodes a 48-kDa polypeptide known to copurify with p125 under some conditions. Expression of human p48 activated p125 binding in hamster cells and increased p125 binding in human cells. No such effects were observed from expression of p48 containing single amino acid substitutions from XP group E cells that lacked binding activity, demonstrating that the p48 gene is defective in those cells. Activation of p125 occurred by a “hit-and-run” mechanism, since the presence of p48 was not required for subsequent binding. Nevertheless, p48 was capable of forming a complex with p125 either bound to UV-damaged DNA or in free solution. It is notable that hamster cells fail to efficiently repair cyclobutane pyrimidine dimers in nontranscribed DNA and fail to express p48, which contains a WD motif with homology to proteins that reorganize chromatin. We propose that p48 plays a role in repairing lesions that would otherwise remain inaccessible in nontranscribed chromatin. PMID:9632823

A novel cyanide-selective colorimetric and fluorescent chemosensor: first molecular security keypad lock based on phosphotungstic acid and CN- inputs.

PubMed

Tavallali, Hossein; Deilamy-Rad, Gohar; Parhami, Abolfath; Hasanli, Nahid

2014-02-15

Rhodamine B (RhB) an available dye has been developed as novel and efficient colorimetric and fluorometric chemosensor for cyanide ions in an absolutely aqueous media. The UV-vis absorption and fluorescent emission titrations experiments have been employed to study the sensing process. RhB could act as an efficient "ON-OFF" fluorescent response for phosphotungstic acid (H3PW12O40 or PTA) based on an ion associate process. Also (RhB(+))3 · PTA(3-) could operate as an "OFF-ON" fluorescent sensor for cyanide anions based on a ligand substitution process. It has been identified as highly sensitive probe for CN(-) which responds at 0.3 and 0.04 μmol L(-1) concentration levels by absorption and fluorescent method respectively. Depending upon the sequence of addition of PTA and CN(-) ions into the solution, RhB could be as a molecular security keypad lock with PTA and CN(-) inputs. The ionic inputs to new fluorophore have been mimicked as a superimposed electronic molecular keypad lock. The results were compared successfully (>96%) with the data of a spectrophotometry approved method (EPA 9014-1) for cyanide ions. Copyright © 2013 Elsevier B.V. All rights reserved.

All-Solid-State UV Transmitter Development for Ozone Sensing Applications

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S.; Singh, Upendra N.; Armstrong, Darrell Jr.

2009-01-01

In this paper, recent progress made in the development of an all-solid-state UV transmitter suitable for ozone sensing applications from space based platforms is discussed. A nonlinear optics based UV setup based on Rotated Image Singly Resonant Twisted Rectangle (RISTRA) optical parametric oscillator (OPO) module was effectively coupled to a diode pumped, single longitudinal mode, conductively cooled, short-pulsed, high-energy Nd:YAG laser operating at 1064 nm with 50 Hz PRF. An estimated 10 mJ/pulse with 10% conversion efficiency at 320 nm has been demonstrated limited only by the pump pulse spatial profile. The current arrangement has the potential for obtaining greater than 200 mJ/pulse. Previously, using a flash-lamp pumped Nd:YAG laser with round, top-hat profile, up to 24% IR-UV conversion efficiency was achieved with the same UV module. Efforts are underway to increase the IR-UV conversion efficiency of the all solid-state setup by modifying the pump laser spatial profile along with incorporating improved OPO crystals.

Designing of a fluoride selective receptor through molecular orbital engineering

NASA Astrophysics Data System (ADS)

Mishra, Rakesh K.; Kumar, Virendra; Diwan, Uzra; Upadhyay, K. K.; Roy Chowdhury, P. K.

2012-11-01

The stepwise substitution of appropriate groups over the 3-[(2,4-dinitro-phenyl)-hydrazono]-butyric acid ethyl ester (R3) lead receptor R1 which showed selectivity towards fluoride in DMSO. The UV-vis and 1H NMR titration studies revealed the details of the binding between receptor R1 and fluoride. The receptor R1 also recognized fluoride in a toothpaste solution to as low as 50 ppm. The theoretical simulations of recognition event at Density Functional Theory (DFT) level using B3LYP/6-31G** basis set and polarizable continuum model (PCM) approach lead a semi-quantitative match with the experimental results.

A Low-Cost Liquid-Chromatography System Using a Spectronic 20-Based Detector.

ERIC Educational Resources Information Center

Jezorek, John R.; And Others

1986-01-01

Describes the design and evaluation of a Spectronic 20-based detector as well as a simple system for postcolumn derivatization useful for metal-ion chromatographic detection. Both detection and derivatization can be performed in the ultra-violet (UV) mode using a low-cost UV-visible spectrophotometer and UV-region derivatization reagents. (JN)

Analyzing Exonuclease-Induced Hyperchromicity by Uv Spectroscopy: An Undergraduate Biochemistry Laboratory Experiment

ERIC Educational Resources Information Center

Ackerman, Megan M.; Ricciardi, Christopher; Weiss, David; Chant, Alan; Kraemer-Chant, Christina M.

2016-01-01

An undergraduate biochemistry laboratory experiment is described that utilizes free online bioinformatics tools along with readily available exonucleases to study the effects of base stacking and hydrogen bonding on the UV absorbance of DNA samples. UV absorbance of double-stranded DNA at the ?[subscript max] is decreased when the DNA bases are…

Synthesis and Characterization of C-Cinnamal Calix [4] Resorsinarena from Cinnamon Oil Waste West Sumatra

NASA Astrophysics Data System (ADS)

Etika, S. B.; Nasra, E.; Rilaztika, I.

2018-04-01

Synthesis and characterization of compound C-Cinnamal Calix [4] Resorsinarena (CCCR) of cinnamon oil waste have been done. This study was aimed to synthesis and characterize C-Cinnamal Calix [4] Resorsinarena from cinnamaldehyde violated cinnamon oil waste. C-Cinnamal Calix [4] Resorsinarena was synthesized by electrophilic substitution reaction of cinnamaldehyde isolated by the acid and resorcinol at 77oC temperature for 2 hour. The data analysis spectrum UV-VIS and FT-IR showed that the compound isolated cinnamaldehyde same as pure cinnamaldehyde compound. The characterization of C-Cinnamal Calix [4] Resorsinarena in the form of reddish-colored solids with melting point 3580C by using UV-VIS showed the presence of double bond, FT-IR showed the absorption at the wave number 3323,94 cm-1 indicating the ‑OH group, the wave number 1610,94 cm-1 showed the vibration C=C, the strong region absorption of 1500,86 cm-1 indicating the presence of an aromatic ring, the at 1442,88 cm-1 wave number indicating the presence of CH3.

Comparative study on major bioactive components in natural, artificial and in-vitro cultured Calculus Bovis.

PubMed

Yan, Shi-Kai; Wu, Yan-Wen; Liu, Run-Hui; Zhang, Wei-Dong

2007-01-01

Major bioactive components in various Calculus Bovis, including natural, artificial and in-vitro cultured Calculus Bovis, were comparatively studied. An approach of high-performance liquid chromatography coupled with ultraviolet and evaporative light scattering detections (HPLC/UV/ELSD) was established to simultaneously determinate six bioactive components thereof, including five bile acids (cholic acid, deoxycholic acid, ursodeoxycholic, chenodeoxycholic acid, hyodeoxycholic acid) and bilirubin. ELSD and UV detector were applied to detect bile acids and bilirubin respectively. The assay was performed on a C(18) column with water-acetonitrile gradient elution and the investigated constituents were authenticated by comparing retention times and mass spectra with those of reference compounds. The proposed method was applied to analyze twenty-one Calculus Bovis extraction samples, and produced data with acceptable linearity, precision, repeatability and accuracy. The result indicated the variations among Calculus Bovis samples under different developmental conditions. Artificial and in-vitro cultured Calculus Bovis, especially in-vitro cultured ones, which contain total bioactive constituents no less than natural products and have the best batch-to-batch uniformity, suffice to be used as substitutes of natural Calculus Bovis.

Bromine incorporation into five DBP classes upon chlorination of water with extremely low SUVA values.

PubMed

Hong, Huachang; Yan, Xiaoqing; Song, Xuhui; Qin, Yanyan; Sun, Hongjie; Lin, Hongjun; Chen, Jianrong; Liang, Yan

2017-07-15

The main objective of this study was to assess the effects of disinfection conditions on bromine incorporation into disinfection by-products (DBPs) during chlorination of water with low specific UV absorbance (SUVA). Five classes of DBPs were included: trihalomethanes (THMs), dihaloacetic acids (di-HAAs), trihaloacetic acids (tri-HAAs), dihaloacetonitriles (DHANs) and trihalonitromethanes (THNMs). Results showed that the bromine utilization in DBPs formation was positive related with reaction time, pH and temperature. On the other hand, the bromine substitution factors (BSFs) of DBPs were generally increased with pH (except tri-HAAs) and bromide concentration, but decreased with the reaction time, temperature and chlorine dose. Moreover, the BSFs values varied with DBP classes with the ranking being as following: THNMs≫DHANs≫tri-HAAs>THM≈di-HAAs. These results were mostly similar with the references, yet the pH effect on BSFs as well as the rank of BSFs for different DBP classes may differ with the specific UV absorbance of organic matter. Copyright © 2017 Elsevier B.V. All rights reserved.

Enantioseparation of α-Hydroxyallylphosphonates and Phosphonoallylic Carbonate Derivatives on Chiral Stationary Phases Using Sequential UV, Polarimetric, and Refractive Index Detection.

PubMed

Hamper, Bruce C; Mannino, Michael P; Mueller, Melissa E; Harrison, Liam T; Spilling, Christopher D

2016-09-01

Chromatographic separation of the enantiomers of parent compounds dimethyl α-hydroxyallyl phosphonate and 1-(dimethoxyphosphoryl) allyl methyl carbonate was demonstrated by high-performance liquid chromatography (HPLC) using Chiralpak AS-H and ad-H chiral stationary phases (CSP), respectively, using a combination of UV, polarimetric, and refractive index detectors. A comparison was made of the separation efficiency and elution order of enantiomeric α-hydroxyallyl phosphonates and their carbonate derivatives on commercially available polysaccharide AS, ad, OD, IC-3, and Whelk-O 1 CSPs. In general, the α-hydroxyallyl phosphonates were resolved on the AS-H CSP, whereas the carbonate derivatives and were preferentially resolved on the ad-H CSP. The impact of aryl substitution on the resolution of analytes and was evaluated. Thermodynamic parameters determined for enantioselective adsorption hydroxyphosphonates and on the AS-H CSP and carbonate on the ad-H CSP demonstrated enthalpic control for separation of the enantiomers. Chirality 28:656-662, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Influence of Iron Doping on Structural, Optical and Magnetic Properties of TiO2 Nanoparticles

NASA Astrophysics Data System (ADS)

Zahid, R.; Manzoor, M.; Rafiq, A.; Ikram, M.; Nafees, M.; Butt, A. R.; Hussain, S. G.; Ali, S.

2018-05-01

In this study, various concentrations of Fe doped TiO2 nanoparticles have been successfully synthesized using the sol-gel method. A variety of characterization techniques as ultra-violet visible (UV-Vis) spectroscopy, X-ray diffractometer (XRD), vibrating sample magnetometry (VSM) and field emission scanning electron microscopy (FESEM) were employed to analyze the prepared nanopowders. XRD measurement confirmed the substitution of Fe ion without disturbing the tetragonal crystal system of TiO2. The crystallite size was found to decrease and lattice strain increases upon doping estimated by Williamson Hall plot. Furthermore, the average grain size calculated by FESEM found was between 10 and 30 nm for pure and doped TiO2. UV-Vis spectroscopy showed an increase in absorption accompanied red shift and increase in band gap energies from 3.36 to 3.62 eV with the addition of Fe. The FTIR spectroscopy was employed to confirm the presence of functional groups in the fabricated nanopowders. Upon mixing the saturation magnetization (Ms) varying from (2.12 to 1.51)10-2 emu/g was observed.

Affinity of guanosine derivatives for polycytidylate revisited

NASA Technical Reports Server (NTRS)

Kanavarioti, A.; Hurley, T. B.; Baird, E. E.

1995-01-01

Evidence is presented for complexation of guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) with polycytidylate (poly(C)) at pH 8.0 and 23 degrees C in the presence of 1.0 M NaCl2 and 0.2 M MgCl2 in water. The association of 2-MeImpG with poly(C) was investigated using UV-vis spectroscopy as well as by monitoring the kinetics of the nucleophilic substitution reaction of the imidazole moiety by amines. The results of both methods are consistent with moderately strong poly(C) 2-MeImpG complexation and the spectrophotometric measurements allowed the construction of a binding isotherm with a concentration of 2-MeImpG equal to 5.55 +/- 0.15 mM at half occupancy. UV spectroscopy was employed to establish the binding of other guanosine derivatives on poly(C). These derivatives are guanosine 5'-monophosphate (5'GMP), guanosine 5'-monophosphate imidazolide (ImpG), and guanosine 5'-monophosphate morpholidate (morpG). Within experimental error these guanosine derivatives exhibit the same affinity for poly(C) as 2-MeImpG.

Recent advances in application of UV light-emitting diodes for degrading organic pollutants in water through advanced oxidation processes: A review.

PubMed

Matafonova, Galina; Batoev, Valeriy

2018-04-01

Over the last decade, ultraviolet light-emitting diodes (UV LEDs) have attracted considerable attention as alternative mercury-free UV sources for water treatment purposes. This review is a comprehensive analysis of data reported in recent years (mostly, post 2014) on the application of UV LED-induced advanced oxidation processes (AOPs) to degrade organic pollutants, primarily dyes, phenols, pharmaceuticals, insecticides, estrogens and cyanotoxins, in aqueous media. Heterogeneous TiO 2 -based photocatalysis in lab grade water using UVA LEDs is the most frequently applied method for treating organic contaminants. The effects of controlled periodic illumination, different TiO 2 -based nanostructures and reactor types on degradation kinetics and mineralization are discussed. UVB and UVC LEDs have been used for photo-Fenton, photo-Fenton-like and UV/H 2 O 2 treatment of pollutants, primarily, in model aqueous solutions. Notably, UV LED-activated persulfate/peroxymonosulfate processes were capable of providing degradation in DOC-containing waters. Wall-plug efficiency, energy-efficiency of UV LEDs and the energy requirements in terms of Electrical Energy per Order (E EO ) are discussed and compared. Despite the overall high degradation efficiency of the UV LED-based AOPs, practical implementation is still limited and at lab scale. More research on real water matrices at more environmentally relevant concentrations, as well as an estimation of energy requirements providing fluence-based kinetic data are required. Copyright © 2018 Elsevier Ltd. All rights reserved.

Transformations of dissolved organic matter induced by UV photolysis, Hydroxyl radicals, chlorine radicals, and sulfate radicals in aqueous-phase UV-Based advanced oxidation processes.

PubMed

Varanasi, Lathika; Coscarelli, Erica; Khaksari, Maryam; Mazzoleni, Lynn R; Minakata, Daisuke

2018-05-15

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H 2 O 2 ), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H 2 O 2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO 4 •- are the predominant pathways in the UV/persulfate system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quality improvement of a rice-substituted fried noodle by utilizing the protein-polyphenol interaction between a pea protein isolate and green tea (Camellia sinensis) extract.

PubMed

Song, Youngwoon; Yoo, Sang-Ho

2017-11-15

The quality of rice-substituted fried noodles was improved by applying interaction between pea protein isolate (PPI) and green tea extract (GTE). Radical-scavenging activities of GTE were stably maintained when exposed to acidic pH, UV light, and fluorescent light, but decreased by approximately 65% when exposed to 80°C for 168h. The RVA profiles of noodle dough showed that peak viscosity and breakdown increased significantly but that setback and final viscosity remained unchanged with 20% rice flour replacement. PPI significantly decreased the viscosity parameters of rice-supplemented dough, and the addition of GTE recovered these values significantly. The cooking loss and viscoelasticity (R max ) of cooked rice-supplemented noodles were fully restored by combined treatment of PPI and GTE. GTE decreased the peroxide value of fried noodles by 14% after storage at 63°C for 16days. Therefore, PPI+GTE treatment has great potential for use in fried noodles owing to the reinforced network and antioxidant activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis and spectroscopic characterization of fluorescent 4-aminoantipyrine analogues: Molecular docking and in vitro cytotoxicity studies

NASA Astrophysics Data System (ADS)

Premnath, D.; Mosae Selvakumar, P.; Ravichandiran, P.; Tamil Selvan, G.; Indiraleka, M.; Jannet Vennila, J.

2016-01-01

Two substituted aromatic carbonyl compounds (compounds 1 and 2) of 4-aminoantipyrine were synthesized by condensation of fluorine substituted benzoyl chlorides and 4-aminoantipyrine. The structures of synthesized derivatives were established on the basis of UV-Vis, IR, and Mass, 1H, 13C NMR and Fluorescence spectroscopy. Both compounds showed significant fluorescence emission and two broad emission bands were observed in the region at 340 nm and 450 nm on excitation at 280 nm. Theoretically to prove that the molecule has anticancer activity against cervical cancer cells, the compounds were analyzed for molecular docking interactions with HPV16-E7 target protein by Glide protocol. Furthermore, 4-aminoantipyrine derivatives were evaluated for their in vitro cytotoxic activity against human cervical cancer cells (SiHa) by MTT assay. Compound 1 showed two fold higher activity (IC50 = 0.912 μM) over compound 2, and its activity was similar to that of Pazopanib, suggesting that although the two compounds were chemically very similar the difference in substituent on the phenyl moiety caused changes in properties.

Effects on structural, optical, and magnetic properties of pure and Sr-substituted MgFe2O4 nanoparticles at different calcination temperatures

NASA Astrophysics Data System (ADS)

Loganathan, A.; Kumar, K.

2016-06-01

In the present work, pure and Sr2+ ions substituted Mg ferrite nanoparticles (NPs) had been prepared by co-precipitation method and their structural, optical, and magnetic properties at different calcination temperatures were studied. On this purpose, thermo gravimetric and differential thermal analysis (TG-DTA), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy, UV-Visible diffused reflectance spectroscopy, impedance spectroscopy, and vibrating sample magnetometer were carried out. The exo- and endothermic processes of synthesized precursors were investigated by TG-DTA measurements. The structural properties of the obtained products were examined by XRD analysis and show that the synthesized NPs are in the cubic spinel structure. The existence of two bands around 578-583 and 430-436 cm-1 in FT-IR spectrum also confirmed the formation of spinel-structured ferrite NPs. The lattice constants and particle size are estimated using XRD data and found to be strongly dependent on calcination temperatures. The optical, electrical, and magnetic properties of ferrite compositions also investigated and found to be strongly dependant on calcination temperatures.

Molecular complexes of l-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: spectral and theoretical investigations.

PubMed

Ganesh, K; El-Mossalamy, E H; Satheshkumar, A; Balraj, C; Elango, K P

2013-12-01

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ(1-4)). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH=7). The interaction of MQ(1-4) with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations. Copyright © 2013 Elsevier B.V. All rights reserved.

Formation and identification of nitrosylmyoglobin by Staphylococcus xylosus in raw meat batters: a potential solution for nitrite substitution in meat products.

PubMed

Li, Peijun; Kong, Baohua; Chen, Qian; Zheng, Dongmei; Liu, Ning

2013-01-01

Staphylococcus xylosus and Pediococcus pentosaceus isolated from Chinese dried sausage were assessed for their ability to convert metmyoglobin into nitrosylmyoglobin in Mann-Rogosa-Sharp broth model systems and raw pork meat batters without the addition of nitrite. The results showed that samples in model systems with S. xylosus cultures had an absorption spectra that is typical of nitrosylmyoglobin, an obvious pink colour (judged by visual inspection) and a significantly higher a-value than the control samples or samples inoculated with P. pentosaceus. In raw meat batters, the a-values of the S. xylosus samples were almost the same as those for the meat with nitrite added. The complementary analysis of meat batter samples by photochemical information from UV-vis, electron spin resonance and resonance Raman spectroscopy revealed that the existing status of the myoglobin in meat batters inoculated with S. xylosus was mainly pentacoordinate nitrosylmyoglobin. This study provides a potential solution for nitrite substitute in meat products. Copyright © 2012 Elsevier Ltd. All rights reserved.

Adsorption and separation of reactive aromatic isomers and generation and stabilization of their radicals within cadmium(II)-triazole metal-organic confined space in a single-crystal-to-single-crystal fashion.

PubMed

Liu, Qi-Kui; Ma, Jian-Ping; Dong, Yu-Bin

2010-05-26

A series of reactive group functionalized aromatics, namely 2-furaldehyde, 3-furaldehyde, 2-thenaldehyde, 3-thenaldehyde, o-toluidine, m-toluidine, p-toluidine, and aniline, can be absorbed by a CdL(2) (1; L = 4-amino-3,5-bis(4-pyridyl-3-phenyl)-1,2,4-triazole) porous framework in both vapor and liquid phases to generate new G(n) [symbol: see text] CdL(2) (n = 1, 2) host-guest complexes. In addition, the CdL(2) framework can be a shield to protect the active functional group (-CHO and -NH(2)) substituted guests from reaction with the outside medium containing their reaction partners. That is, aldehyde-substituted guests within the CdL(2) host become "stable" in the aniline phase and vice versa. Moreover, 1 displays a very strict selectivity for these reactive group substituted aromatic isomers and can completely separate these guest isomers under mild conditions (i.e., 2-furaldehyde vs 3-furaldehyde, 2-thenaldehyde vs 3-thenaldehyde, and o-toluidine vs m-toluidine vs p-toluidine). All adsorptions and separations are directly performed on the single crystals of 1. More interestingly, these reactive group substituted aromatics readily transform to the corresponding radicals within the CdL(2) host upon ambient light or UV light (355 nm) irradiation. Furthermore, the generated organic radicals are alive for 1 month within the interior cavity in air under ambient conditions. Simple organic radicals are highly reactive short-lived species, and they cannot be generally isolated and conserved under ambient conditions. Thus, the CdL(2) host herein could be considered as a radical generator and storage vessel.

Nucleophilic substitution reaction for post-functionalization of polyoxometalates

DOE PAGES

Yin, Panchao; Li, Qiang; Zhang, Jin; ...

2015-07-06

In this study, a hexamolybdate-based organic inorganic hybrid molecule containing a chloralkane fragment is synthesized and its Cl atom can be substituted by iodine and nitrate through nucleophilic substitution reactions in high yields, which provide a post-functionalization protocol to bring in various additional functional groups into polyoxometalate-based hybrid materials under mild conditions.

UV plasmonic device for sensing ethanol and acetone

NASA Astrophysics Data System (ADS)

Honda, Mitsuhiro; Ichikawa, Yo; Rozhin, Alex G.; Kulinich, Sergei A.

2018-01-01

In the present study, we demonstrate efficient detection of volatile organic vapors with improved sensitivity, exploiting the localized surface plasmon resonance of indium nanograins in the UV range (UV-LSPR). The sensitivity of deep-UV-LSPR measurements toward ethanol was observed to be 0.004 nm/ppm, which is 10 times higher than that of a previously reported visible-LSPR device based on Ag nanoprisms [Sensors 11, 8643 (2011)]. Although practical issues such as improving detection limits are still remaining, the results of the present study suggest that the new approach based on UV-LSPR may open new avenues to the detection of organic molecules in solid, liquid, and gas phases using plasmonic sensors.

Improved functionality of graphene and carbon nanotube hybrid foam architecture by UV-ozone treatment

NASA Astrophysics Data System (ADS)

Wang, Wei; Ruiz, Isaac; Lee, Ilkeun; Zaera, Francisco; Ozkan, Mihrimah; Ozkan, Cengiz S.

2015-04-01

Optimization of the electrode/electrolyte double-layer interface is a key factor for improving electrode performance of aqueous electrolyte based supercapacitors (SCs). Here, we report the improved functionality of carbon materials via a non-invasive, high-throughput, and inexpensive UV generated ozone (UV-ozone) treatment. This process allows precise tuning of the graphene and carbon nanotube hybrid foam (GM) transitionally from ultrahydrophobic to hydrophilic within 60 s. The continuous tuning of surface energy can be controlled by simply varying the UV-ozone exposure time, while the ozone-oxidized carbon nanostructure maintains its integrity. Symmetric SCs based on the UV-ozone treated GM foam demonstrated enhanced rate performance. This technique can be readily applied to other CVD-grown carbonaceous materials by taking advantage of its ease of processing, low cost, scalability, and controllability.Optimization of the electrode/electrolyte double-layer interface is a key factor for improving electrode performance of aqueous electrolyte based supercapacitors (SCs). Here, we report the improved functionality of carbon materials via a non-invasive, high-throughput, and inexpensive UV generated ozone (UV-ozone) treatment. This process allows precise tuning of the graphene and carbon nanotube hybrid foam (GM) transitionally from ultrahydrophobic to hydrophilic within 60 s. The continuous tuning of surface energy can be controlled by simply varying the UV-ozone exposure time, while the ozone-oxidized carbon nanostructure maintains its integrity. Symmetric SCs based on the UV-ozone treated GM foam demonstrated enhanced rate performance. This technique can be readily applied to other CVD-grown carbonaceous materials by taking advantage of its ease of processing, low cost, scalability, and controllability. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06795a

Synthesis, characterization, molecular docking and biological studies of self assembled transition metal dithiocarbamates of substituted pyrrole-2-carboxaldehyde.

PubMed

Nami, Shahab A A; Ullah, Irfan; Alam, Mahboob; Lee, Dong-Ung; Sarikavakli, Nursabah

2016-07-01

A series of self assembled 3d transition metal dithiocarbamate, M(pdtc) [where M=Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)] have been synthesized and spectroscopically characterized. The bidentate dithiocarbamate ligand Na2pdtc (Disodium-1,4-phenyldiaminobis (pyrrole-1-sulfino)dithioate) was prepared by insertion reaction of carbondisulfide with Schiff base, N,N'-bis-(1H-pyrrol-2-ylmethylene)-benzene-1,4-diamine (L1) in basic medium. The simple substitution reaction between the metal halide and Na2pdtc yielded the title complexes in moderate yields. However, the in situ procedure gives high yield with the formation of single product as evident by TLC. Elemental analysis, IR, (1)H and (13)C NMR spectra, UV-vis., magnetic susceptibility and conductance measurements were done to characterize the complexes, M(pdtc). All the evidences suggest that the complexes have tetrahedral geometry excepting Cu(II) which is found to be square planar. A symmetrical bidentate coordination of the dithiocarbamato moiety has been observed in all the complexes. The conductivity data show that the complexes are non-electrolyte in nature. The anti-oxidant activity of the ligand, Na2pdtc and its transition metal complexes, M(pdtc) have been carried out using DPPH and Cu(pdtc) was found to be most effective. The anti-microbial activity of the Na2pdtc and M(pdtc) complexes have been carried out and on this basis the molecular docking study of the most effective complex, Cu(pdtc) has also been reported. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular Mechanism of Terbinafine Resistance in Saccharomyces cerevisiae

PubMed Central

Leber, Regina; Fuchsbichler, Sandra; Klobučníková, Vlasta; Schweighofer, Natascha; Pitters, Eva; Wohlfarter, Kathrin; Lederer, Mojca; Landl, Karina; Ruckenstuhl, Christoph; Hapala, Ivan; Turnowsky, Friederike

2003-01-01

Ten mutants of the yeast Saccharomyces cerevisiae resistant to the antimycotic terbinafine were isolated after chemical or UV mutagenesis. Molecular analysis of these mutants revealed single base pair exchanges in the ERG1 gene coding for squalene epoxidase, the target of terbinafine. The mutants did not show cross-resistance to any of the substrates of various pleiotropic drug resistance efflux pumps tested. The ERG1 mRNA levels in the mutants did not differ from those in the wild-type parent strains. Terbinafine resistance was transmitted with the mutated alleles in gene replacement experiments, proving that single amino acid substitutions in the Erg1 protein were sufficient to confer the resistance phenotype. The amino acid changes caused by the point mutations were clustered in two regions of the Erg1 protein. Seven mutants carried the amino acid substitutions F402L (one mutant), F420L (one mutant), and P430S (five mutants) in the C-terminal part of the protein; and three mutants carried an L251F exchange in the central part of the protein. Interestingly, all exchanges identified involved amino acids which are conserved in the squalene epoxidases of yeasts and mammals. Two mutations that were generated by PCR mutagenesis of the ERG1 gene and that conferred terbinafine resistance mapped in the same regions of the Erg1 protein, with one resulting in an L251F exchange and the other resulting in an F433S exchange. The results strongly indicate that these regions are responsible for the interaction of yeast squalene epoxidase with terbinafine. PMID:14638499

Synthesis, Photophysical and Computational Study of Novel Coumarin-based Organic Dyes.

PubMed

Kumbar, Mahadev N; Sannaikar, Madivalagouda S; Shaikh, Saba Kauser J; Kamble, Atulkumar A; Wari, Manjunath N; Inamdar, Sanjeev R; Qiao, Qiquan; Revanna, Bhavya N; Madegowda, Mahendra; Dasappa, Jagadeesh P; Kamble, Ravindra R

2018-03-01

A series of novel coumarin pyrazoline moieties combined with tetrazoles, 3-(1-phenyl-4-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl)-2H-chromen-2-one, 6-chloro-3-(1-phenyl-4-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl)-2H-chromen-2-one, 6-bromo-3-(1-phenyl-4-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl)-2H-chromen-2-one and 6-bromo-3-(1-(4-bromophenyl)-4-(1H-tetrazol-5-yl)-1H pyrazol-3-yl)-2H-chromen-2-one7(a-d), were designed and synthesized. Single crystal X-ray diffraction and their interactions were studied by Hirshfeld surface analysis. Thermal stabilities and electrochemical properties of these compounds were examined from differential scanning calorimetry (DSC), thermogravimetric (TGA) and cyclic voltammetric (CV) studies. Their spectroscopic properties were analyzed in various alcohols and general solvents by UV-Vis absorption, fluorescence and time-resolved spectroscopy. In addition, the ground and excited state electronic properties were investigated using density functional theory (DFT). The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and energy band gap (E g ) values have revealed the effect of substitution of halogens. The substitution has equally affected the ground and excited states of 7(a-d) compounds. The solvatochromism on absorption, fluorescence spectra and fluorescence lifetimes of these compounds was investigated. All these results showed the chromen-2-one of pyrazoline tetrazole derivatives could play an important role in photonic and electronic devices. © 2017 The American Society of Photobiology.

Synthesis, Structure, and Film Properties of Novel low-k UV-active Polycarbosilanes with Embedded Disilacyclobutanes

NASA Astrophysics Data System (ADS)

LeFevre, Scott W.

The phenylene-bridged cyclolinear polycarbosilane (PBCLPCS) was synthesized via Grignard coupling from 1,4-bis(bromomagnesio)benzene with 1,3-dichloro-, and 1,3-diethoxy-1,3-disilacyclobutanes (DCDSCB, and DEDSCB respectively). Investigation of the resulting chemical structures by nuclear magnetic resonance spectroscopy (NMR) revealed a wide array of possible end groups and thus termination mechanisms. Temperature-gradient interaction chromatography (TGIC) was employed as an effective separation tool to achieve a predominantly monomer-by-monomer separation of the low molecular weight reaction products. Further analysis of the TGIC fractions by matrix-assisted laser desorption ionization mass spectrometry with time of flight detection (MALDI-ToF) allowed for a much more detailed study of chemical structure, revealing very different primary modes of termination for the two synthesis schemes. While the slightly more reactive Si-Cl groups from DCDSCB are more sensitive to multiple side reactions including hydrolysis, it was shown that the primary end groups were phenyl rings, indicating a possible imbalance in stoichiometry favoring the aryl-Grignard reagent. The DEDSCB-based synthesis has fewer side reactions, as indicated by few groupings of MALDI peaks at regular intervals equal to the repeat unit molecular weight; however the primary end groups were unreacted ethoxy moieties, and a bromine terminated phenyl ring. This indicates that the primary modes of termination were either limited chain growth from the less reactive ethoxy groups, or incomplete formation of the di-Grignard. The optical, UV-curing and thin film characteristics of PBCLPCS were investigated to gain an understanding of the unique film properties of this new class of material. Upon UV-curing PBCLPCS, the chromophore blue shifts 11nm but still absorbs appreciably at 254nm, leading to UV attenuation at greater depths within a film. The thickness dependent UV-curing characteristics were investigated and it was found that the apparent quantum efficiencies for 20 nm and 210 nm thick films are 2.75 and 2% respectively, corresponding to 180mJ and 2.5J of UV irradiation required to achieve a fully cured sample. A UV-dosage dependent film thickness relationship was derived from confocal Raman depth profiles, and it was found that the maximum thickness attainable is 40 microns. The physical effects on thin films of PBCLPCS before and after UV irradiation was examined, and while it was found that there is approximately 17% shrinkage in film thickness that occurs, this is accompanied by a reduction in film roughness. For the thickest films (> 150nm), the surface roughness drops from roughly 14% to 7% in height variation, while for films <100nm a final surface roughness of 1-2% is consistently observed. The films also retain a high degree of hydrophobicity after curing (>100° water contact angle). To test the photoresist capabilities of these films various photomasks were employed showing feature sizes down to 1mum in width with surface roughness variations consistent with that of non-patterned films. There was a 18%-50% expansion of cured polymer beyond the photomask, depending on the feature size. Finally the synthesis of 1-(4-(dimethyl(phenyl)silyl)phenyl)-1,3,3-trimethyl-1,3-disilacyclobutane (DMPSP-DSCB), an extended chromophore (SiDSCB-C6H4-Si-C 6H4-) small molecule variant of PBCLPCS was carried out, where SiDSCB represents silicon atoms within a disilacyclobutane ring. The UV absorption and molar absorptivity at longer wavelengths was shown to increase along with the observed secondary absorption bands. A red shift of approximately 2 nm was observed compared to its trimethylsilylbenzene-DSCB (TMSB-DSCB) analogue. The observed red shift in UV absorption allows for improved ring-opening (RO) conversion efficiencies of the disilacyclobutane ring by 30% after 2 hours irradiation of the compared to the single Ph substituted chromophore (Si DSCB-C6H4-Si) 1,1,3-trimethyl-3-(4-(trimethylsilyl)phenyl)-1,3-disilacyclobutane.

An Enhanced UV-Vis-NIR an d Flexible Photodetector Based on Electrospun ZnO Nanowire Array/PbS Quantum Dots Film Heterostructure.

PubMed

Zheng, Zhi; Gan, Lin; Zhang, Jianbing; Zhuge, Fuwei; Zhai, Tianyou

2017-03-01

ZnO nanostructure-based photodetectors have a wide applications in many aspects, however, the response range of which are mainly restricted in the UV region dictated by its bandgap. Herein, UV-vis-NIR sensitive ZnO photodetectors consisting of ZnO nanowires (NW) array/PbS quantum dots (QDs) heterostructures are fabricated through modified electrospining method and an exchanging process. Besides wider response region compared to pure ZnO NWs based photodetectors, the heterostructures based photodetectors have faster response and recovery speed in UV range. Moreover, such photodetectors demonstrate good flexibility as well, which maintain almost constant performances under extreme (up to 180°) and repeat (up to 200 cycles) bending conditions in UV-vis-NIR range. Finally, this strategy is further verified on other kinds of 1D nanowires and 0D QDs, and similar enhancement on the performance of corresponding photodetecetors can be acquired, evidencing the universality of this strategy.

Soy-based polyols

DOEpatents

Suppes, Galen; Lozada, Zueica; Lubguban, Arnold

2013-06-25

The invention provides processes for preparing soy-based oligomeric polyols or substituted oligomeric polyols, as well as urethane bioelasteromers comprising the oligomeric polyols or substituted oligomeric polyols.

High-Performance Visible-Blind UV Phototransistors Based on n-Type Naphthalene Diimide Nanomaterials.

PubMed

Song, Inho; Lee, Seung-Chul; Shang, Xiaobo; Ahn, Jaeyong; Jung, Hoon-Joo; Jeong, Chan-Uk; Kim, Sang-Wook; Yoon, Woojin; Yun, Hoseop; Kwon, O-Pil; Oh, Joon Hak

2018-04-11

This study investigates the performance of single-crystalline nanomaterials of wide-band gap naphthalene diimide (NDI) derivatives with methylene-bridged aromatic side chains. Such materials are found to be easily used as high-performance, visible-blind near-UV light detectors. NDI single-crystalline nanoribbons are assembled using a simple solution-based process (without solvent-inclusion problems), which is then applied to organic phototransistors (OPTs). Such OPTs exhibit excellent n-channel transistor characteristics, including an average electron mobility of 1.7 cm 2 V -1 s -1 , sensitive UV detection properties with a detection limit of ∼1 μW cm -2 , millisecond-level responses, and detectivity as high as 10 15 Jones, demonstrating the highly sensitive organic visible-blind UV detectors. The high performance of our OPTs originates from the large face-to-face π-π stacking area between the NDI semiconducting cores, which is facilitated by methylene-bridged aromatic side chains. Interestingly, NDI-based nanoribbon OPTs exhibit a distinct visible-blind near-UV detection with an identical detection limit, even under intense visible light illumination (for example, 10 4 times higher intensity than UV light intensity). Our findings demonstrate that wide-band gap NDI-based nanomaterials are highly promising for developing high-performance visible-blind UV photodetectors. Such photodetectors could potentially be used for various applications including environmental and health-monitoring systems.

Improving the assessment of prescribing: use of a 'substitution index'.

PubMed

Kunisawa, Susumu; Otsubo, Tetsuya; Lee, Jason; Imanaka, Yuichi

2013-07-01

To analyse the current and potential utilization of generic drugs in Japan, to examine the maximum possible cost savings from generic drug use and to develop a fairer measure to assess the level of generic drug substitution. We conducted a cross-sectional retrospective analysis of nine million dispensing records during January to March 2010 in Kyoto Prefecture. Maximum potential quantity-based shares were defined as the quantity of generic drugs used plus the quantity of branded drugs that could have been replaced by generic drugs divided by the quantity of all drugs dispensed. We developed a 'substitution index', defined as the proportion of generic drugs out of the total drugs substitutable with generic drugs (based on quantity rather than cost). Generic drugs had a quantity-based share of 17.9%, a cost-based share of 8.9% and a maximum potential quantity-based share of 50.1%, which is lower than the actual generic drug shares of some other countries. The maximum possible cost savings as a result of generic drug substitution was 16.5%. We also observed wide variations in maximum potential quantity-based shares between health care sectors and health care institutions. Simple comparisons based on quantity-based shares may misrepresent the actual generic drug use. A substitution index that takes into account the maximum potential quantity-based share of generic drugs as a fairer measure may promote more realistic goals and encourage generic drug usage.

LED-based UV source for monitoring spectroradiometer properties

NASA Astrophysics Data System (ADS)

Sildoja, Meelis-Mait; Nevas, Saulius; Kouremeti, Natalia; Gröbner, Julian; Pape, Sven; Pendsa, Stefan; Sperfeld, Peter; Kemus, Fabian

2018-06-01

A compact and stable UV monitoring source based on state-of-the-art commercially available ultraviolet light emitting diodes (UV-LEDs) has been developed. It is designed to trace the radiometric stability—both responsivity and wavelength scale—of array spectroradiometers measuring direct solar irradiance in the wavelength range between 300 nm and 400 nm. The spectral irradiance stability of the UV-LED-based light source observed in the laboratory after seasoning (burning-in) the individual LEDs was better than 0.3% over a 12 h period of continuous operation. The integral irradiance measurements of the source over a period of several months, where the UV-LED source was not operated continuously between the measurements, showed stability within 0.3%. In-field measurements of the source with an array spectroradiometer indicated the stability of the source to be within the standard uncertainty of the spectroradiometer calibration, which was within 1% to 2%.

UV and Optical Detectors: Status and Prospects

NASA Technical Reports Server (NTRS)

Woodgate, Bruce; Oegerle, William (Technical Monitor)

2002-01-01

UV and visible detectors - status and prospects. The status and prospects for UV and visible detectors for space astrophysics missions will be described, based on the findings of the NASA working group roadmap report, hopefully updated.

UV Lidar Receiver Analysis for Tropospheric Sensing of Ozone

NASA Technical Reports Server (NTRS)

Pliutau, Denis; DeYoung, Russell J.

2013-01-01

A simulation of a ground based Ultra-Violet Differential Absorption Lidar (UV-DIAL) receiver system was performed under realistic daytime conditions to understand how range and lidar performance can be improved for a given UV pulse laser energy. Calculations were also performed for an aerosol channel transmitting at 3 W. The lidar receiver simulation studies were optimized for the purpose of tropospheric ozone measurements. The transmitted lidar UV measurements were from 285 to 295 nm and the aerosol channel was 527-nm. The calculations are based on atmospheric transmission given by the HITRAN database and the Modern Era Retrospective Analysis for Research and Applications (MERRA) meteorological data. The aerosol attenuation is estimated using both the BACKSCAT 4.0 code as well as data collected during the CALIPSO mission. The lidar performance is estimated for both diffuseirradiance free cases corresponding to nighttime operation as well as the daytime diffuse scattered radiation component based on previously reported experimental data. This analysis presets calculations of the UV-DIAL receiver ozone and aerosol measurement range as a function of sky irradiance, filter bandwidth and laser transmitted UV and 527-nm energy

Sb2O3/Ag/Sb2O3 Multilayer Transparent Conducting Films For Ultraviolet Organic Light-emitting Diode

NASA Astrophysics Data System (ADS)

Song, Chunyan; Zhang, Nan; Lin, Jie; Guo, Xiaoyang; Liu, Xingyuan

2017-01-01

A novel UV transparent conducting films based on Sb2O3/Ag/Sb2O3 (SAS) structure, which were prepared by an electron-beam thermal evaporation at room temperature. This SAS exhibits excellent electrical, optical and stable properties. Especially for UV region, the SAS has high transmittance of 80% at 306 nm and 92% at 335 nm, meanwhile achieving low sheet resistance ( ≤ 10 Ω sq-1). The UV OLED based on the SAS show competitive device performance. The UV OLED obtains the peak of UV electroluminescence at 376 nm and shows a very high maximum EQE of 4.1% with the maximum output power density of 5.18 mW cm-2. These results indicate that the potential of SAS applications in deep UV transparent electrodes and large-scale flexible transparent electronics.

Sb2O3/Ag/Sb2O3 Multilayer Transparent Conducting Films For Ultraviolet Organic Light-emitting Diode.

PubMed

Song, Chunyan; Zhang, Nan; Lin, Jie; Guo, Xiaoyang; Liu, Xingyuan

2017-01-25

A novel UV transparent conducting films based on Sb 2 O 3 /Ag/Sb 2 O 3 (SAS) structure, which were prepared by an electron-beam thermal evaporation at room temperature. This SAS exhibits excellent electrical, optical and stable properties. Especially for UV region, the SAS has high transmittance of 80% at 306 nm and 92% at 335 nm, meanwhile achieving low sheet resistance ( ≤ 10 Ω sq -1 ). The UV OLED based on the SAS show competitive device performance. The UV OLED obtains the peak of UV electroluminescence at 376 nm and shows a very high maximum EQE of 4.1% with the maximum output power density of 5.18 mW cm -2 . These results indicate that the potential of SAS applications in deep UV transparent electrodes and large-scale flexible transparent electronics.

Sb2O3/Ag/Sb2O3 Multilayer Transparent Conducting Films For Ultraviolet Organic Light-emitting Diode

PubMed Central

Song, Chunyan; Zhang, Nan; Lin, Jie; Guo, Xiaoyang; Liu, Xingyuan

2017-01-01

A novel UV transparent conducting films based on Sb2O3/Ag/Sb2O3 (SAS) structure, which were prepared by an electron-beam thermal evaporation at room temperature. This SAS exhibits excellent electrical, optical and stable properties. Especially for UV region, the SAS has high transmittance of 80% at 306 nm and 92% at 335 nm, meanwhile achieving low sheet resistance ( ≤ 10 Ω sq−1). The UV OLED based on the SAS show competitive device performance. The UV OLED obtains the peak of UV electroluminescence at 376 nm and shows a very high maximum EQE of 4.1% with the maximum output power density of 5.18 mW cm−2. These results indicate that the potential of SAS applications in deep UV transparent electrodes and large-scale flexible transparent electronics. PMID:28120888

Effect of the polymeric coating thickness on the photocurrent performance of titanium dioxide nanorod arrays-polyaniline composite-based UV photosensor

NASA Astrophysics Data System (ADS)

Yusoff, M. M.; Mamat, M. H.; Malek, M. F.; Othman, , N.; Ismail, A. S.; Saidi, S. A.; Mohamed, R.; Suriani, A. B.; Khusaimi, Z.; Rusop, M.

2018-05-01

Titanium dioxide (TiO2) nanorod arrays (TNAs) were synthesized and deposited on fluorine tin oxide (FTO)-coated glass substrate using a one-step immersion method in a glass container. The effect of the polymeric coating thickness of p-type polyaniline (PANI) on the n-type TNAs was investigated in the p-n heterojunction photodiode (PD) for the application of ultraviolet (UV) photosensor. The fabricated photosensor demonstrated an increased photocurrent under UV irradiation in correlation with the thickness layer of PANI. The measured UV response showed the highest photocurrent of 0.014 µA at 1.0 V of reverse bias with low dark current under the UV radiation (365 nm, 750 µW/cm2). The thickness of the PANI film improved the photocurrent of the fabricated TNAs/PANI composite-based UV photosensor.

UV-POSIT: Web-Based Tools for Rapid and Facile Structural Interpretation of Ultraviolet Photodissociation (UVPD) Mass Spectra

NASA Astrophysics Data System (ADS)

Rosenberg, Jake; Parker, W. Ryan; Cammarata, Michael B.; Brodbelt, Jennifer S.

2018-04-01

UV-POSIT (Ultraviolet Photodissociation Online Structure Interrogation Tools) is a suite of web-based tools designed to facilitate the rapid interpretation of data from native mass spectrometry experiments making use of 193 nm ultraviolet photodissociation (UVPD). The suite includes four separate utilities which assist in the calculation of fragment ion abundances as a function of backbone cleavage sites and sequence position; the localization of charge sites in intact proteins; the calculation of hydrogen elimination propensity for a-type fragment ions; and mass-offset searching of UVPD spectra to identify unknown modifications and assess false positive fragment identifications. UV-POSIT is implemented as a Python/Flask web application hosted at http://uv-posit.cm.utexas.edu. UV-POSIT is available under the MIT license, and the source code is available at https://github.com/jarosenb/UV_POSIT. [Figure not available: see fulltext.

UV-POSIT: Web-Based Tools for Rapid and Facile Structural Interpretation of Ultraviolet Photodissociation (UVPD) Mass Spectra.

PubMed

Rosenberg, Jake; Parker, W Ryan; Cammarata, Michael B; Brodbelt, Jennifer S

2018-06-01

UV-POSIT (Ultraviolet Photodissociation Online Structure Interrogation Tools) is a suite of web-based tools designed to facilitate the rapid interpretation of data from native mass spectrometry experiments making use of 193 nm ultraviolet photodissociation (UVPD). The suite includes four separate utilities which assist in the calculation of fragment ion abundances as a function of backbone cleavage sites and sequence position; the localization of charge sites in intact proteins; the calculation of hydrogen elimination propensity for a-type fragment ions; and mass-offset searching of UVPD spectra to identify unknown modifications and assess false positive fragment identifications. UV-POSIT is implemented as a Python/Flask web application hosted at http://uv-posit.cm.utexas.edu . UV-POSIT is available under the MIT license, and the source code is available at https://github.com/jarosenb/UV_POSIT . Graphical Abstract.

UV dose measurements of photosensitive dermatosis patients by polycrystalline GaN-based portable self-data-acquisition UV monitors.

PubMed

Yagi, Shigeru; Iwanaga, Takeshi; Kojima, Hiroshi; Shoji, Yoshio; Suzuki, Seiji; Seno, Kunihiro; Mori, Hisayoshi; Tokura, Yoshiki; Takigawa, Masahiro; Moriwaki, Shin-Ichi

2002-12-01

We have developed a UV monitor with polycrystalline (poly-) gallium nitride (GaN) UV sensors and evaluated its performance from the viewpoint of its effectiveness for use with photosensitive dermatosis patients. The poly-GaN UV sensor is sensitive to UV light from 280 to 410 nm even without optical filters. The UV monitor is a portable self-data-acquisition instrument with a minimum detection level (defined as average UV intensity over 290 to 400 nm) of 2 microW/cm2 and can store UV dose data for 128 days. It allows easy measurement of four orders of magnitude of ambient UV intensity and dose from indoor light to direct solar radiation in summer. Trial use of the UV monitor by five xeroderma pigmentosum patients started in June 2000 and was carried out for 1 year. It was demonstrated that the UV monitor was useful in improving their quality of life.

Simulation and comparative study on the oxidation kinetics of atrazine by UV/H₂O₂, UV/HSO₅⁻ and UV/S₂O₈²⁻.

PubMed

Luo, Congwei; Ma, Jun; Jiang, Jin; Liu, Yongze; Song, Yang; Yang, Yi; Guan, Yinghong; Wu, Daoji

2015-09-01

This study comparatively investigated atrazine (ATZ) degradation by irradiation at the wavelength of 254 nm in the presence of peroxides including hydrogen peroxide (H2O2), peroxymonosulfate (HSO5(-)), and persulfate (S2O8(2-)) at various initial ATZ concentrations and oxidant dosages. The effects of water matrix, such as carbonate/bicarbonate (HCO3(-)/CO3(2-)), chloride ions (Cl(-)), and natural organic matter (NOM), were evaluated on these three advanced oxidation processes. A simple steady-state kinetic model was developed based on the initial rates of ATZ destruction, which could well describe the apparent pseudo-first-order rate constants (k(app), s(-1)) of ATZ degradation in these three processes. The specific roles of reactive species (i.e., HO·, SO4(-·), CO3(-·), and Cl2(-·)) under various experimental conditions were quantitatively evaluated based on their steady-state concentrations obtained from this model. Modeling results showed that the steady-state concentrations of HO· and SO4(-·) decreased with the increase of CO3(2-)/HCO3(-) concentration, and the relative contribution of HO· to ATZ degradation significantly decreased in UV/H2O2 and UV/HSO5(-) systems. On the other hand, the scavenging effect of HCO3(-)/CO3(2-) on the relative contribution of SO4(-·) to ATZ degradation was lower than that on HO·. The presence of Cl(-) (0.5-10 mM) significantly scavenged SO4(-·) but had slightly scavenging effect on HO· at the present experimental pH, resulting in greater decrease of k(app) in the UV/S2O8(2-) than UV/H2O2 and UV/HSO5(-) systems. Higher levels of Cl2(-·) were generated in the UV/S2O8(2-) than those in the UV/H2O2 and UV/HSO5(-) systems at the same Cl(-) concentrations. NOM significantly decreased k(app) due to its effects of competitive UV absorption and radical scavenging with the latter one being dominant. These results improve the understanding of the effects of water constituents for ATZ degradation in the UV-based oxidation processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Micropollutants removal by full-scale UV-C/sulfate radical based Advanced Oxidation Processes.

PubMed

Rodríguez-Chueca, J; Laski, E; García-Cañibano, C; Martín de Vidales, M J; Encinas, Á; Kuch, B; Marugán, J

2018-07-15

The high chemical stability and the low biodegradability of a vast number of micropollutants (MPs) impede their correct treatment in urban wastewater treatment plants. In most cases, the chemical oxidation is the only way to abate them. Advanced Oxidation Processes (AOPs) have been experimentally proved as efficient in the removal of different micropollutants at lab-scale. However, there is not enough information about their application at full-scale. This manuscript reports the application of three different AOPs based on the addition of homogeneous oxidants [hydrogen peroxide, peroxymonosulfate (PMS) and persulfate anions (PS)], in the UV-C tertiary treatment of Estiviel wastewater treatment plant (Toledo, Spain) previously designed and installed in the facility for disinfection. AOPs based on the photolytic decomposition of oxidants have been demonstrated as more efficient than UV-C radiation alone on the removal of 25 different MPs using low dosages (0.05-0.5 mM) and very low UV-C contact time (4-18 s). Photolysis of PMS and H 2 O 2 reached similar average MPs removal in all the range of oxidant dosages, obtaining the highest efficiency with 0.5 mM and 18 s of contact time (48 and 55% respectively). Nevertheless, PMS/UV-C reached slightly higher removal than H 2 O 2 /UV-C at low dosages. So, these treatments are selective to degrade the target compounds, obtaining different removal efficiencies for each compound regarding the oxidizing agent, dosages and UV-C contact time. In all the cases, H 2 O 2 /UV-C is more efficient than PMS/UV-C, comparing the ratio cost:efficiency (€/m 3 ·order). Even H 2 O 2 /UV-C treatments are more efficient than UV-C alone. Thus, the addition of 0.5 mM of H 2 O 2 compensates the increased of UV-C contact time and therefore the increase of electrical consumption, that it should be need to increase the removal of MPs by UV-C treatments alone. Copyright © 2018 Elsevier B.V. All rights reserved.

The Canadian Ozone Watch and UV-B advisory programs

NASA Technical Reports Server (NTRS)

Kerr, J. B.; Mcelroy, C. T.; Tarasick, D. W.; Wardle, D. I.

1994-01-01

The Ozone Watch, initiated in March, 1992, is a weekly bulletin describing the state of the ozone layer over Canada. The UV-B advisory program, which started in May, 1992, produces daily forecasts of clear-sky UV-B radiation. The forecast procedures use daily ozone measurements from the eight-station monitoring network, the output from the Canadian operational forecast model and a UV-B algorithm based on three years of spectral UV-B measurements with the Brewer spectrophotometer.

Validation and in vivo assessment of an innovative satellite-based solar UV dosimeter for a mobile app dedicated to skin health.

PubMed

Morelli, M; Masini, A; Simeone, E; Khazova, M

2016-08-31

We present an innovative satellite-based solar UV (ultraviolet) radiation dosimeter with a mobile app interface that has been validated by exploiting both ground-based measurements and an in vivo assessment of the erythemal effects on some volunteers having controlled exposure to solar radiation. The app with this satellite-based UV dosimeter also includes other related functionalities such as the provision of safe sun exposure time updated in real-time and end exposure visual/sound alert. Both validations showed that the system has a good accuracy and reliability needed for health-related applications. This app will be launched on the market by siHealth Ltd in May 2016 under the name of "HappySun" and is available for both Android and iOS devices (more info on ). Extensive R&D activities are on-going for the further improvement of the satellite-based UV dosimeter's accuracy.

Effects of GaN/AlGaN/Sputtered AlN nucleation layers on performance of GaN-based ultraviolet light-emitting diodes

PubMed Central

Hu, Hongpo; Zhou, Shengjun; Liu, Xingtong; Gao, Yilin; Gui, Chengqun; Liu, Sheng

2017-01-01

We report on the demonstration of GaN-based ultraviolet light-emitting diodes (UV LEDs) emitting at 375 nm grown on patterned sapphire substrate (PSS) with in-situ low temperature GaN/AlGaN nucleation layers (NLs) and ex-situ sputtered AlN NL. The threading dislocation (TD) densities in GaN-based UV LEDs with GaN/AlGaN/sputtered AlN NLs were determined by high-resolution X-ray diffraction (XRD) and cross-sectional transmission electron microscopy (TEM), which revealed that the TD density in UV LED with AlGaN NL was the highest, whereas that in UV LED with sputtered AlN NL was the lowest. The light output power (LOP) of UV LED with AlGaN NL was 18.2% higher than that of UV LED with GaN NL owing to a decrease in the absorption of 375 nm UV light in the AlGaN NL with a larger bandgap. Using a sputtered AlN NL instead of the AlGaN NL, the LOP of UV LED was further enhanced by 11.3%, which is attributed to reduced TD density in InGaN/AlInGaN active region. In the sputtered AlN thickness range of 10–25 nm, the LOP of UV LED with 15-nm-thick sputtered AlN NL was the highest, revealing that optimum thickness of the sputtered AlN NL is around 15 nm. PMID:28294166

UV-Assisted Photochemical Synthesis of Reduced Graphene Oxide/ZnO Nanowires Composite for Photoresponse Enhancement in UV Photodetectors

PubMed Central

Zhou, Peng; Wang, Na; Ma, Yang

2018-01-01

The weak photon absorption and high recombination rate of electron-hole pairs in disordered zinc oxide nanowires (ZNWs) limit its application in UV photodetection. This limitation can be overcome by introducing graphene sheets to the ZNWs. Herein we report a high-performance photodetector based on one-dimensional (1D) wide band-gap semiconductor disordered ZNWs composited with reduced graphene oxide (RGO) for ultraviolet (UV) photoresponse enhancement. The RGO/ZNWs composites have been successfully synthetized through UV-assisted photochemical reduction of GO in ZNWs suspension. The material characterizations in morphology, Raman scattering, and Ultraviolet-visible light absorption verified the formation of graphene sheets attached in ZNWs network and the enhancement of UV absorption due to the introduction of graphene. In comparison with photodetectors based on pure ZNWs, the photodetectors based on RGO/ZNWs composite exhibit enhanced photoresponse with photocurrent density of 5.87 mA·cm−2, on/off current ratio of 3.01 × 104, and responsivity of 1.83 A·W−1 when a UV irradiation of 3.26 mW·cm−2 and 1.0 V bias were used. Theory analysis is also presented to get insight into the inherent mechanisms of separation and transportation of photo-excited carriers in RGO/ZNWs composite. PMID:29303994

UV-Assisted Photochemical Synthesis of Reduced Graphene Oxide/ZnO Nanowires Composite for Photoresponse Enhancement in UV Photodetectors.

PubMed

Chen, Changsong; Zhou, Peng; Wang, Na; Ma, Yang; San, Haisheng

2018-01-05

The weak photon absorption and high recombination rate of electron-hole pairs in disordered zinc oxide nanowires (ZNWs) limit its application in UV photodetection. This limitation can be overcome by introducing graphene sheets to the ZNWs. Herein we report a high-performance photodetector based on one-dimensional (1D) wide band-gap semiconductor disordered ZNWs composited with reduced graphene oxide (RGO) for ultraviolet (UV) photoresponse enhancement. The RGO/ZNWs composites have been successfully synthetized through UV-assisted photochemical reduction of GO in ZNWs suspension. The material characterizations in morphology, Raman scattering, and Ultraviolet-visible light absorption verified the formation of graphene sheets attached in ZNWs network and the enhancement of UV absorption due to the introduction of graphene. In comparison with photodetectors based on pure ZNWs, the photodetectors based on RGO/ZNWs composite exhibit enhanced photoresponse with photocurrent density of 5.87 mA·cm -2 , on/off current ratio of 3.01 × 10⁴, and responsivity of 1.83 A·W -1 when a UV irradiation of 3.26 mW·cm -2 and 1.0 V bias were used. Theory analysis is also presented to get insight into the inherent mechanisms of separation and transportation of photo-excited carriers in RGO/ZNWs composite.

Structures, molecular orbitals and UV-vis spectra investigations on methyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate: a computational study.

PubMed

Wang, Tsang-Hsiu; Chu, Hsing-Yu; Wang, I-Teng

2014-10-15

The methyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate (C11H11N3O2) has been studied by theoretically methods. The structure of this compound is optimized by density functional theory (DFT), the second-order Møller-Plesset perturbation theory (MP2) and G3 theory (G3(MP2)) levels. Our calculation results are in very good agreement with experimental values. Compared to a perfect pentagonal structure, the geometrical structures of C11H11N3O2 show a little distortion of 1,2,3-triazole ring due to the highly electronegativity of substitution groups. In addition, dipole moment and frontier molecular orbitals (FMOs) of the C11H11N3O2 are calculated as well. Because of solvent effect, the HOMO-LUMO energy gap in methanol is predicted to be smaller than in gas phase by 0.367eV. The simulated UV-vis spectra are investigated by time-dependent density functional theory (TD-DFT), and two obviously absorption features have been predicted. These two absorption features are located between 170nm and 210nm, which is in ultraviolet C range. Moreover, the UV absorption features in methanol are predicted to be more intense than in gas phase; besides, the red shift is predicted in methanol as well. Copyright © 2014 Elsevier B.V. All rights reserved.

A novel P53/POMC/Gαs/SASH1 autoregulatory feedback loop activates mutated SASH1 to cause pathologic hyperpigmentation.

PubMed

Zhou, Ding'an; Wei, Zhiyun; Kuang, Zhongshu; Luo, Huangchao; Ma, Jiangshu; Zeng, Xing; Wang, Ke; Liu, Beizhong; Gong, Fang; Wang, Jing; Lei, Shanchuan; Wang, Dongsheng; Zeng, Jiawei; Wang, Teng; He, Yong; Yuan, Yongqiang; Dai, Hongying; He, Lin; Xing, Qinghe

2017-04-01

p53-Transcriptional-regulated proteins interact with a large number of other signal transduction pathways in the cell, and a number of positive and negative autoregulatory feedback loops act upon the p53 response. P53 directly controls the POMC/α-MSH productions induced by ultraviolet (UV) and is associated with UV-independent pathological pigmentation. When identifying the causative gene of dyschromatosis universalis hereditaria (DUH), we found three mutations encoding amino acid substitutions in the gene SAM and SH3 domain containing 1 (SASH1), and SASH1 was associated with guanine nucleotide-binding protein subunit-alpha isoforms short (Gαs). However, the pathological gene and pathological mechanism of DUH remain unknown for about 90 years. We demonstrate that SASH1 is physiologically induced by p53 upon UV stimulation and SASH and p53 is reciprocally induced at physiological and pathophysiological conditions. SASH1 is regulated by a novel p53/POMC/α-MSH/Gαs/SASH1 cascade to mediate melanogenesis. A novel p53/POMC/Gαs/SASH1 autoregulatory positive feedback loop is regulated by SASH1 mutations to induce pathological hyperpigmentation phenotype. Our study demonstrates that a novel p53/POMC/Gαs/SASH1 autoregulatory positive feedback loop is regulated by SASH1 mutations to induce pathological hyperpigmentation phenotype. © 2016 The Authors. Journal of Cellular and Molecular Medicine published by John Wiley & Sons Ltd and Foundation for Cellular and Molecular Medicine.

Synthesis, physiochemical and optical properties of chitosan based dye containing naphthalimide group.

PubMed

Kumar, Santosh; Koh, Joonseok

2013-04-15

A new biopolymer dye containing naphthalimide moiety was synthesized by reaction of N-naphthaloyl chitosan with 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-piperazino-3-quinolinecarboxylic acid. N-naphthaloyl chitosan was synthesized by reaction of chitosan with 4-bromo-1,8-naphthalic anhydride in aqueous media by greener approach. The degree of substitution of chitosan biopolymer dye is 0.55 with a yield of 70%. The synthesized materials were characterized by using UV-vis, (1)H NMR, FTIR, and FT-Raman spectroscopy. Some physical properties and surface morphology were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Optical properties of chitosan biopolymer dye were evaluated by photoluminescence (PL) spectroscopy that showed red shift (λ(em)) peak at 442 nm and 551 nm at excitation wavelength 325 nm in comparison to chitosan. The solubility of chitosan biopolymer dye increased in most of the organic solvents. These results may provide new perspectives in biomedical applications as an optical and sensitive biosensor material. Copyright © 2013 Elsevier Ltd. All rights reserved.

Theoretical and experimental study of electron-deficient core substitution effect of diketopyrrolopyrrole derivatives on optoelectrical and charge transport properties

NASA Astrophysics Data System (ADS)

Ding, Guodong; Mahmood, Asif; Tang, Ailing; Chen, Fan; Zhou, Erjun

2018-01-01

Three new diketopyrrolopyrrole based compounds with Acceptor-Donor-Acceptor-Donor-Acceptor (A-D-A-D-A) skeletons were designed and synthesized through varying the electron-deficient core from diphenylquinoxaline (DP-Qx), thieno[3,4-c]pyrrole-4,6-dione (DP-TPD) to 2-dodecyl-6,7-diphenyl-2H-[1,2,3]triazole[4,5-g]quinoxaline (DP-TQx). We have calculated and studied the effect of central acceptor units on electronic, optical and non-optical properties. As well as, we have predicted the charge transport properties. Results indicate that change of central acceptor unit remarkably affects the molecular electronic, optical and non-optical properties. And the molecular band gap and UV/vis adsorption spectra are significantly changed. It should be noted that Compound 3 with 2-dodecyl-6,7-diphenyl-2H-[1,2,3]triazole[4,5-g]quinoxaline as core show superior non-optical properties as compare to other compounds. Our study here indicate that inserting the strong electron-deficient moieties improves intramolecular charge transfer (ICT) and charge transport properties dramatically.

Detailed solvent, structural, quantum chemical study and antimicrobial activity of isatin Schiff base

NASA Astrophysics Data System (ADS)

Brkić, Dominik R.; Božić, Aleksandra R.; Marinković, Aleksandar D.; Milčić, Miloš K.; Prlainović, Nevena Ž.; Assaleh, Fathi H.; Cvijetić, Ilija N.; Nikolić, Jasmina B.; Drmanić, Saša Ž.

2018-05-01

The ratios of E/Z isomers of sixteen synthesized 1,3-dihydro-3-(substituted phenylimino)-2H-indol-2-one were studied using experimental and theoretical methodology. Linear solvation energy relationships (LSER) rationalized solvent influence of the solvent-solute interactions on the UV-Vis absorption maxima shifts (νmax) of both geometrical isomers using the Kamlet-Taft equation. Linear free energy relationships (LFER) in the form of single substituent parameter equation (SSP) was used to analyze substituent effect on pKa, NMR chemical shifts and νmax values. Electron charge density was obtained by the use of Quantum Theory of Atoms in Molecules, i.e. Bader's analysis. The substituent and solvent effect on intramolecular charge transfer (ICT) were interpreted with the aid of time-dependent density functional (TD-DFT) method. Additionally, the results of TD-DFT calculations quantified the efficiency of ICT from the calculated charge-transfer distance (DCT) and amount of transferred charge (QCT). The antimicrobial activity was evaluated using broth microdilution method. 3D QSAR modeling was used to demonstrate the influence of substituents effect as well as molecule geometry on antimicrobial activity.

Evaluation of capillary zone electrophoresis for the determination of protein composition in therapeutic immunoglobulins and human albumins.

PubMed

Christians, Stefan; van Treel, Nadine Denise; Bieniara, Gabriele; Eulig-Wien, Annika; Hanschmann, Kay-Martin; Giess, Siegfried

2016-07-01

Capillary zone electrophoresis (CZE) provides an alternative means of separating native proteins on the basis of their inherent electrophoretic mobilities. The major advantage of CZE is the quantification by UV detection, circumventing the drawbacks of staining and densitometry in the case of gel electrophoresis methods. The data of this validation study showed that CZE is a reliable assay for the determination of protein composition in therapeutic preparations of human albumin and human polyclonal immunoglobulins. Data obtained by CZE are in line with "historical" data obtained by the compendial method, provided that peak integration is performed without time correction. The focus here was to establish a rapid and reliable test to substitute the current gel based zone electrophoresis techniques for the control of protein composition of human immunoglobulins or albumins in the European Pharmacopoeia. We believe that the more advanced and modern CZE method described here is a very good alternative to the procedures currently described in the relevant monographs. Copyright © 2016 International Alliance for Biological Standardization. Published by Elsevier Ltd. All rights reserved.

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX

PubMed Central

Bobe, Mr Sharad R; Al Kobaisi, Mohammad; Bhosale, Sheshanath V; Bhosale, Sidhanath V

2015-01-01

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π–π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine. PMID:26478848

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX.

PubMed

Bobe, Mr Sharad R; Al Kobaisi, Mohammad; Bhosale, Sheshanath V; Bhosale, Sidhanath V

2015-08-01

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π-π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine.

Synthesis and Characterization of Degradable Bioconjugated Hydrogels with Hyperbranched Multifunctional Crosslinkers

PubMed Central

Pedrón, Sara; Peinado, Carmen; Bosch, Paula; S.Anseth, Kristi

2010-01-01

Hyperbranched poly(ester amide) polymer (Hybrane™ S1200; Mn 1200 g/mol) was functionalized with maleic anhydride (MA) and propylene sulfide, to obtain multifunctional crosslinkers with fumaric and thiol-end groups, S1200MA and S1200SH, respectively. The degree of substitution of maleic acid groups (DS) was controlled by varying the molar ratio of MA to S1200 in the reaction mixture. Hydrogels were obtained by UV crosslinking of functionalized S1200 and poly(ethyleneglycol) diacrylate (PEGDA) in aqueous solutions. Compressive modulus increased with decreasing the S1200/PEG ratio and also depended on the DS of the multifunctional crosslinker (S1200). Also, heparin-based macromonomers together with functionalized hyperbranched polymers were used to construct novel functional hydrogels. The multivalent hyperbranched polymers allowed high crosslinking densities in heparin modified gels while introducing biodegradation sites. Both heparin presence and acrylate/thiol ratio have an impact on degradation profiles and morphologies. Hyperbranched crosslinked hydrogels showed no evidence of cell toxicity. Overall, the multifunctional crosslinkers afford hydrogels with promising properties that suggest that these may be suitable for tissue engineering applications. PMID:20561601

Mono azo dyes derived from 5-nitroanthranilic acid: Synthesis, absorption properties and DFT calculations

NASA Astrophysics Data System (ADS)

Karabacak Atay, Çiğdem; Gökalp, Merve; Kart, Sevgi Özdemir; Tilki, Tahir

2017-08-01

Four new azo dyes: 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A), 2-[(3-hydroxy-5-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (B), 2-[(3,5-dimethyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (C) and 2-[(5-amino-3-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (D) which have the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups are synthesized in this work. The structures and spectroscopic properties of these new azo dyes are characterized by using spectroscopic methods such as FT-IR, 1H NMR, 13C NMR and UV-vis. Their solvatochromic properties in chloroform, acetic acid, methanol, dimethylformamide (DMF) and dimethylsulphoxide (DMSO) are studied. Moreover, molecular structures and some spectroscopic properties of azo dyes are investigated by utilizing the quantum computational chemistry method based on Density Functional Theory (DFT) employing B3LYP hybrid functional level with 6-31G(d) basis set. It is seen that experimental and theoretical results are compatible with each other.

Molecular structure activity on pharmaceutical applications of Phenacetin using spectroscopic investigation

NASA Astrophysics Data System (ADS)

Madanagopal, A.; Periandy, S.; Gayathri, P.; Ramalingam, S.; Xavier, S.

2017-01-01

The pharmaceutical compound; Phenacetin was investigated by analyzing FT-IR, FT-Raman and 1H &13C NMR spectra. The hybrid efficient computational calculations performed for computing physical and chemical parameters. The cause of pharmaceutical activity due to the substitutions; carboxylic, methyl and amine groups in appropriate positions on the pedestal compound was deeply investigated. Moreover, 13C NMR and 1H NMR chemical shifts correlated with TMS standard to explain the truth of compositional ratio of base and ligand groups. The bathochromic shift due to chromophores over the energy levels in UV-Visible region was strongly emphasized the Anti-inflammatory chemical properties. The chemical stability was pronounced by the strong kubo gap which showed the occurring of charge transformation within the molecule. The occurrence of the chemical reaction was feasibly interpreted by Gibbs free energy profile. The standard vibrational analysis stressed the active participation of composed ligand groups for the existence of the analgesic as well as antipyretic properties of the Phenacetin compound. The strong dipole interaction energy utilization for the transition among non-vanishing donor and acceptor for composition of the molecular structure was interpreted.

Deep-UV sensors based on SAW oscillators using low-temperature-grown AlN films on sapphires.

PubMed

Laksana, Chipta; Chen, Meei-Ru; Liang, Yen; Tzou, An-Jyeg; Kao, Hui-Ling; Jeng, Erik; Chen, Jyh; Chen, Hou-Guang; Jian, Sheng-Rui

2011-08-01

High-quality epitaxial AlN films were deposited on sapphire substrates at low growth temperature using a helicon sputtering system. SAW filters fabricated on the AlN films exhibited excellent characteristics, with center frequency of 354.2 MHz, which corresponds to a phase velocity of 5667 m/s. An oscillator fabricated using AlN-based SAW devices is presented and applied to deep-UV light detection. A frequency downshift of about 43 KHz was observed when the surface of SAW device was illuminated by a UV source with dominant wavelength of around 200 nm. The results indicate the feasibility of developing remote sensors for deep-UV measurement using AlN-based SAW oscillators.

Modeling Alkyl p-Methoxy Cinnamate (APMC) as UV absorber based on electronic transition using semiempirical quantum mechanics ZINDO/s calculation

NASA Astrophysics Data System (ADS)

Salmahaminati; Azis, Muhlas Abdul; Purwiandono, Gani; Arsyik Kurniawan, Muhammad; Rubiyanto, Dwiarso; Darmawan, Arif

2017-11-01

In this research, modeling several alkyl p-methoxy cinnamate (APMC) based on electronic transition by using semiempirical mechanical quantum ZINDO/s calculation is performed. Alkyl cinnamates of C1 (methyl) up to C7 (heptyl) homolog with 1-5 example structures of each homolog are used as materials. Quantum chemistry-package software Hyperchem 8.0 is used to simulate the drawing of the structure, geometry optimization by a semiempirical Austin Model 1 algorithm and single point calculation employing a semiempirical ZINDO/s technique. ZINDO/s calculations use a defined criteria that singly excited -Configuration Interaction (CI) where a gap of HOMO-LUMO energy transition and maximum degeneracy level are 7 and 2, respectively. Moreover, analysis of the theoretical spectra is focused on the UV-B (290-320 nm) and UV-C (200-290 nm) area. The results show that modeling of the compound can be used to predict the type of UV protection activity depends on the electronic transition in the UV area. Modification of the alkyl homolog relatively does not change the value of wavelength absorption to indicate the UV protection activity. Alkyl cinnamate compounds are predicted as UV-B and UV-C sunscreen.

Assessment of a low-cost, point-of-use, ultraviolet water disinfection technology.

PubMed

Brownell, Sarah A; Chakrabarti, Alicia R; Kaser, Forest M; Connelly, Lloyd G; Peletz, Rachel L; Reygadas, Fermin; Lang, Micah J; Kammen, Daniel M; Nelson, Kara L

2008-03-01

We describe a point-of-use (POU) ultraviolet (UV) disinfection technology, the UV Tube, which can be made with locally available resources around the world for under $50 US. Laboratory and field studies were conducted to characterize the UV Tube's performance when treating a flowrate of 5 L/min. Based on biological assays with MS2 coliphage, the UV Tube delivered an average fluence of 900+/-80 J/m(2) (95% CI) in water with an absorption coefficient of 0.01 cm(-1). The residence time distribution in the UV Tube was characterized as plug flow with dispersion (Peclet Number = 19.7) and a mean hydraulic residence time of 36 s. Undesirable compounds were leached or produced from UV Tubes constructed with unlined ABS, PVC, or a galvanized steel liner. Lining the PVC pipe with stainless steel, however, prevented production of regulated halogenated organics. A small field study in two rural communities in Baja California Sur demonstrated that the UV Tube reduced E. coli concentrations to less than 1/100 ml in 65 out of 70 samples. Based on these results, we conclude that the UV Tube is a promising technology for treating household drinking water at the point of use.

Intensified depolymerization of aqueous polyacrylamide solution using combined processes based on hydrodynamic cavitation, ozone, ultraviolet light and hydrogen peroxide.

PubMed

Prajapat, Amrutlal L; Gogate, Parag R

2016-07-01

The present work deals with intensification of depolymerization of polyacrylamide (PAM) solution using hydrodynamic cavitation (HC) reactors based on a combination with hydrogen peroxide (H2O2), ozone (O3) and ultraviolet (UV) irradiation. Effect of inlet pressure in hydrodynamic cavitation reactor and power dissipation in the case of UV irradiation on the extent of viscosity reduction has been investigated. The combined approaches such as HC+UV, HC+O3, HC+H2O2, UV+H2O2 and UV+O3 have been subsequently investigated and found to be more efficient as compared to individual approaches. For the approach based on HC+UV+H2O2, the extent of viscosity reduction under the optimized conditions of HC (3 bar inlet pressure)+UV (8 W power)+H2O2 (0.2% loading) was 97.27% in 180 min whereas individual operations of HC (3 bar inlet pressure) and UV (8 W power) resulted in about 35.38% and 40.83% intrinsic viscosity reduction in 180 min respectively. In the case of HC (3 bar inlet pressure)+UV (8 W power)+ozone (400 mg/h flow rate) approach, the extent of viscosity reduction was 89.06% whereas individual processes of only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate)+HC (3 bar inlet pressure) and ozone (400 mg/h flow rate)+UV (8 W power) resulted in lower extent of viscosity reduction as 50.34%, 60.65% and 75.31% respectively. The chemical structure of the treated PAM by all approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant chemical structure changes were obtained during the treatment. Overall, it can be said that the combination of HC+UV+H2O2 is an efficient approach for the depolymerization of PAM solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetics and mechanisms of cylindrospermopsin destruction by sulfate radical-based advanced oxidation processes.

PubMed

He, Xuexiang; de la Cruz, Armah A; O'Shea, Kevin E; Dionysiou, Dionysios D

2014-10-15

Cylindrospermopsin (CYN) is a potent cyanobacterial toxin frequently found in water bodies worldwide raising concerns over the safety of drinking and recreational waters. A number of technologies have been investigated to remove and/or degrade cyanotoxins with advanced oxidation processes (AOPs) being among the most promising and effective for water detoxification. In this study, the degradation of CYN by sulfate radical-based UV-254 nm-AOPs was evaluated. The UV/S2O8(2-) (UV/peroxydisulfate) was more efficient than UV/HSO5(-) (UV/peroxysulfate) and UV/H2O2 (UV/hydrogen peroxide) processes when natural water samples were used as reaction matrices. The observed UV fluence based pseudo-first-order rate constants followed the expected order of radical quantum yields. The presence of 200 μM natural organic matter (NOM) as carbon slightly inhibited the destruction of CYN; 1.24 mg L(-1)NO3(-) (nitrate) had no significant influence on the removal efficiency and 50 μg L(-1) Fe(2+) [iron (2+)] or Cu(2+) [copper (2+)] improved the performance of UV/S2O8(2-). The addition of tert-butyl alcohol (t-BuOH; hydroxyl radical scavenger) in the reaction yielded byproducts that indicated specific sites in CYN preferentially attacked by sulfate radicals (SRs). The predominant CYN degradation byproduct was P448 consistent with fragmentation of the C5C6 bond of the uracil ring. The subsequent formation of P420 and P392 through a stepwise loss of carbonyl group(s) further supported the fragmentation pathway at C5C6. The byproduct P432 was identified exclusively as mono-hydroxylation of CYN at tricyclic guanidine ring, whereas P414 was detected as dehydrogenation at the tricyclic ring. The elimination of sulfate group and the opening of tricyclic ring were also observed. The possible degradation pathways of CYN by SR-AOP were presented. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biochemical traits and proteomic changes in postharvest flowers of medicinal chrysanthemum exposed to enhanced UV-B radiation.

PubMed

Yao, Xiaoqin; Chu, Jian-Zhou; Ma, Chun-Hui; Si, Chao; Li, Ji-Gang; Shi, Xiao-Fei; Liu, Chao-Nan

2015-08-01

The article studied UV-B effects on biochemical traits and proteomic changes in postharvest flowers of medicinal chrysanthemum. The experiment about UV-B effects on biochemical traits in flowers included six levels of UV-B treatments (0 (UV0), 50 (UV50), 200 (UV200), 400 (UV400), 600 (UV600) and 800 (UV800) μWcm(-2)). UV400, UV600 and UV800 treatments significantly increased the contents of hydrogen peroxide, malondialdehyde and UV-B absorbing compounds, and the activity of phenylalanine ammonia lyase enzyme over the control. The contents of chlorogenic acid and flavone in flowers were significantly increased by UV-B treatments (except for UV50 and UV800). Two-dimensional gel electrophoresis was utilized to analyze proteomic changes in flowers with or without UV-B radiation. Results indicated that 43 protein spots (>1.5-fold difference in volume) were detected, including 19 spots with a decreasing trend and 24 spots with an increasing trend, and 19 differentially expressed protein spots were successfully indentified by MALDI-TOF MS. The indentified proteins were classified based on functions, the most of which were involved in photosynthesis, respiration, protein biosynthesis and degradation and defence. An overall assessment using biochemical and differential proteomic data revealed that UV-B radiation could affect biochemical reaction and promote secondary metabolism processes in postharvest flowers. Copyright © 2015 Elsevier B.V. All rights reserved.

UV-biosensor for visual indication of vitamin D synthesis

NASA Astrophysics Data System (ADS)

Orlova, T. N.; Terenetskaya, I. P.

2008-04-01

Excessive UV doses have adverse effects on human health, but proper amount of UV is beneficial for people and is essential in the natural production of vitamin D# in skin. Most of broadband UV-radiometers that have an output in sunburn units are incapable to record correctly the vitamin D synthetic capacity of sunlight because of the difference between the CIE erythema and 'Vitamin D synthesis' action spectra. The liquid-crystalline UV sensor based on provitamin D photoconversions has been developed for direct observation of vitamin D synthesis under UV irradiation. UV-induced transformation of provitamin D in cholesteric liquid-crystalline matrix is accompanied by the change of cholesteric pitch value in the LC cell. The developed UV biosensor makes possible both instrumental and visual monitoring of the vitamin D synthetic capacity of sunlight and/or artificial UV source.

Elimination study of the chemotherapy drug tamoxifen by different advanced oxidation processes: Transformation products and toxicity assessment.

PubMed

Ferrando-Climent, Laura; Gonzalez-Olmos, Rafael; Anfruns, Alba; Aymerich, Ignasi; Corominas, Lluis; Barceló, Damià; Rodriguez-Mozaz, Sara

2017-02-01

Tamoxifen is a chemotherapy drug considered as recalcitrant contaminant (with low biodegradability in conventional activated sludge wastewater treatment), bioaccumulative, ubiquitous, and potentially hazardous for the environment. This work studies the removal of Tamoxifen from water by advanced oxidation processes, paying special attention to the formation of transformation products (TPs) and to the evolution of toxicity (using the Microtox ® bioassay) during the oxidation processes. Five types of treatments were evaluated combining different technologies based on ozone, hydrogen peroxide and UV radiation: i) O 3 , ii) O 3 /UV, iii) O 3 /H 2 O 2 (peroxone), iv) UV and v) UV/H 2 O 2 . Complete removal of tamoxifen was achieved after 30 min for all the treatments carried out with O 3 while a residual concentration (about 10% of initial one) was observed in the treatments based on UV and UV/H 2 O 2 after 4 h of reaction. Eight TPs were tentatively identified and one (non-ionizable molecule) was suspected to be present by using ultra high performance liquid chromatography coupled to high resolution mass spectrometry. An increase of toxicity was observed during all the oxidation processes. In the case of ozone-based treatments that increase was attributed to the presence of some of the TPs identified, whereas in the case of UV-based treatments there was no clear correlation between toxicity and the identified TPs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Luminescence enhancement of (Sr1-x Mx )2 SiO4 :Eu2+ phosphors with M (Ca2+ /Zn2+ ) partial substitution for white light-emitting diodes.

PubMed

Wang, Yulong; Zhang, Wentao; Gao, Yang; Long, Jianping; Li, Junfeng

2017-02-01

Eu 2 + -doped Sr 2 SiO 4 phosphor with Ca 2 + /Zn 2 + substitution, (Sr 1-x M x ) 2 SiO 4 :Eu 2 + (M = Ca, Zn), was prepared using a high-temperature solid-state reaction method. The structure and luminescence properties of Ca 2 + /Zn 2 + partially substituted Sr 2 SiO 4 :Eu 2 + phosphors were investigated in detail. With Ca 2 + or Zn 2 + added to the silicate host, the crystal phase could be transformed between the α-form and the β-form of the Sr 2 SiO 4 structure. Under UV excitation at 367 nm, all samples exhibit a broad band emission from 420 to 680 nm due to the 4f 6 5d 1  → 4f 7 transition of Eu 2 + ions. The broad emission band consists of two peaks at 482 and 547 nm, which correspond to Eu 2 + ions occupying the ten-fold oxygen-coordinated Sr.(I) site and the nine-fold oxygen-coordinated Sr.(II) site, respectively. The luminescence properties, including the intensity and lifetime of Sr 2 SiO 4 :Eu 2 + phosphors, improved remarkably on Ca 2 + /Zn 2 + addition, and promote its application in white light-emitting diodes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Broad hexagonal columnar mesophases formation in bioinspired transition-metal complexes of simple fatty acid meta-octaester derivatives of meso-tetraphenyl porphyrins.

PubMed

Wu, Bin; Chen, Keyang; Deng, Yuchen; Chen, Jian; Liu, Chengjie; Cheng, Rongshi; Chen, Dongzhong

2015-02-23

A series of meta-substituted fatty acid octaester derivatives and their transition-metal complexes of meso- tetraphenyl porphyrins (TPP-8OOCR, with R = C(n-1)H(2n-1), n = 8, 12, or 16) have been prepared through very simple synthesis protocols. The thermotropic phase behavior and the liquid crystalline (LC) organization structures of the synthesized porphyrin derivatives were systematically investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable-temperature small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) techniques. The shorter octanoic acid ester substituted porphyrin (C8-TPP) did not show liquid crystallinity and its metal porphyrins exhibited an uncommon columnar mesophase. The lauric acid octaester (C12-TPP) and the palmitic acid octaester (C16-TPP) series porphyrins generated hexagonal columnar mesophase Colh. Moreover, the metal porphyrins C12-TPPM and C16-TPPM with M = Zn, Cu, or Ni, exhibited well-organized Colh mesophases of broad LC temperature ranges increasing in the order of TPPNi

Comets in UV

NASA Astrophysics Data System (ADS)

Shustov, B.; Sachkov, M.; Gómez de Castro, A. I.; Vallejo, J. C.; Kanev, E.; Dorofeeva, V.

2018-04-01

Comets are important "eyewitnesses" of Solar System formation and evolution. Important tests to determine the chemical composition and to study the physical processes in cometary nuclei and coma need data in the UV range of the electromagnetic spectrum. Comprehensive and complete studies require additional ground-based observations and in situ experiments. We briefly review observations of comets in the ultraviolet (UV) and discuss the prospects of UV observations of comets and exocomets with space-borne instruments. A special reference is made to the World Space Observatory-Ultraviolet (WSO-UV) project.

New approach to predict photoallergic potentials of chemicals based on murine local lymph node assay.

PubMed

Maeda, Yosuke; Hirosaki, Haruka; Yamanaka, Hidenori; Takeyoshi, Masahiro

2018-05-23

Photoallergic dermatitis, caused by pharmaceuticals and other consumer products, is a very important issue in human health. However, S10 guidelines of the International Conference on Harmonization do not recommend the existing prediction methods for photoallergy because of their low predictability in human cases. We applied local lymph node assay (LLNA), a reliable, quantitative skin sensitization prediction test, to develop a new photoallergy prediction method. This method involves a three-step approach: (1) ultraviolet (UV) absorption analysis; (2) determination of no observed adverse effect level for skin phototoxicity based on LLNA; and (3) photoallergy evaluation based on LLNA. Photoallergic potential of chemicals was evaluated by comparing lymph node cell proliferation among groups treated with chemicals with minimal effect levels of skin sensitization and skin phototoxicity under UV irradiation (UV+) or non-UV irradiation (UV-). A case showing significant difference (P < .05) in lymph node cell proliferation rates between UV- and UV+ groups was considered positive for photoallergic reaction. After testing 13 chemicals, seven human photoallergens tested positive and the other six, with no evidence of causing photoallergic dermatitis or UV absorption, tested negative. Among these chemicals, both doxycycline hydrochloride and minocycline hydrochloride were tetracycline antibiotics with different photoallergic properties, and the new method clearly distinguished between the photoallergic properties of these chemicals. These findings suggested high predictability of our method; therefore, it is promising and effective in predicting human photoallergens. Copyright © 2018 John Wiley & Sons, Ltd.

Bias Selectable Dual Band AlGaN Ultra-violet Detectors

NASA Technical Reports Server (NTRS)

Yan, Feng; Miko, Laddawan; Franz, David; Guan, Bing; Stahle, Carl M.

2007-01-01

Bias selectable dual band AlGaN ultra-violet (UV) detectors, which can separate UV-A and UV-B using one detector in the same pixel by bias switching, have been designed, fabricated and characterized. A two-terminal n-p-n photo-transistor-like structure was used. When a forward bias is applied between the top electrode and the bottom electrode, the detectors can successfully detect W-A and reject UV-B. Under reverse bias, they can detect UV-B and reject UV-A. The proof of concept design shows that it is feasible to fabricate high performance dual-band UV detectors based on the current AlGaN material growth and fabrication technologies.

Are We Correctly Measuring Star-Formation Rates?

NASA Astrophysics Data System (ADS)

McQuinn, Kristen B.; Skillman, Evan D.; Dolphin, Andrew E.; Mitchell, Noah P.

2017-01-01

Integrating our knowledge of star formation (SF) traced by observations at different wavelengths is essential for correctly interpreting and comparing SF activity in a variety of systems and environments. This study compares extinction-corrected, integrated ultraviolet (UV) emission from resolved galaxies with color-magnitude diagram (CMD) based star-formation rates (SFRs) derived from resolved stellar populations and CMD fitting techniques in 19 nearby starburst and post-starburst dwarf galaxies. The data sets are from the panchromatic Starburst Irregular Dwarf Survey (STARBIRDS) and include deep legacy GALEX UV imaging, Hubble Space Telescope optical imaging, and Spitzer MIPS imaging. For the majority of the sample, the integrated near-UV fluxes predicted from the CMD-based SFRs—using four different models—agree with the measured, extinction corrected, integrated near-UV fluxes from GALEX images, but the far-UV (FUV) predicted fluxes do not. Furthermore, we find a systematic deviation between the SFRs based on integrated FUV luminosities and existing scaling relations, and the SFRs based on the resolved stellar populations. This offset is not driven by different SF timescales, variations in SFRs, UV attenuation, nor stochastic effects. This first comparison between CMD-based SFRs and an integrated FUV emission SFR indicator suggests that the most likely cause of the discrepancy is the theoretical FUV-SFR calibration from stellar evolutionary libraries and/or stellar atmospheric models. We present an empirical calibration of the FUV-based SFR relation for dwarf galaxies, with uncertainties, which is ˜53% larger than previous relations. These results have signficant implications for measuring FUV-based SFRs of high-redshift galaxies.

A comparison of UV cross-linking and vacuum baking for nucleic acid immobilization and retention

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

Nierzwicki-Bauer, S.A.; Gebhardt, J.S.; Linkkila, L.

The effectiveness of UV cross-linking and in vacuo baking for the immobilization and retention of DNA to various solid supports was investigated. Optimal immobilization treatments for supported and unsupported nitrocellulose and nylon membranes were: UV cross-linking at 254 nm with an exposure of 120 milliJoules/cm{sup 2}, or baking in vacuo for two hours at 80{degrees}C. UV-immobilized nitrocellulose-based membranes showed no increase in sensitivity when compared to baked membranes. An increase in sensitivity was observed for UV-immobilized nylon membranes as compared with baked nylon membranes in some instances, although this varied within lots of the membranes tested. Repeated strippings and heterologousmore » reprobings resulted in loss of target DNA from UV-immobilized nylon membranes as compared to baked nylon membranes. Loss of target DNA from UV-immobilized nitrocellulose-based membranes due to repeated strippings and reprobings was even more pronounced. In vacuo baking of supported and unsupported nitrocellulose and nylon membranes was more effective for immobilization, and more importantly, for retention of target DNA through many reprobings of the same blot.« less

Effect of substituents in benzoxazole derivatives of biphenyl on the optical properties and photostability of their thin films

NASA Astrophysics Data System (ADS)

Chaplanova, Zh. D.; Mikhailovskii, Yu. K.; Agabekov, V. E.; Ol'Khovik, V. K.; Vasilevskii, D. A.; Galinovskii, N. A.; Zhavnerko, G. K.

2009-07-01

We have studied the characteristic features of the luminescence of thin films, formed by deposition from solutions and thermal vacuum deposition (TVD), of 4,4'-bis[(E)-1-(1,3-benzoxazol-2-yl)-2-ethenyl]-2-fluorobiphenyl (BPh-1) and 4,4'-bis[(E)-1-(1,3-benzoxazol-2-yl)-2-ethenyl]-2,2'-difluorobiphenyl (BPh-2). We have established that fluorine atoms in the biphenyl moiety of the benzoxasole derivatives significantly improve the stability of the TVD films relative to oxidative aging compared with hexyloxy substituents. Irradiation with UV light stimulates quenching of luminescence and structuring of the TVD film of the difluoro-substituted derivative.

Study of structure and dielectric properties of 1:2 type modified Barium Niobates in bulk and thin film forms

NASA Astrophysics Data System (ADS)

Bishnoi, Bhagwanti Ben S.

In view of the processing and environmental issues pertaining to lead based ferroelectric materials, investigations on lead free ferroelectrics are carried intensively in recent years. These materials are interesting because, they are flexible with respect to structural changes and functional properties. These materials have potential device applications such as capacitors, sensors, actuators, and memory storage and microwave devices. This thesis is an attempt to elucidate the effect of substitution of isovalent ions (Sr, Ca) at the 'A' site of Hexagonal structured Barium Magnesium Niobate Ba(Mgl/3Nb 2/3)O3 (BMN) as well as effect of simultaneous substitution of divalent ions (Co2+ and Cu2+) on the 'B'-site' of Ba(Mg1/3Nb2/3)O3 (BMN) and Sr(Mg 1/3Nb2/3)O3 (SMN). Their structural, morphological, dielectric, impedance and optical properties are investigated. The XRD study on the ceramic compositions (SMN) showed single phase monoclinic hexagonal perovskite structure at room temperature. The SEM micrograph shows that the grains are uniformly distributed throughout the surface and the average grain size decreases with the substitution of divalent ion doping in Sr(Mg 1/3Nb2/3)O3 ceramic. The diffusivity of ceramics increases with increase in divalent ions substitution. The dielectric study confirmed that the relaxor nature is introduced in the Barium Niobate on replacement by other divalent ions at the A- or B'-site. Among various compositions in Sr(Cu1/3Nb2/3)O3 we obtained most promising dielectric properties. The impedance and modulus spectroscopy were employed to evaluate the different electrical properties of the grain and grain boundary of the ceramics. Ac Conductivity shows the two types of hopping conduction mechanism in frequency exponent vs temperature plots after the divalent ions replacement. The optical band gaps were calculated from UV-Visible spectroscopy ceramic suggested the presence of intermediately energy levels within the band gap. The single phase thin films of various compositions with A- and B'-site substitutions were successfully made using Pulsed laser deposition technique. Over all properties of films are identical to the respective bulk compositions except for some of the samples which exhibited relaxor behaviour only in the film form. Compared to O7+ irradiation the Ag15+ irradiation due to type of defects it created is more effective in reducing lattice strain induced dielectric losses along with marginal loss of dielectric constant. Significant increase in dielectric constant with low loss, on O 7+ as well as Ag15+ ion irradiation, may enhance the electro-optical properties which in turn increase compounds tuneablility for device applications.

Biologically effective surface UV climatology at Rome and Aosta, Italy

NASA Astrophysics Data System (ADS)

Siani, Anna Maria; Modesti, Sarah; Casale, Giuseppe Rocco; Diemoz, Henri; Colosimo, Alfredo

2013-05-01

Given the beneficial and harmful effects of UV radiation on human health, our study aims to provide a characterization of erythemal and vitamin D dose rates at two Italian sites, Rome and Aosta, subject to quite different environmental conditions. Based on the respective UV climatologies, exposure times needed to induce erythema or vitamin D photoproduction are provided as a function of the UV index.

UV shielding with visible transparency based properties of poly (styrene-co-acrylonitrile)/Ag doped ZnO nanocomposite

NASA Astrophysics Data System (ADS)

Singh, Rajender; Verma, Karan; Singh, Tejbir; Barman, P. B.; Sharma, Dheeraj

2018-02-01

Development of ultraviolet (UV) shielding with visible transparency based thermoplastic polymer nanocomposite (PNs) presents an important requisite in terms of their efficiency and cost. Present study contributed for the same approach by dispersion of Ag doped ZnO nanoparticles upto 10 wt% in poly (styrene-co-acrylonitrile) matrix by insitu emulsion polymerization method. The crystal and chemical structure of PNs has been analyzed by x-ray diffraction (XRD) and fourier infrared spectrometer (FTIR) techniques. The morphological and elemental information of synthesized nanomaterial has been studied by field emission scanning electron microscope (FESEM) and energy dispersive spectroscopy (EDS) technique. The optical properties of PNs has been studied by UV-visible spectroscopy technique. The incorporation of nanoparticles in polymer matrix absorb the complete UV light with visible transparency. The present reported polymer nanocomposite (PNs) have tuned refractive index with UV blocking and visible transparency based properties which can serve as a viable alternative as compared to related conventional materials.

Several cases of undesirable effects caused by methacrylate ultraviolet-curing nail polish for non-professional use.

PubMed

Dahlin, Jakob; Berne, Berit; Dunér, Kari; Hosseiny, Sara; Matura, Mihály; Nyman, Gunnar; Tammela, Monica; Isaksson, Marléne

2016-09-01

Ultraviolet (UV)-curing nail polishes based on acrylates or methacrylates are currently also available for non-professional use. The Swedish Medical Products Agency recently prohibited one brand of UV-curing polish, because several consumers reported undesirable effects after using it. To investigate whether consumers with undesirable effects after using the UV-curing nail polish that was later prohibited were contact allergic to the polish and its individual ingredients. Eight patients who had reported severe skin reactions after the use of the UV-curing polish were patch tested with two coatings of the nail polish and its ingredients at five dermatology departments in Sweden. All patients tested except one showed contact allergic reactions to one or several of the acrylate-based or methacrylate-based ingredients in the nail polish. The non-professional use of UV-curing nail polishes poses a risk of sensitization from acrylates and methacrylates. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Selection of UV Resins for Nanostructured Molds for Thermal-NIL.

PubMed

Jia, Zheng; Choi, Junseo; Park, Sunggook

2018-06-18

Nanoimprint molds made of soft polymeric materials have advantages of low demolding force and low fabrication cost over Si or metal-based hard molds. However, such advantages are often sacrificed by their reduced replication fidelity associated with the low mechanical strength. In this paper, we studied replication fidelity of different UV-resin molds copied from a Si master mold via UV nanoimprint lithography (NIL) and their thermal imprinting performance into a thermoplastic polymer. Four different UV resins were studied: two were high surface energy UV resins based on tripropyleneglycol diacrylate (TPGDA resin) and polypropyleneglycol diacrylate (PPGDA resin), and the other two were commercially available, low surface energy poly-urethane acrylate (PUA resin) and fluorine-containing (MD 700) UV resins. The replication fidelity among the four UV-resins during UV nanoimprint lithograph from a Si master with sharp nanostructures was in the increasing order of (poorest) PUA resin < MD 700 < PPGDA resin < TPGDA resin (best). The results show that the high surface energy and small monomer size are keys to achieving good UV resin filling into sharp nanostructures over the viscosity of the resin solution. When the four UV-resin molds were used for thermal-NIL into a thermoplastic polymer, the replication fidelity was in the increasing order of (poorest) MD 700 < TPGDA resin < PUA resin (best), which follows the same order of their Young's moduli. Our results indicate that the selection of an appropriate UV resin for NIL molds requires consideration of the replication fidelities in the mold fabrication and the subsequent thermal-NIL into thermoplastic polymers. © 2018 IOP Publishing Ltd.

The effectiveness of UV-C radiation for facility-wide environmental disinfection to reduce health care-acquired infections.

PubMed

Napolitano, Nathanael A; Mahapatra, Tanmay; Tang, Weiming

2015-12-01

Health care-acquired infections (HAIs) constitute an increasing threat for patients worldwide. Potential contributors of HAIs include environmental surfaces in health care settings, where ultraviolet-C radiation (UV-C) is commonly used for disinfection. This UV-C intervention-based pilot study was conducted in a hospital setting to identify any change in the incidence of HAIs before and after UV-C intervention, and to determine the effectiveness of UV-C in reducing pathogens. In a hospital in Culver City, CA, during 2012-2013, bactericidal doses of UV-C radiation (254 nm) were delivered through a UV-C-based mobile environmental decontamination unit. The UV-C dosing technology and expertise of the specifically trained personnel were provided together as a dedicated service model by a contracted company. The incidence of HAIs before and after the intervention period were determined and compared. The dedicated service model dramatically reduced HAIs (incidence difference, 1.3/1000 patient-days, a 34.2% reduction). Reductions in the total number and incidence proportions (28.8%) of HAIs were observed after increasing and maintaining the coverage of UV-C treatments. The dedicated service model was found to be effective in decreasing the incidence of HAIs, which could reduce disease morbidity and mortality in hospitalized patients. This model provides a continuously monitored and frequently UV-C-treated patient environment. This approach to UV-C disinfection was associated with a decreased incidence of HAIs. Copyright © 2015 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Elsevier Inc. All rights reserved.

Evaluation of advanced oxidation processes for water and wastewater treatment - A critical review.

PubMed

Miklos, David B; Remy, Christian; Jekel, Martin; Linden, Karl G; Drewes, Jörg E; Hübner, Uwe

2018-03-22

This study provides an overview of established processes as well as recent progress in emerging technologies for advanced oxidation processes (AOPs). In addition to a discussion of major reaction mechanisms and formation of by-products, data on energy efficiency were collected in an extensive analysis of studies reported in the peer-reviewed literature enabling a critical comparison of various established and emerging AOPs based on electrical energy per order (E EO ) values. Despite strong variations within reviewed E EO values, significant differences could be observed between three groups of AOPs: (1) O 3 (often considered as AOP-like process), O 3 /H 2 O 2 , O 3 /UV, UV/H 2 O 2 , UV/persulfate, UV/chlorine, and electron beam represent median E EO values of <1 kWh/m 3 , while median energy consumption by (2) photo-Fenton, plasma, and electrolytic AOPs were significantly higher (E EO values in the range of 1-100 kWh/m 3 ). (3) UV-based photocatalysis, ultrasound, and microwave-based AOPs are characterized by median values of >100 kWh/m 3 and were therefore considered as not (yet) energy efficient AOPs. Specific evaluation of 147 data points for the UV/H 2 O 2 process revealed strong effects of operational conditions on reported E EO values. Besides water type and quality, a major influence was observed for process capacity (lab-vs. pilot-vs. full-scale applications) and, in case of UV-based processes, of the lamp type. However, due to the contribution of other factors, correlation of E EO values with specific water quality parameters such as UV absorbance and dissolved organic carbon were not substantial. Also, correlations between E EO and compound reactivity with OH-radicals were not significant (photolytically active compounds were not considered). Based on these findings, recommendations regarding the use of the E EO concept, including the upscaling of laboratory results, were derived. Copyright © 2018 Elsevier Ltd. All rights reserved.

Efficient Ultraviolet Light Detector Based on a Crystalline Viologen-Based Metal-Organic Framework with Rapid Visible Color Change under Irradiation.

PubMed

Hu, Shuzhi; Zhang, Jie; Chen, Shuhuang; Dai, Jingcao; Fu, Zhiyong

2017-11-22

A convenient colorimetric molecular system constructed by the zinc viologen-carboxylate framework is developed for naked eye detection of instantaneous UV exposure levels. Only narrow-band absorption in UV regions and a unique interpenetrated structure of its colorless crystal enable the system to give a fast response toward UV irradiance with intensity as low as 0.001 mw/cm 2 .

207-nm UV light - a promising tool for safe low-cost reduction of surgical site infections. I: in vitro studies.

PubMed

Buonanno, Manuela; Randers-Pehrson, Gerhard; Bigelow, Alan W; Trivedi, Sheetal; Lowy, Franklin D; Spotnitz, Henry M; Hammer, Scott M; Brenner, David J

2013-01-01

0.5% to 10% of clean surgeries result in surgical-site infections, and attempts to reduce this rate have had limited success. Germicidal UV lamps, with a broad wavelength spectrum from 200 to 400 nm are an effective bactericidal option against drug-resistant and drug-sensitive bacteria, but represent a health hazard to patient and staff. By contrast, because of its limited penetration, ~200 nm far-UVC light is predicted to be effective in killing bacteria, but without the human health hazards to skin and eyes associated with conventional germicidal UV exposure. The aim of this work was to test the biophysically-based hypothesis that ~200 nm UV light is significantly cytotoxic to bacteria, but minimally cytotoxic or mutagenic to human cells either isolated or within tissues. A Kr-Br excimer lamp was used, which produces 207-nm UV light, with a filter to remove higher-wavelength components. Comparisons were made with results from a conventional broad spectrum 254-nm UV germicidal lamp. First, cell inactivation vs. UV fluence data were generated for methicillin-resistant S. aureus (MRSA) bacteria and also for normal human fibroblasts. Second, yields of the main UV-associated pre-mutagenic DNA lesions (cyclobutane pyrimidine dimers and 6-4 photoproducts) were measured, for both UV radiations incident on 3-D human skin tissue. We found that 207-nm UV light kills MRSA efficiently but, unlike conventional germicidal UV lamps, produces little cell killing in human cells. In a 3-D human skin model, 207-nm UV light produced almost no pre-mutagenic UV-associated DNA lesions, in contrast to significant yields induced by a conventional germicidal UV lamp. As predicted based on biophysical considerations, 207-nm light kills bacteria efficiently but does not appear to be significantly cytotoxic or mutagenic to human cells. Used appropriately, 207-nm light may have the potential for safely and inexpensively reducing surgical-site infection rates, including those of drug-resistant origin.

Destruction of microcystins (cyanotoxins) by UV-254 nm-based direct photolysis and advanced oxidation processes (AOPs): influence of variable amino acids on the degradation kinetics and reaction mechanisms.

PubMed

He, Xuexiang; de la Cruz, Armah A; Hiskia, Anastasia; Kaloudis, Triantafyllos; O'Shea, Kevin; Dionysiou, Dionysios D

2015-05-01

Hepatotoxic microcystins (MCs) are the most frequently detected group of cyanobacterial toxins. This study investigated the degradation of common MC variants in water, MC-LR, MC-RR, MC-YR and MC-LA, by UV-254 nm-based processes, UV only, UV/H2O2, UV/S2O8(2-) and UV/HSO5(-). Limited direct photolysis of MCs was observed, while the addition of an oxidant significantly improved the degradation efficiency with an order of UV/S2O8(2-) > UV/HSO5(-) > UV/H2O2 at the same initial molar concentration of the oxidant. The removal of MC-LR by UV/H2O2 appeared to be faster than another cyanotoxin, cylindrospermopsin, at either the same initial molar concentration or the same initial organic carbon concentration of the toxin. It suggested a faster reaction of MC-LR with hydroxyl radical, which was further supported by the determined second-order rate constant of MCs with hydroxyl radical. Both isomerization and photohydration byproducts were observed in UV only process for all four MCs; while in UV/H2O2, hydroxylation and diene-Adda double bond cleavage byproducts were detected. The presence of a tyrosine in the structure of MC-YR significantly promoted the formation of monohydroxylation byproduct m/z 1061; while the presence of a second arginine in MC-RR led to the elimination of a guanidine group and the absence of double bond cleavage byproducts. It was therefore demonstrated in this study that the variable amino acids in the structure of MCs influenced not only the degradation kinetics but also the preferable reaction mechanisms. Copyright © 2015 Elsevier Ltd. All rights reserved.

Visualizing and quantifying dose distribution in a UV reactor using three-dimensional laser-induced fluorescence.

PubMed

Gandhi, Varun N; Roberts, Philip J W; Kim, Jae-Hong

2012-12-18

Evaluating the performance of typical water treatment UV reactors is challenging due to the complexity in assessing spatial and temporal variation of UV fluence, resulting from highly unsteady, turbulent nature of flow and variation in UV intensity. In this study, three-dimensional laser-induced fluorescence (3DLIF) was applied to visualize and quantitatively analyze a lab-scale UV reactor consisting of one lamp sleeve placed perpendicular to flow. Mapping the spatial and temporal fluence delivery and MS2 inactivation revealed the highest local fluence in the wake zone due to longer residence time and higher UV exposure, while the lowest local fluence occurred in a region near the walls due to short-circuiting flow and lower UV fluence rate. Comparing the tracer based decomposition between hydrodynamics and IT revealed similar coherent structures showing the dependency of fluence delivery on the reactor flow. The location of tracer injection, varying the height and upstream distance from the lamp center, was found to significantly affect the UV fluence received by the tracer. A Lagrangian-based analysis was also employed to predict the fluence along specific paths of travel, which agreed with the experiments. The 3DLIF technique developed in this study provides new insight on dose delivery that fluctuates both spatially and temporally and is expected to aid design and optimization of UV reactors as well as validate computational fluid dynamics models that are widely used to simulate UV reactor performances.

CRYPTOCHROME mediates behavioral executive choice in response to UV light

PubMed Central

Baik, Lisa S.; Fogle, Keri J.; Roberts, Logan; Galschiodt, Alexis M.; Chevez, Joshua A.; Recinos, Yocelyn; Nguy, Vinh; Holmes, Todd C.

2017-01-01

Drosophila melanogaster CRYPTOCHROME (CRY) mediates behavioral and electrophysiological responses to blue light coded by circadian and arousal neurons. However, spectroscopic and biochemical assays of heterologously expressed CRY suggest that CRY may mediate functional responses to UV-A (ultraviolet A) light as well. To determine the relative contributions of distinct phototransduction systems, we tested mutants lacking CRY and mutants with disrupted opsin-based phototransduction for behavioral and electrophysiological responses to UV light. CRY and opsin-based external photoreceptor systems cooperate for UV light-evoked acute responses. CRY mediates behavioral avoidance responses related to executive choice, consistent with its expression in central brain neurons. PMID:28062690

Bright Points and Subflares in UV Lines and in X-Rays

NASA Technical Reports Server (NTRS)

Rovira, M.; Schmieder, B.; Demoulin, P.; Simnett, G. M.; Hagyard, M. J.; Reichmann, E.; Tandberg-Hanssen, E.

1998-01-01

We have analysed an active region which was observed in Halpha (MSDP), UV lines (SMM/UVSP), and in X rays (SMM/HXIS). In this active region there were only a few subflares and many small bright points visible in UV and in X rays. Using an extrapolation based on the Fourier transform we have computed magnetic field lines connecting different photospheric magnetic polarities from ground-based magnetograms. Along the magnetic inversion lines we find 2 different zones: 1. a high shear region (less than 70 degrees) where subflares occur 2. a low shear region along the magnetic inversion line where UV bright points are observed.

UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene

PubMed Central

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-01-01

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o-chloronitrobenzene (o-CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o-CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o-CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο-CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H2 pressure, 100% conversion of o-CNB, and 81.1% o-CAN selectivity were obtained, even at high molar ratio (8000:1) of o-CNB to Pd. PMID:29662004

UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene.

PubMed

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-04-14

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o -chloronitrobenzene ( o -CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o -CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o -CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο -CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H₂ pressure, 100% conversion of o -CNB, and 81.1% o -CAN selectivity were obtained, even at high molar ratio (8000:1) of o -CNB to Pd.

Modeling the natural UV irradiation and comparative UV measurements at Moussala BEO (BG)

NASA Astrophysics Data System (ADS)

Tyutyundzhiev, N.; Angelov, Ch; Lovchinov, K.; Nitchev, Hr; Petrov, M.; Arsov, T.

2018-03-01

Studies of and modeling the impact of natural UV irradiation on the human population are of significant importance for human activity and economics. The sharp increase of environmental problems – extraordinary temperature changes, solar irradiation abnormalities, icy rains – raises the question of developing novel means of assessing and predicting potential UV effects. In this paper, we discuss new UV irradiation modeling based on recent real-time measurements at Moussala Basic Environmental Observatory (BEO) on Moussala Peak (2925 m ASL) in Rila Mountain, Bulgaria, and highlight the development and initial validation of portable embedded devices for UV-A, UV-B monitoring using open-source software architecture, narrow bandpass UV sensors, and the popular Arduino controllers. Despite the high temporal resolution of the VIS and UV irradiation measurements, the results obtained reveal the need of new assumptions in order to minimize the discrepancy with available databases.

Tunable ferromagnetic resonance in La-Co substituted barium hexaferrites at millimeter wave frequencies

NASA Astrophysics Data System (ADS)

Korolev, Konstantin A.; Wu, Chuanjian; Yu, Zhong; Sun, Ke; Afsar, Mohammed N.; Harris, Vincent G.

2018-05-01

Transmittance measurements have been performed on La-Co substituted barium hexaferrites in millimeter waves. Broadband millimeter-wave measurements have been carried out using the free space quasi-optical spectrometer, equipped with a set of high power backward wave oscillators covering the frequency range of 30 - 120 GHz. Strong absorption zones have been observed in the millimeter-wave transmittance spectra of all La-Co substituted barium hexaferrites due to the ferromagnetic resonance. Linear shift of ferromagnetic resonance frequency as functions of La-Co substitutions have been found. Real and imaginary parts of dielectric permittivity of La-Co substituted barium hexaferrites have been calculated using the analysis of recorded high precision transmittance spectra. Frequency dependences of magnetic permeability of La-Co substituted barium hexaferrites, as well as saturation magnetization and anisotropy field have been determined based on Schlömann's theory for partially magnetized ferrites. La-Co substituted barium hexaferrites have been further investigated by DC magnetization to assess magnetic behavior and compare with millimeter wave data. Consistency of saturation magnetization determined independently by both millimeter wave absorption and DC magnetization have been found for all La-Co substituted barium hexaferrites. These materials seem to be quite promising as tunable millimeter wave absorbers, filters, circulators, based on the adjusting of their substitution parameters.

Impacts of Vehicle Weight Reduction via Material Substitution on Life-Cycle Greenhouse Gas Emissions.

PubMed

Kelly, Jarod C; Sullivan, John L; Burnham, Andrew; Elgowainy, Amgad

2015-10-20

This study examines the vehicle-cycle and vehicle total life-cycle impacts of substituting lightweight materials into vehicles. We determine part-based greenhouse gas (GHG) emission ratios by collecting material substitution data and evaluating that alongside known mass-based GHG ratios (using and updating Argonne National Laboratory's GREET model) associated with material pair substitutions. Several vehicle parts are lightweighted via material substitution, using substitution ratios from a U.S. Department of Energy report, to determine GHG emissions. We then examine fuel-cycle GHG reductions from lightweighting. The fuel reduction value methodology is applied using FRV estimates of 0.15-0.25, and 0.25-0.5 L/(100km·100 kg), with and without powertrain adjustments, respectively. GHG breakeven values are derived for both driving distance and material substitution ratio. While material substitution can reduce vehicle weight, it often increases vehicle-cycle GHGs. It is likely that replacing steel (the dominant vehicle material) with wrought aluminum, carbon fiber reinforced plastic (CRFP), or magnesium will increase vehicle-cycle GHGs. However, lifetime fuel economy benefits often outweigh the vehicle-cycle, resulting in a net total life-cycle GHG benefit. This is the case for steel replaced by wrought aluminum in all assumed cases, and for CFRP and magnesium except for high substitution ratio and low FRV.

Production of a Novel Mineral-based Sun Lotion for Protecting the Skin from Biohazards of Electromagnetic Radiation in the UV Region.

PubMed

Movahedi, M M; Alipour, A; Mortazavi, S A R; Tayebi, M

2014-03-01

Sun protection materials have been one of the major concerns in pharmaceutical in-dustry since almost one century ago. Various materials have been found to have such an effect but there are still many unknown substances that have not been discovered. Objective : To introduce a novel mineral-based sun lotion with considerable UV absorption properties compared to commercially available sunscreens.  UV absorption properties of transparent plas-tic sheets covered by a uniform cream layer of different mineral-based sun lotions and a commercially available sun lotion were tested. Sun lotions containing specific proportion of bentonite and zeolite minerals were capable of absorbing the highest level of UV light com-pared to that of the commercially available sun lotion. Mineral-based sun lotions can be considered as cost effective alternatives for current commercial sunscreens.

Production of a Novel Mineral-based Sun Lotion for Protecting the Skin from Biohazards of Electromagnetic Radiation in the UV Region

PubMed Central

Movahedi, M M; Alipour, A; Mortazavi, S A R; Tayebi, M

2014-01-01

Background: Sun protection materials have been one of the major concerns in pharmaceutical in­dustry since almost one century ago. Various materials have been found to have such an effect but there are still many unknown substances that have not been discovered. Objective: To introduce a novel mineral-based sun lotion with considerable UV absorption properties compared to commercially available sunscreens. Method:  UV absorption properties of transparent plas­tic sheets covered by a uniform cream layer of different mineral-based sun lotions and a commercially available sun lotion were tested. Results: Sun lotions containing specific proportion of bentonite and zeolite minerals were capable of absorbing the highest level of UV light com­pared to that of the commercially available sun lotion. Conclusion: Mineral-based sun lotions can be considered as cost effective alternatives for current commercial sunscreens. PMID:25505763

COMPARATIVE DISINFECTION EFFICIENCY OF PULSED AND CONTINUOUS-WAVE UV IRRADIATION TECHNOLOGIES

EPA Science Inventory

Pulsed UV (PUV) is novel UV irradiation system that is a non-mercury lamp based alternative to currently used continuous-wave systems for water disinfection. To compare the polychromatic PUV irradiation disinfection efficiency with that from continuous wave monochromatic low-pre...

AOX removal from industrial wastewaters using advanced oxidation processes: assessment of a combined chemical-biological oxidation.

PubMed

Luyten, J; Sniegowski, K; Van Eyck, K; Maertens, D; Timmermans, S; Liers, Sven; Braeken, L

2013-01-01

In this paper, the abatement of adsorbable halogenated organic compounds (AOX) from an industrial wastewater containing relatively high chloride concentrations by a combined chemical and biological oxidation is assessed. For chemical oxidation, the O(3)/UV, H(2)O(2)/UV and photo-Fenton processes are evaluated on pilot scale. Biological oxidation is simulated in a 4 h respirometry experiment with periodic aeration. The results show that a selective degradation of AOX with respect to the matrix compounds (expressed as chemical oxygen demand) could be achieved. For O(3)/UV, lowering the ratio of O(3) dosage to UV intensity leads to a better selectivity for AOX. During O(3)-based experiments, the AOX removal is generally less than during the H(2)O(2)-based experiments. However, after biological oxidation, the AOX levels are comparable. For H(2)O(2)/UV, optimal operating parameters for UV and H(2)O(2) dosage are next determined in a second run with another wastewater sample.

Visible-Blind UV Photodetector Based on Single-Walled Carbon Nanotube Thin Film/ZnO Vertical Heterostructures.

PubMed

Li, Guanghui; Suja, Mohammad; Chen, Mingguang; Bekyarova, Elena; Haddon, Robert C; Liu, Jianlin; Itkis, Mikhail E

2017-10-25

Ultraviolet (UV) photodetectors based on heterojunctions of conventional (Ge, Si, and GaAs) and wide bandgap semiconductors have been recently demonstrated, but achieving high UV sensitivity and visible-blind photodetection still remains a challenge. Here, we utilized a semitransparent film of p-type semiconducting single-walled carbon nanotubes (SC-SWNTs) with an energy gap of 0.68 ± 0.07 eV in combination with a molecular beam epitaxy grown n-ZnO layer to build a vertical p-SC-SWNT/n-ZnO heterojunction-based UV photodetector. The resulting device shows a current rectification ratio of 10 3 , a current photoresponsivity up to 400 A/W in the UV spectral range from 370 to 230 nm, and a low dark current. The detector is practically visible-blind with the UV-to-visible photoresponsivity ratio of 10 5 due to extremely short photocarrier lifetimes in the one-dimensional SWNTs because of strong electron-phonon interactions leading to exciton formation. In this vertical configuration, UV radiation penetrates the top semitransparent SC-SWNT layer with low losses (10-20%) and excites photocarriers within the n-ZnO layer in close proximity to the p-SC-SWNT/n-ZnO interface, where electron-hole pairs are efficiently separated by a high built-in electric field associated with the heterojunction.

Correlation between ionic size and valence state of tetra, penta and hexavalent B-site substitution with solubility limit, phase transformation and multiferroic properties of Bi0.875Eu0.125FeO3

NASA Astrophysics Data System (ADS)

Mumtaz, Fiza; Jaffari, G. Hassnain; Hassan, Qadeer ul; Shah, S. Ismat

2018-06-01

We present detailed comparative study of effect of isovalent i.e. Eu+3 substitution at A-site and tetra (Ti+4, Zr+4), penta (V+5) and hexavalent (W+6) substitutions at B-site in BiFeO3. Eu+3 substitution led to phase transformation and exhibited mixed phases i.e. rhombohedral and orthorhombic, while tetravalent substituents (Ti+4 and Zr+4) led to stabilization of cubic phase. In higher valent (i.e. V+5 and W+6) cases solubility limit was significantly reduced where orthorhombic phase was observed as in the case of parent compound. Phase transformation as a consequence of increase in microstrain and chemical pressure induced by the substituent has been discussed. Solubility limit of different B-site dopants i.e. Zr, W and V was extracted to 5%, 2% and 2%, respectively. Extra phases in various cases were Bi2Fe4O9, Bi25FeO40, Bi14W2O27, and Bi23V4O44.5 and their fractional amount have been quantified. Ti was substituted up to 15% and has been observed to be completely soluble in the parent compound. Solubility limits depends on ionic radii mismatch and valance difference of Fe+3 and dopant, in which valance difference plays more dominant role. Solubility limit and phase transformation has been explained in terms of change in bond strength and tolerance factor induced by incorporation of dopant which depend on its size and valence state. Detail optical, dielectric, ferroelectric, magnetic and transport properties of Eu and Ti co-doped samples and selected low concentration B-site doped compositions (i.e. 2%) have presented and discussed. Two d-d transitions and three charge transfer transitions were observed within UV-VIS range. Both change in cell volume for the same phase and transformation in crystal structure affects the band gap. Increase in room temperature dielectric constant and saturation polarization was also found to increase in case of Eu-Ti co-doped samples with increasing concentration of Ti. Substitution of Eu at A-site and Ti at B-site led to observation of weak ferromagnetism. Effect of extra phases on ferroelectricity and transport properties have also been discussed.

An ab initio mechanism for efficient population of triplet states in cytotoxic sulfur substituted DNA bases: the case of 6-thioguanine.

PubMed

Martínez-Fernández, Lara; González, Leticia; Corral, Inés

2012-02-18

The deactivation mechanism of the cytotoxic 6-thioguanine, the 6-sulfur-substituted analogue of the canonical DNA base, is unveiled by ab initio calculations. Oxygen-by-sulfur substitution leads to efficient population of triplet states-the first step for generating singlet oxygen-which is responsible for its cytotoxicity. This journal is © The Royal Society of Chemistry 2012

Footprints of the sun: memory of UV and light stress in plants

PubMed Central

Müller-Xing, Ralf; Xing, Qian; Goodrich, Justin

2014-01-01

Sunlight provides the necessary energy for plant growth via photosynthesis but high light and particular its integral ultraviolet (UV) part causes stress potentially leading to serious damage to DNA, proteins, and other cellular components. Plants show adaptation to environmental stresses, sometimes referred to as “plant memory.” There is growing evidence that plants memorize exposure to biotic or abiotic stresses through epigenetic mechanisms at the cellular level. UV target genes such as CHALCONE SYNTHASE (CHS) respond immediately to UV treatment and studies of the recently identified UV-B receptor UV RESISTANCE LOCUS 8 (UVR8) confirm the expedite nature of UV signaling. Considering these findings, an UV memory seems redundant. However, several lines of evidence suggest that plants may develop an epigenetic memory of UV and light stress, but in comparison to other abiotic stresses there has been relatively little investigation. Here we summarize the state of knowledge about acclimation and adaptation of plants to UV light and discuss the possibility of chromatin based epigenetic memory. PMID:25278950

Effect of particle size of calcium phosphate based bioceramic drug delivery carrier on the release kinetics of ciprofloxacin hydrochloride: an in vitro study

NASA Astrophysics Data System (ADS)

Sasikumar, Swamiappan

2013-09-01

Hydroxyapatite (HAP) is the constituent of calcium phosphate based bone cement and it is extensively used as a bone substitute and drug delivery vehicle in various biomedical applications. In the present study we investigated the release kinetics of ciprofloxacin loaded HAP and analyzed its ability to function as a targeted and sustained release drug carrier. Synthesis of HAP was carried out by combustion method using tartaric acid as a fuel and nitric acid as an oxidizer. Powder XRD and FTIR techniques were employed to characterize the phase purity of the drug carrier and to verify the chemical interaction between the drug and carrier. The synthesized powders were sieve separated to make two different drug carriers with different particle sizes and the surface topography of the pellets of the drug carrier was imaged by AFM. Surface area and porosity of the drug carrier was carried out using surface area analyzer. The in-vitro drug release kinetics was performed in simulated body fluid, at 37.3°C. The amount of ciprofloxacin released is measured using UV-visible spectroscopy following the characteristic λ max of 278 nm. The release saturates around 450 h which indicates that it can be used as a targeted and sustained release carrier for bone infections.

Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect.

PubMed

Wohlmuth da Silva, Salatiel; Arenhart Heberle, Alan Nelson; Pereira Santos, Alexia; Siqueira Rodrigues, Marco Antônio; Pérez-Herranz, Valentín; Moura Bernardes, Andréa

2018-05-29

Antibiotics are not efficiently removed in conventional wastewater treatments. In fact, different advanced oxidation process (AOPs), including ozone, peroxide, UV radiation, among others, are being investigated in the elimination of microcontaminants. Most of AOPs proved to be efficient on the degradation of antibiotics, but the mineralization is on the one hand not evaluated or on the other hand not high. At this work, the UV-based hybrid process, namely Photo-assisted electrochemical oxidation (PEO), was applied, aiming the mineralization of microcontaminants such as the antibiotics Amoxicillin (AMX), Norfloxacin (NOR) and Azithromycin (AZI). The influence of the individual contributions of electrochemical oxidation (EO) and the UV-base processes on the hybrid process (PEO) was analysed. Results showed that AMX and NOR presented higher mineralization rate under direct photolysis than AZI due to the high absorption of UV radiation. For the EO processes, a low mineralization was found for all antibiotics, what was associated to a mass-transport limitation related to the low concentration of contaminants (200 µg/L). Besides that, an increase in mineralization was found, when heterogeneous photocatalysis and EO are compared, due to the influence of UV radiation, which overcomes the mass-transport limitations. Although the UV-based processes control the reaction pathway that leads to mineralization, the best results to mineralize the antibiotics were achieved by PEO hybrid process. This can be explained by the synergistic effect of the processes that constitute them. A higher mineralization was achieved, which is an important and useful finding to avoid the discharge of microcontaminants in the environment.

Cholesteric liquid crystals as sensor materials for bioequivalent UV-dosimetry

NASA Astrophysics Data System (ADS)

Lisetski, Longin N.; Vashchenko, O. V.; Panikarskaya, V. D.; Sidletskiy, O. T.; Terenetskaya, Irina P.

2003-12-01

Selective reflection spectra have been studied for cholesteric matrices doped with certain steroids of vitamin D group, and substantial effect of the dopants upon the helical pitch was noted. Under UV irradiation, shifts of selective reflection peaks were observed. It is argued that the effect studied can be used for monitoring of vitamin D formation reactions induced by UV irradiation, thus being a base of bioequivalent UV dosimetry.

Development of green betaine-based deep eutectic solvent aqueous two-phase system for the extraction of protein.

PubMed

Li, Na; Wang, Yuzhi; Xu, Kaijia; Huang, Yanhua; Wen, Qian; Ding, Xueqin

2016-05-15

Six kinds of new type of green betaine-based deep eutectic solvents (DESs) have been synthesized. Deep eutectic solvent aqueous two-phase systems (DES-ATPS) were established and successfully applied in the extraction of protein. Betaine-urea (Be-U) was selected as the suitable extractant. Single factor experiments were carried out to determine the optimum conditions of the extraction process, such as the salt concentration, the mass of DES, the separation time, the amount of protein, the temperature and the pH value. The extraction efficiency could achieve to 99.82% under the optimum conditions. Mixed sample and practical sample analysis were discussed. The back extraction experiment was implemented and the back extraction efficiency could reach to 32.66%. The precision experiment, repeatability experiment and stability experiment were investigated. UV-vis, FT-IR and circular dichroism (CD) spectra confirmed that the conformation of protein was not changed during the process of extraction. The mechanisms of extraction were researched by dynamic light scattering (DLS), the measurement of the conductivity and transmission electron microscopy (TEM). DES-protein aggregates and embraces phenomenon play considerable roles in the separation process. All of these results indicated that betaine-based DES-ATPS may provide a potential substitute new method for the separation of proteins. Copyright © 2016 Elsevier B.V. All rights reserved.

The halosol process for water disinfection and dehalogenation

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

Acra, A.; Jurdi, M.; Mu'allem, H.

Substitution of chlorine and its derivatives as agents to disinfect water and wastewater effluents because of concern for the formation of the mutagenic and carcinogenic trihalomethanes (THM) may be a protracted endeavor. Excess chlorine residuals need to be controlled by dechlorinated agents, e.g., SO{sub 2}, to avoid esthetic objections voiced by consumers and the risk to aquatic environments. We focused on the phenomenon of photodecomposition and aqueons halogen solutions by sunlight. The halosol process, a batch system for solar dehalogenation, was developed into a flow-through system for the halosol disinfection of water. A prototype facility incorporated a solar reactor, throughmore » which chlorinated water flowed, made of borosilicate glass tube with a serpentine shape supported by a frame. Disinfection is induced by two cooperative biocidal agents (a halogen and sunlight) with sequential solar dehalogenation. An overall mean photodechlorination rate, K, of 0.238 m{sup 2}/W-h was obtained. The calculated solar UV-A fluence required to reduce the initial chlorine residuals by 90% and 99% was 9.65 and 19.30 W-h/m{sup 2}. The most effective photodechlorination components of sunlight were in the UV-A region of the spectrum: effectiveness decreased exponentially with wavelength.« less

A chemosensor for micro- to nano-molar detection of Ag+ and Hg2+ ions in pure aqueous media and its applications in cell imaging.

PubMed

Nandre, Jitendra P; Patil, Samadhan R; Sahoo, Suban K; Pradeep, Chullikkattil P; Churakov, Andrei; Yu, Fabiao; Chen, Lingxin; Redshaw, Carl; Patil, Ashok A; Patil, Umesh D

2017-10-24

The pyridine substituted thiourea derivative PTB-1 was synthesized and characterized by spectroscopic techniques as well as by single crystal X-ray crystallography. The metal ion sensing ability of PTB-1 was explored by various experimental (naked-eye, UV-Vis, fluorescence, mass spectrometry and 1 H NMR spectroscopy) and theoretical (B3LYP/6-31G**/LANL2DZ) methods. PTB-1 exhibited a highly selective naked-eye detectable color change from colorless to dark brown and UV-Vis spectral changes for the detection of Ag + with a detection limit of 3.67 μM in aqueous medium. The detection of Ag + ions was achieved by test paper strip and supported silica methods. In contrast, PTB-1 exhibited a 23-fold enhanced emission at 420 nm in the presence of Hg 2+ ions with a nano-molar detection limit of 0.69 nM. Finally, the sensor PTB-1 was applied successfully for the intracellular detection of Hg 2+ ions in a HepG2 liver cell line, which was monitored by the use of confocal imaging techniques.

Progression in structural, magnetic and electrical properties of La-doped group IV elements

NASA Astrophysics Data System (ADS)

Deepapriya, S.; Annie Vinosha, P.; Rodney, John D.; Jerome Das, S.

2018-04-01

Progression of group IV elements such as zinc ferrite (ZnFe2O4), cobalt ferrite (CoFe2O4) was synthesized by doping lanthanum (La), via adopting a facile co-precipitation method. Doping hefty rare earth ion in spinel structure can amend to the physical properties of the lattice, which can be used in the enhancement of magnetic and electrical properties of the as-synthesized nanomaterial, it is vital to metamorphose and optimize its micro structural and magnetic features. The structural properties of the samples was analysed by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), Transmission electron microscopy (TEM) and UV-visible spectral analysis (UV-vis) reveals the optical property and optical band gap. The magnetic properties were evaluated using a vibrating sample magnetometer (VSM), the presence of functional group was confirmed by FTIR. XRD analyses elucidates that the synthesized samples zinc and cobalt had a spinel structure. From TEM analyses the morphology and diameter of the particle was observed. The substituted rare earth ions in Zinc ferrite inhibit the grain growth of the materials in an efficient manner compared with that of the Cobalt ferrite.

Med5(Nut1) and Med17(Srb4) Are Direct Targets of Mediator Histone H4 Tail Interactions

PubMed Central

Liu, Zhongle; Myers, Lawrence C.

2012-01-01

The Mediator complex transmits activation signals from DNA bound transcription factors to the core transcription machinery. In addition to its canonical role in transcriptional activation, recent studies have demonstrated that S. cerevisiae Mediator can interact directly with nucleosomes, and their histone tails. Mutations in Mediator subunits have shown that Mediator and certain chromatin structures mutually impact each other structurally and functionally in vivo. We have taken a UV photo cross-linking approach to further delineate the molecular basis of Mediator chromatin interactions and help determine whether the impact of certain Mediator mutants on chromatin is direct. Specifically, by using histone tail peptides substituted with an amino acid analog that is a UV activatible crosslinker, we have identified specific subunits within Mediator that participate in histone tail interactions. Using Mediator purified from mutant yeast strains we have evaluated the impact of these subunits on histone tail binding. This analysis has identified the Med5 subunit of Mediator as a target for histone tail interactions and suggests that the previously observed effect of med5 mutations on telomeric heterochromatin and silencing is direct. PMID:22693636

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

Gawai, U. P.; Dole, B. N.; Khawal, H. A.

Ag doped ZnO nanocrystals were synthesized by co-precipitation method with the nominal compositions (x=0.00, 0.02, 0.04, 0.06). The as-synthesized Ag doped ZnO nanocrystals were characterized by X-ray diffraction (XRD), FTIR and UV-Vis. From XRD patterns samples shows hexagonal structure. The average crystallite size is in the range of 41-47 nm. All as synthesized Zn{sub 1−x}Ag{sub x}O nanocrystals are highly textured, with wurtzite structure along the (101) growth direction. The energy band gap of pure and Ag doped ZnO were calculated from UV-Vis spectra. FTIR spectra were confirmed that Ag substituted into ZnO. Chemical species of the samples were detected using FTIRmore » spectra An increase in the hexagonal lattice parameters of ZnO is observed on increasing the Ag concentration. An optical absorption study shows an increment in the band gap with increasing Ag content. From optical study the samples determines blue shift. Atomic packing fraction (APF) and c/a ratio were calculated using XRD data. It confirms the formation of ZnO with the stretching vibrational mode around at 506 to 510 cm{sup −1}.« less

PCR synthesis of double stranded DNA labeled with 5-bromouridine. A step towards finding a bromonucleoside for clinical trials.

PubMed

Michalska, Barbara; Sobolewski, Ireneusz; Polska, Katarzyna; Zielonka, Justyna; Zylicz-Stachula, Agnieszka; Skowron, Piotr; Rak, Janusz

2011-12-05

Incorporation of 5-bromouridine (5BrdU) into DNA makes it sensitive to UV and ionizing radiation, which opens up a prospective route for the clinical usage of 5-bromouridine and other halonucleosides. In the present work the polymerase chain reaction (PCR) protocol, which enables a long DNA fragment (resembling DNA synthesized in the cell in the presence of halonucleosides) to be completely substituted with 5BrdU, was optimized. Using HPLC coupled to enzymatic digestion, it was demonstrated that the actual amounts of native nucleosides and 5BrdU correspond very well to those calculated from the sequence of PCR products. The synthesized DNA is photosensitive to photons of 300nm. HPLC analysis demonstrated that the photolysis of labeled PCR products leads to a significant decrease in the 5BrdU signal and the simultaneous occurrence of a uridine peak. Agarose and polyacrylamide gel electrophoresis suggest that single strand breaks and cross-links are formed as a result of UV irradiation. The PCR protocol described in the current paper may be employed for labeling DNA not only with BrdU but also with other halonucleosides. Copyright © 2011 Elsevier B.V. All rights reserved.

Piezo-Phototronic Enhanced UV Sensing Based on a Nanowire Photodetector Array.

PubMed

Han, Xun; Du, Weiming; Yu, Ruomeng; Pan, Caofeng; Wang, Zhong Lin

2015-12-22

A large array of Schottky UV photodetectors (PDs) based on vertical aligned ZnO nanowires is achieved. By introducing the piezo-phototronic effect, the performance of the PD array is enhanced up to seven times in photoreponsivity, six times in sensitivity, and 2.8 times in detection limit. The UV PD array may have applications in optoelectronic systems, adaptive optical computing, and communication. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Web service substitution method based on service cluster nets

NASA Astrophysics Data System (ADS)

Du, YuYue; Gai, JunJing; Zhou, MengChu

2017-11-01

Service substitution is an important research topic in the fields of Web services and service-oriented computing. This work presents a novel method to analyse and substitute Web services. A new concept, called a Service Cluster Net Unit, is proposed based on Web service clusters. A service cluster is converted into a Service Cluster Net Unit. Then it is used to analyse whether the services in the cluster can satisfy some service requests. Meanwhile, the substitution methods of an atomic service and a composite service are proposed. The correctness of the proposed method is proved, and the effectiveness is shown and compared with the state-of-the-art method via an experiment. It can be readily applied to e-commerce service substitution to meet the business automation needs.

A new insight into the oxidative mechanism of caffeine and related methylxanthines in aprotic medium: May caffeine be really considered as an antioxidant?

PubMed

Petrucci, Rita; Zollo, Giuseppe; Curulli, Antonella; Marrosu, Giancarlo

2018-05-12

Antioxidant properties have been recently suggested for caffeine that seems showing protective effects against damages caused by oxidative stress. In particular, a HO scavenging activity has been ascribed to caffeine. Even if the oxidation of caffeine has been widely studied, the antioxidant mechanism is still far to be understood. The electrochemical behavior of caffeine, theobromine and theophylline was studied in aprotic medium by cyclic voltammetry and electrolysis in UV-vis cell; a computational analysis of the molecular structures based on the Density Functional Theory was performed; the reactivity of all substrates towards lead dioxide, superoxide and galvinoxyl radical was followed by UV-vis spectrophotometry. Results supported the mono-electronic oxidation of the C 4 C 5 bond for all substrates at high oxidation potentials, the electron-transfer process leading to a radical cation or a neutral radical according to the starting methylxanthine N 7 -substituted (caffeine and theobromine) or N 7 -unsubstituted (theophylline), respectively. A different following chemical fate might be predicted for the radical cation or the neutral radical. No interaction was evidenced towards the tested reactive oxygen species. No reactivity via H-atom transfer was evidenced for all studied compounds, suggesting that an antiradical activity should be excluded. Some reactivity only with strong oxidants could be predicted via electron-transfer. The acclaimed HO scavenging activity should be interpreted in these terms. The study suggested that CAF might be hardly considered an antioxidant. Beyond the experimental methods used, the discussion of the present results might provide food for thought to the wide audience working on antioxidants. Copyright © 2018. Published by Elsevier B.V.

Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

DOE PAGES

Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; ...

2016-08-25

Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN –) ligands and one 2,2'-bipyridine (bpy) ligand. This enablesmore » MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN) 4(bpy)] 2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN) 4(bpy)] 2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine) 3] 2+ by more than two orders of magnitude.« less

A Facile pH Controlled Citrate-Based Reduction Method for Gold Nanoparticle Synthesis at Room Temperature.

PubMed

Tyagi, Himanshu; Kushwaha, Ajay; Kumar, Anshuman; Aslam, Mohammed

2016-12-01

The synthesis of gold nanoparticles using citrate reduction process has been revisited. A simplified room temperature approach to standard Turkevich synthesis is employed to obtain fairly monodisperse gold nanoparticles. The role of initial pH alongside the concentration ratio of reactants is explored for the size control of Au nanoparticles. The particle size distribution has been investigated using UV-vis spectroscopy and transmission electron microscope (TEM). At optimal pH of 5, gold nanoparticles obtained are highly monodisperse and spherical in shape and have narrower size distribution (sharp surface plasmon at 520 nm). For other pH conditions, particles are non-uniform and polydisperse, showing a red-shift in plasmon peak due to aggregation and large particle size distribution. The room temperature approach results in highly stable "colloidal" suspension of gold nanoparticles. The stability test through absorption spectroscopy indicates no sign of aggregation for a month. The rate of reduction of auric ionic species by citrate ions is determined via UV absorbance studies. The size of nanoparticles under various conditions is thus predicted using a theoretical model that incorporates nucleation, growth, and aggregation processes. The faster rate of reduction yields better size distribution for optimized pH and reactant concentrations. The model involves solving population balance equation for continuously evolving particle size distribution by discretization techniques. The particle sizes estimated from the simulations (13 to 25 nm) are close to the experimental ones (10 to 32 nm) and corroborate the similarity of reaction processes at 300 and 373 K (classical Turkevich reaction). Thus, substitution of experimentally measured rate of disappearance of auric ionic species into theoretical model enables us to capture the unusual experimental observations.

Tetrabenzoporphyrin and -mono-, -cis-di- and Tetrabenzotriazaporphyrin Derivatives: Electrochemical and Spectroscopic Implications of meso CH Group Replacement with Nitrogen.

PubMed

van As, Adele; Joubert, Chris C; Buitendach, Blenerhassitt E; Erasmus, Elizabeth; Conradie, Jeanet; Cammidge, Andrew N; Chambrier, Isabelle; Cook, Michael J; Swarts, Jannie C

2015-06-01

Nonperipherally hexyl-substituted metal-free tetrabenzoporphyrin (2H-TBP, 1a) tetrabenzomonoazaporphyrin (2H-TBMAP, 2a), tetrabenzo-cis-diazaporphyrin (2H-TBDAP, 3a), tetrabenzotriazaporphyrin (2H-TBTAP, 4a), and phthalocyanine (2H-Pc, 5a), as well as their copper complexes (1b-5b), were synthesized. As the number of meso nitrogen atoms increases from zero to four, λmax of the Q-band absorption peak becomes red-shifted by almost 100 nm, and extinction coefficients increased at least threefold. Simultaneously the blue-shifted Soret (UV) band substantially decreased in intensity. These changes were related to the relative electron-density of each macrocycle expressed as the group electronegativity sum of all meso N and CH atom groups, ∑χR. X-ray photoelectron spectroscopy differentiated between the three different types of macrocyclic nitrogen atoms (the Ninner, (NH)inner, and Nmeso) in the metal-free complexes. Binding energies of the Nmeso and Ninner,Cu atoms in copper chelates could not be resolved. Copper insertion lowered especially the cathodic redox potentials, while all four observed redox processes occurred at larger potentials as the number of meso nitrogens increased. Computational chemical methods using density functional theory confirmed 1b to exhibit a Cu(II) reduction prior to ring-based reductions, while for 2b, Cu(II) reduction is the first reductive step only if the nonperipheral substituents are hydrogen. When they are methyl groups, it is the second reduction process; when they are ethyl, propyl, or hexyl, it becomes the third reductive process. Spectro-electrochemical measurements showed redox processes were associated with a substantial change in intensity of at least two main absorbances (the Q and Soret bands) in the UV spectra of these compounds.

Synthesis and structural characterization of new oxovanadium(IV) complexes derived from azo-5-pyrazolone with prospective medical importance

NASA Astrophysics Data System (ADS)

Bagdatli, Emine; Altuntas, Eylem; Sayin, Ulku

2017-01-01

Four novel o-hydroxy substituted aryl-(msbnd H, sbnd Cl, sbnd Br, sbnd CH3) azo-5-pyrazolone compounds (2a-d, respectively) were synthesized as azo-group containing ligands by diazotization of aryl amines then coupled with 1-(4-chlorophenyl)-3-isopropyl-1H-pyrazol-5(4H)-one (1) and the structures were confirmed by FTIR, UV-Visible, GC-MS or ESI-LCMS and NMR spectroscopic techniques. As a result, the first synthesis of azo-5-pyrazolone based oxovanadium(IV) complexes (3a-d) was achieved by interaction of 2a-d with half equivalent of vanadyl sulphate pentahydrate in a methanolic medium with moderate to high yields (67, 74, 60, 71 for 3a-d, respectively). The resulting complexes were characterized using FTIR, UV-Visible, ESI-LCMS and EPR spectroscopic techniques as well as with thermogravimetric (TG/DTG) analysis. They have the composition [VO(L)2]·H2O; (3a-c) or [VO(L)2]·CH3OH; (3d) where LH is an azo-5-pyrazolone compound as the ligand (2a-d). The electronic spectra of the complexes are typical of oxovanadium(IV) complexes showing a low intensity band near 500 nm. Spectroscopic results have shown that azo-5-pyrazolone compounds have acted bidendate and the coordination sites are hydroxyl-substituent on the -azo phenyl-aromatic ring and the pyrazolone carbonyl-moiety. The thermal data confirm that the complexes have methanol (3a-c) or water (3d) molecule outside the coordination sphere and the complexes show similar thermogravimetric decomposition fragments which are consistent with the proposed structures. A distorted octahedral geometry has been proposed for these complexes mainly with EPR and the other spectral techniques.

Co-precipitation synthesis and characterization of tin-doped α-Fe2O3 nanoparticles with enhanced photocatalytic activities

NASA Astrophysics Data System (ADS)

Mansour, Houda; Bargougui, Radhouane; Autret-Lambert, Cécile; Gadri, Abdellatif; Ammar, Salah

2018-03-01

In this study, Sn-doped hematite (α-Fe2O3) nanoparticles with various dopant concentrations ranging from 1 to 6 mol% were prepared successfully using a simple co-precipitation technique. The effects of Sn doping on the structural, morphological, optical, and magnetic properties were determined using X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy, and a superconducting quantum interference device. XRD analysis showed that all of the samples had a typical hematite-type hexagonal structure of Fe2O3 without any additional peaks due to spurious phases. The cell parameters a and c decreased monotonically as the Sn content increased, thereby indicating that Sn ions were substituted into the α-Fe2O3 lattice. These results and the TEM analyses showed that the size of the nanoparticles decreased to 10 nm as the Sn doping concentration increased. UV-visible absorption measurements showed that the decrease in particle size was accompanied by a decrease in the band gap value from 2.07 eV for α-Fe2O3 to 1.87 eV with 6 mol% Sn doping. Furthermore, the magnetic properties demonstrated that all of the samples exhibited ferromagnetic behavior at room temperature. The photocatalytic activities of the samples were studied based on the degradation of methylene blue as a model compound, where the results showed that an appropriate amount of Sn dopant could greatly increase the amount of hydroxyl radicals generated by α-Fe2O3 nanoparticles, which were responsible for the obvious increase in the photocatalytic activity.

Characterization of prepared In2O3 thin films: The FT-IR, FT-Raman, UV-Visible investigation and optical analysis.

PubMed

Panneerdoss, I Joseph; Jeyakumar, S Johnson; Ramalingam, S; Jothibas, M

2015-08-05

In this original work, the Indium oxide (In2O3) thin film is deposited cleanly on microscope glass substrate at different temperatures by spray pyrolysis technique. The physical properties of the films are characterized by XRD, SEM, AFM and AFM measurements. The spectroscopic investigation has been carried out on the results of FT-IR, FT-Raman and UV-Visible. XRD analysis exposed that the structural transformation of films from stoichiometric to non-stoichiometric orientation of the plane vice versa and also found that, the film is polycrystalline in nature having cubic crystal structure with a preferred grain orientation along (222) plane. SEM and AFM studies revealed that, the film with 0.1M at 500°C has spherical grains with uniform dimension. The complete vibrational analysis has been carried out and the optimized parameters are calculated using HF and DFT (CAM-B3LYP, B3LYP and B3PW91) methods with 3-21G(d,p) basis set. Furthermore, NMR chemical shifts are calculated by using the gauge independent atomic orbital (GIAO) technique. The molecular electronic properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, molecular electrostatic potential energy (MEP) analysis and Polarizability first order hyperpolarizability calculations are performed by time dependent DFT (TD-DFT) approach. The energy excitation on electronic structure is investigated and the assignment of the absorption bands in the electronic spectra of steady compound is discussed. The calculated HOMO and LUMO energies showed the enhancement of energy gap by the addition of substitutions with the base molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) at different temperatures are calculated and interpreted in gas phase. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Substituent effects and pH profiles for stability constants of arylboronic acid diol esters.

PubMed

Martínez-Aguirre, Mayte A; Villamil-Ramos, Raul; Guerrero-Alvarez, Jorge A; Yatsimirsky, Anatoly K

2013-05-17

Stability constants of boronic acid diol esters in aqueous solution have been determined potentiometrically for a series of meta-, para-substituted phenylboronic acids and diols of variable acidity. The constants β(11-1) for reactions between neutral forms of reactants producing the anionic ester plus proton follow the Hammett equation with ρ depending on pKa of diol and varying from 2.0 for glucose to 1.29 for 4-nitrocatechol. Observed stability constants (K(obs)) measured by UV-vis and fluorometric titrations at variable pH for esters of 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron) generally agree with those expected on the basis of β(11-1) values, but the direct fitting of K(obs) vs pH profiles gives shifted pKa values both for boronic acids and diol as a result of significant interdependence of fitting parameters. The subsituent effects on absorption and fluorescence spectra of Tiron arylboronate esters are characterized. The K(obs) for Tiron determined by (11)B NMR titrations are approximately 1 order of magnitude smaller than those determined by UV-vis titrations under identical conditions. A general equation, which makes possible an estimate of β(11-1) for any pair of boronic acid and diol from their pKa values, is proposed on the basis of established Brönsted-type correlation of Hammett parameters for β(11-1) with acidity of diols. The equation allows one to calculate stability constants expected only on basis of acid-base properties of the components, thus permitting more strict evaluation of contributions of additional factors such as steric or charge effects to the ester stability.

Effect of UV irradiation on the apoptosis and necrosis of Jurkat cells using UV LEDs

NASA Astrophysics Data System (ADS)

Inada, Shunko A.; Amano, Hiroshi; Akasaki, Isamu; Morita, Akimichi; Kobayashi, Keiko

2009-02-01

Phototherapy is a very effective method for treating most of the incurable skin diseases. A fluorescent light bulb is used as a conventional UV light source for this type of therapy. However, infrared radiation from the light source sometimes causes serious problems on patient's health. In addition, the normal part of the skin is irradiated when a large fluorescent light bulb is used. Moreover, a conventional UV irradiation system is heavy and has a short lifetime and a high electrical power consumption. Therefore, a new UV light source for solving the problems of phototherapy is required. To realize low-power-consumption, lightweight and long-lifetime systems, group III nitride-based UV-A1 light-emitting diodes (LEDs) were investigated. We examined the UV LED irradiation of Jurkat cell, which is a tumor cell and more sensitive to UV light than a healthy cell. The numbers of apoptotic and necrotic cells were confirmed to be the same using a UV LED and a conventional lamp system. The UV LED showed the possibility of realizing a new UV light source for phototherapy.

Effect of Ga3+ and Gd3+ ions substitution on the structural and optical properties of Ce3+ -doped yttrium aluminium garnet phosphor nanopowders.

PubMed

Wako, A H; Dejene, F B; Swart, H C

2016-11-01

The structural and optical properties of commercially obtained Y 3 Al 5 O 12 :Ce 3 + phosphor were investigated by replacing Al 3 + with Ga 3 + and Y 3 + with Gd 3 + in the Y 3 Al 5 O 12 :Ce 3 + structure to form Y 3 (Al,Ga) 5 O 12 :Ce 3 + and (Y,Gd) 3 Al 5 O 12 :Ce 3 + . X-Ray diffraction (XRD) results showed slight 2-theta peak shifts to lower angles when Ga 3 + was used and to higher angles when Gd 3 + was used, with respect to peaks from Y 3 Al 5 O 12 :Ce 3 + and JCPDS card no. 73-1370. This could be attributed to induced crystal-field effects due to the different ionic sizes of Ga 3 + and Gd 3 + compared with Al 3 + and Y 3 + . The photoluminescence (PL) spectra showed broad excitation from 350 to 550 nm with a maximum at 472 nm, and broad emission bands from 500 to 650 nm, centred at 578 nm for Y 3 Al 5 O 12 :Ce 3 + arising from the 5d → 4f transition of Ce 3 + . PL revealed a blue shift for Ga 3 + substitution and a red shift for Gd 3 + substitution. UV-Vis showed two absorption peaks at 357 and 457 nm for Y 3 Al 5 O 12 :Ce 3 + , with peaks shifting to 432 nm for Ga 3 + and 460 nm for Gd 3 + substitutions. Changes in the trap levels or in the depth and number of traps due to Ce 3 + were analysed using thermoluminescence (TL) spectroscopy. This revealed the existence of shallow and deep traps. It was observed that Ga 3 + substitution contributes to the shallowest traps at 74 °C and fewer deep traps at 163 °C, followed by Gd 3 + with shallow traps at 87 °C and deep traps at 146 °C. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Wavelength dependent recovery of UV-mediated damage: Tying up the loose ends of optical based powdery mildew management.

PubMed

Suthaparan, Aruppillai; Pathak, Ranjana; Solhaug, Knut Asbjørn; Gislerød, Hans Ragnar

2018-01-01

Controlled environment chamber experiments at Petri dish level were conducted to examine the wavelength and dose dependent efficacy of ultraviolet (UV) radiation, the recovery action potential of optical radiation applied concomitantly/subsequently to effective UV treatment, and the lapse time between UV treatment and subsequent exposure to recovery wavelength on germination efficiency of Oidium neolycopersici conidia. Conidia of eight- to nine-day-old colonies were dusted on water agar surface in Petri dishes and exposed to UV treatments (without lid). Immediately after UV treatments, Petri dishes were sealed and incubated in darkness or differing optical environments generated using seven different radiation sources (range 290nm to 780nm). Twenty-four hours after UV treatment, fifty conidia from each sample were assessed for germination. Compared to non-UV controls, <10% of the conidia germinated after 30s of exposure to 254nm or 283nm UV and subsequent dark incubation. Conidia germination was almost negligible if the exposure duration increased to 4min. Germination was about 60% with broad spectrum UV after 1min of exposure, and about 35% after 2 to 4min of exposure. There was no reduction of conidia germination with the exposure of ≤4min with 310nm. With the tested wavelength and dose ranges, germination recovery was effective in the 350nm to 500nm range. Germination efficiency of conidia treated with effective UV was significantly higher (>73%) if incubated subsequently in the 350nm to 500nm range (germination recovery). Furthermore, germination recovery depends on the characteristics of UV treatment (wavelength, and duration of exposure) and the lapse time between UV treatment and subsequent exposure to optical radiation in the recovery range. The findings of this study provide key criteria for wavelength selection, combination and application time in the optical radiation range, enabling improved design of optical based management strategies against powdery mildews. Copyright © 2017 Elsevier B.V. All rights reserved.

Antiprotozoal glutathione derivatives with flagellar membrane binding activity against T. brucei rhodesiense.

PubMed

Daunes, Sylvie; Yardley, Vanessa; Croft, Simon L; D'Silva, Claudius

2017-02-15

A new series of N-substituted S-(2,4-dinitrophenyl)glutathione dibutyl diesters were synthesized to improve in vitro anti-protozoal activity against the pathogenic parasites Trypanosoma brucei rhodesiense, Trypanosoma cruzi and Leishmania donovani. The results obtained indicate that N-substituents enhance the inhibitory properties of glutathione diesters whilst showing reduced toxicity against KB cells as in the cases of compounds 5, 9, 10, 16, 18 and 19. We suggest that the interaction of N-substituted S-(2,4-dinitrophenyl) glutathione dibutyl diesters with T. b. brucei occurs mainly by weak hydrophobic interactions such as London and van der Waals forces. A QSAR study indicated that the inhibitory activity of the peptide is associated negatively with the average number of C atoms, N C and positively to S ZX, the ZX shadow a geometric descriptor related to molecular size and orientation of the compound. HPLC-UV studies in conjunction with optical microscopy indicate that the observed selectivity of inhibition of these compounds against bloodstream form T. b. brucei parasites in comparison to L. donovani under the same conditions is due to intracellular uptake via endocytosis in the flagellar pocket. Copyright © 2016. Published by Elsevier Ltd.

Copper Mesh Templated by Breath-Figure Polymer Films as Flexible Transparent Electrodes for Organic Photovoltaic Devices.

PubMed

Zhou, Weixin; Chen, Jun; Li, Yi; Wang, Danbei; Chen, Jianyu; Feng, Xiaomiao; Huang, Zhendong; Liu, Ruiqing; Lin, Xiujing; Zhang, Hongmei; Mi, Baoxiu; Ma, Yanwen

2016-05-04

Metal mesh is a significant candidate of flexible transparent electrodes to substitute the current state-of-the-art material indium tin oxide (ITO) for future flexible electronics. However, there remains a challenge to fabricate metal mesh with order patterns by a bottom-up approach. In this work, high-quality Cu mesh transparent electrodes with ordered pore arrays are prepared by using breath-figure polymer films as template. The optimal Cu mesh films present a sheet resistance of 28.7 Ω·sq(-1) at a transparency of 83.5%. The work function of Cu mesh electrode is tuned from 4.6 to 5.1 eV by Ag deposition and the following short-time UV-ozone treatment, matching well with the PSS (5.2 eV) hole extraction layer. The modified Cu mesh electrodes show remarkable potential as a substitute of ITO/PET in the flexible OPV and OLED devices. The OPV cells constructed on our Cu mesh electrodes present a similar power conversion efficiency of 2.04% as those on ITO/PET electrodes. The flexible OLED prototype devices can achieve a brightness of 10 000 cd at an operation voltage of 8 V.

Effect of halo-substituted aromatic salts on counterion binding constants obtained from cationic nanoparticle catalyzed reactions of piperidine and phenyl salicylate

NASA Astrophysics Data System (ADS)

Fagge, Ibrahim I.; Yusof, Nor Saadah M.; Zain, Sharifuddin Md; Khan, M. Niyaz

2017-12-01

Halo-substitutions at 3-position of benzene ring of the salts of aromatic carboxylate, MX, revealed the effect of two different halide ions (Br- and Cl-) on the counterion binding constants obtained from cationic nanoparticle catalyzed piperidinolysis of ionized phenyl salicylate (PhS-). The values of observed rate constant, kobs, determined at a constant total concentration of cetyltrimethylammonium bromide, [CTABr]T, piperidine, ([P]T), [PhS-]T, NaOH, and various concentration of MX (MX = 3-BrC6H4CO2Na and 3-ClC6H4CO2Na), were determined using UV-visible X spectrophotometric technique at 35 °C and 370 nm. The average value of nanoparticle binding constant, KXBr, for X- = 3-BrC6H4CO2- (RXBr = 57) was found to be about 2-fold larger than that for X- = 3-ClC6H4CO2- (RXBr = 30). These XX values were dependent of substituents 3-Br and 3-Cl, and independent of [CTABr]T. Both are related to the presence of different extent of viscoelastic worm-like nanoparticles formation in the [CTABr]T of 6 and 10 mM.

Anaerobic biodegradability of alkylphenols and fuel oxygenates in the presence of alternative electron acceptors.

PubMed

Puig-Grajales, L; Tan, N G; van der Zee, F; Razo-Flores, E; Field, J A

2000-11-01

Alkylphenols and fuel oxygenates are important environmental pollutants produced by the petrochemical industry. A batch biodegradability test was conducted with selected ortho-substituted alkylphenols (2-cresol, 2,6-dimethylphenol and 2-ethylphenol), fuel oxygenates (methyl tert-butyl ether, ethyl tert-butyl ether and tert-amylmethyl ether) and tert-butyl alcohol (TBA) as model compounds. The ortho-substituted alkylphenols were not biodegraded after 100 days of incubation under methanogenic, sulfate-, or nitrate-reducing conditions. However, biodegradation of 2-cresol and 2-ethylphenol (150 mg l(-1)) was observed in the presence of Mn (IV) as electron acceptor. The biodegradation of these two compounds took place in less than 15 days and more than 90% removal was observed for both compounds. Mineralization was indicated since no UV-absorbing metabolites accumulated after 23 days of incubation. These alkylphenols were also slowly chemically oxidized by Mn (IV). No biodegradation of fuel oxygenates or TBA (1 g l(-1)) was observed after 80 or more days of incubation under methanogenic, Fe (III)-, or Mn (IV)-reducing conditions, suggesting that these compounds are recalcitrant under anaerobic conditions. The fuel oxygenates caused no toxicity towards acetoclastic methanogens activity in anaerobic granular sludge.

Enhanced persistent red luminescence in Mn2+-doped (Mg,Zn)GeO3 by electron trap and conduction band engineering

NASA Astrophysics Data System (ADS)

Katayama, Yumiko; Kayumi, Tomohiro; Ueda, Jumpei; Tanabe, Setsuhisa

2018-05-01

The effect of Zn substitution on the persistent luminescence properties of MgGeO3:Mn2+-Ln3+ (Ln = Eu and Yb) red phosphors was investigated. The intensity of the persistent luminescence of the Eu3+ co-doped phosphors increased with increasing Zn content, whereas that of the Yb3+ co-doped samples decreased. For both series of lanthanide co-doped samples, the thermoluminescence (TL) glow peak shifted to the lower temperature side with increasing Zn content. These persistent luminescence properties were well explained in terms of lowering of the bottom of the conduction band relative to the ground state of the divalent lanthanide ions. Especially, in Eu3+ co-doped system, TL peak shifted from 520 K to 318 K by 50% Zn substitution. The persistent radiance of the (Mg0.5 Zn0.5)GeO3: Mn2+-Eu3+ sample at 1 h after ceasing UV light was 46 times stronger than that of MgGeO3:Mn2+-Eu3+, and 11 times stronger than that of ZnGa2O4: Cr3+ standard deep red persistent phosphor.

Understanding the properties of chitosan aryl substituted thioureas in their role and potential as antibacterial agents

NASA Astrophysics Data System (ADS)

Khairul, Wan M.; Daud, Adibah Izzati; Ismail, Noraznawati

2018-02-01

In this study, the effort was to design and synthesize a series of thiourea-chitosan derivatives featuring five aryl substituted members namely N-chitosan-N'-(4-nitrobenzoyl) thiourea (1), N-chitosan-N'-(4-chlorobenzoyl) thiourea (2), N-chitosan-N'-(4-methylbenzoyl) thiourea (3), N-chitosan-N'-(2-iodobenzoyl) thiourea (4), and N-chitosan-N'-(2-methylbenzoyl) thiourea (5) via SN2 reaction pathway having different donating and withdrawing groups. Their molecular structures were then characterised by FT-IR, UV-Vis, and thermogravimetric analysis (TGA). The antimicrobial activities of these derivatives against four species bacteria Bacillus cereus, Staphylococcus aureus, Salmonella typhi, and Escherichia coli of both Gram-positive and Gram-negative type bacteria at minimum concentration 6mg/ml were carried out to investigate their potential as antibacterial agents. Compound 1 exhibited specific activity as it can only inhibit Gram-positive bacteria while other compounds 2-5 showed broad range spectrum activity as they were able to inhibit both Gram-positive and Gram-negative bacteria. Therefore, 1-5 showed good antibacterial activity and have high potential to be further developed as active materials in pharmaceutical interests.

Effects of Al-Impurity Type on Formation Energy, Crystal Structure, Electronic Structure, and Optical Properties of ZnO by Using Density Functional Theory and the Hubbard-U Method.

PubMed

Wu, Hsuan-Chung; Chen, Hsing-Hao; Zhu, Yu-Ren

2016-08-01

We systematically investigated the effects of Al-impurity type on the formation energy, crystal structure, charge density, electronic structure, and optical properties of ZnO by using density functional theory and the Hubbard-U method. Al-related defects, such as those caused by the substitution of Zn and O atoms by Al atoms (Al s(Zn) and Al s(O) , respectively) and the presence of an interstitial Al atom at the center of a tetrahedron (Al i(tet) ) or an octahedron (Al i(oct) ), and various Al concentrations were evaluated. The calculated formation energy follows the order E f (Al s(Zn) ) < E f (Al i(tet) ) < E f (Al i(oct) ) < E f (Al s(O) ). Electronic structure analysis showed that the Al s(Zn) , Al s(O) , Al i(tet) , and Al i(oct) models follow n -type conduction, and the optical band gaps are higher than that of pure ZnO. The calculated carrier concentrations of the Al s(O) and Al i(tet) /Al i(oct) models are higher than that of the Al s(Zn) model. However, according to the curvature of the band structure, the occurrence of interstitial Al atoms or the substitution of O atoms by Al atoms results in a high effective mass, possibly reducing the carrier mobility. The average transmittance levels in the visible light and ultraviolet (UV) regions of the Al s(Zn) model are higher than those of pure ZnO. However, the presence of an interstitial Al atom within the ZnO crystal reduces transmittance in the visible light region; Al s(O) substantially reduces the transmittance in the visible light and UV regions. In addition, the properties of ZnO doped with various Al s(Zn) concentrations were analyzed.

Activation of the manganese(I) tricarbonyl core by selective variation of bidentate ligands (L,L'-Bid = N,N' and N,O donor atom sets) in fac-[Mn(CO)3(L,L'-Bid)(CH3OH)](n) complexes.

PubMed

Twala, T N; Schutte-Smith, M; Roodt, A; Visser, H G

2015-02-21

A range of fac-[Mn(CO)3(L,L'-Bid)(H2O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N' and N,O, 1,10-phenanthroline, 2,2'-bipyridine, 2-picolinate, 2,4-quinolinate; n = 0, +1) has been synthesized and the methanol substitution has been investigated for the first time. The complexes were characterized by UV/vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Mn(CO)3(Bipy)(H2O)][CF3SO3] () and fac-[Mn(CO)3(Phen)(H2O)][CF3SO3] () are reported. A two order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k1, M(-1) s(-1); k-1, s(-1); K1, M(-1)) for pyridine as entering nucleophile are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (2.39 ± 5) × 10(-3), (1.5 ± 0.3) × 10(-5), 159 ± 32; fac-[Mn(CO)3(2,4-QuinH)(CH3OH)] (4.5 ± 0.2), (4 ± 1) × 10(-2), 113 ± 29. Activation parameters (ΔH, kJ mol(-1); ΔS, J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (bromide ions) 66.7 ± 0.6, -27 ± 2; (pyridine) 80 ± 3, -25 ± 11; fac-[Mn(CO)3(Pico)(CH3OH)] (bromide ions) 68 ± 2, -24 ± 5. A dissociative interchange mechanism is proposed.

Microbial UV fluence-response assessment using a novel UV-LED collimated beam system.

PubMed

Bowker, Colleen; Sain, Amanda; Shatalov, Max; Ducoste, Joel

2011-02-01

A research study has been performed to determine the ultraviolet (UV) fluence-response of several target non-pathogenic microorganisms to UV light emitting diodes (UV-LEDs) by performing collimated beam tests. UV-LEDs do not contain toxic mercury, offer design flexibility due to their small size, and have a longer operational life than mercury lamps. Comsol Multiphysics was utilized to create an optimal UV-LED collimated beam design based on number and spacing of UV-LEDs and distance of the sample from the light source while minimizing the overall cost. The optimized UV-LED collimated beam apparatus and a low-pressure mercury lamp collimated beam apparatus were used to determine the UV fluence-response of three surrogate microorganisms (Escherichia coli, MS-2, T7) to 255 nm UV-LEDs, 275 nm UV-LEDs, and 254 nm low-pressure mercury lamps. Irradiation by low-pressure mercury lamps produced greater E. coli and MS-2 inactivation than 255 nm and 275 nm UV-LEDs and similar T7 inactivation to irradiation by 275 nm UV-LEDs. The 275 nm UV-LEDs produced more efficient T7 and E. coli inactivation than 255 nm UV-LEDs while both 255 nm and 275 nm UV-LEDs produced comparable microbial inactivation for MS-2. Differences may have been caused by a departure from the time-dose reciprocity law due to microbial repair mechanisms. Copyright © 2010 Elsevier Ltd. All rights reserved.

Explicit Substitutions and All That

NASA Technical Reports Server (NTRS)

Ayala-Rincon, Mauricio; Munoz, Cesar

2000-01-01

Explicit substitution calculi are extensions of the lambda-calculus where the substitution mechanism is internalized into the theory. This feature makes them suitable for implementation and theoretical study of logic-based tools such as strongly typed programming languages and proof assistant systems. In this paper we explore new developments on two of the most successful styles of explicit substitution calculi: the lambda sigma- and lambda S(e)-calculi.

Explicit Substitutions and All That

NASA Technical Reports Server (NTRS)

Ayala-Rincon, Mauricio; Munoz, Cesar; Busnell, Dennis M. (Technical Monitor)

2000-01-01

Explicit substitution calculi are extensions of the Lambda-calculus where the substitution mechanism is internalized into the theory. This feature makes them suitable for implementation and theoretical study of logic-based tools such as strongly typed programming languages and proof assistant systems. In this paper we explore new developments on two of the most successful styles of explicit substitution calculi: the lambda(sigma)- and lambda(s(e))-calculi.

Glass-Based Transparent Conductive Electrode: Its Application to Visible-to-Ultraviolet Light-Emitting Diodes.

PubMed

Lee, Tae Ho; Kim, Kyeong Heon; Lee, Byeong Ryong; Park, Ju Hyun; Schubert, E Fred; Kim, Tae Geun

2016-12-28

Nitride-based ultraviolet light-emitting diodes (UV LEDs) are promising replacements for conventional UV lamps. However, the external quantum efficiency of UV LEDs is much lower than for visible LEDs due to light absorption in the p-GaN contact and electrode layers, along with p-AlGaN growth and doping issues. To minimize such absorption, we should obtain direct ohmic contact to p-AlGaN using UV-transparent ohmic electrodes and not use p-GaN as a contact layer. Here, we propose a glass-based transparent conductive electrode (TCE) produced using electrical breakdown (EBD) of an AlN thin film, and we apply the thin film to four (Al)GaN-based visible and UV LEDs with thin buffer layers for current spreading and damage protection. Compared to LEDs with optimal ITO contacts, our LEDs with AlN TCEs exhibit a lower forward voltage, higher light output power, and brighter light emission for all samples. The ohmic transport mechanism for current injection and spreading from the metal electrode to p-(Al)GaN layer via AlN TCE is also investigated by analyzing the p-(Al)GaN surface before and after EBD.

UV Radiation and the Skin

PubMed Central

D’Orazio, John; Jarrett, Stuart; Amaro-Ortiz, Alexandra; Scott, Timothy

2013-01-01

UV radiation (UV) is classified as a “complete carcinogen” because it is both a mutagen and a non-specific damaging agent and has properties of both a tumor initiator and a tumor promoter. In environmental abundance, UV is the most important modifiable risk factor for skin cancer and many other environmentally-influenced skin disorders. However, UV also benefits human health by mediating natural synthesis of vitamin D and endorphins in the skin, therefore UV has complex and mixed effects on human health. Nonetheless, excessive exposure to UV carries profound health risks, including atrophy, pigmentary changes, wrinkling and malignancy. UV is epidemiologically and molecularly linked to the three most common types of skin cancer, basal cell carcinoma, squamous cell carcinoma and malignant melanoma, which together affect more than a million Americans annually. Genetic factors also influence risk of UV-mediated skin disease. Polymorphisms of the melanocortin 1 receptor (MC1R) gene, in particular, correlate with fairness of skin, UV sensitivity, and enhanced cancer risk. We are interested in developing UV-protective approaches based on a detailed understanding of molecular events that occur after UV exposure, focusing particularly on epidermal melanization and the role of the MC1R in genome maintenance. PMID:23749111

UV radiation and the skin.

PubMed

D'Orazio, John; Jarrett, Stuart; Amaro-Ortiz, Alexandra; Scott, Timothy

2013-06-07

UV radiation (UV) is classified as a "complete carcinogen" because it is both a mutagen and a non-specific damaging agent and has properties of both a tumor initiator and a tumor promoter. In environmental abundance, UV is the most important modifiable risk factor for skin cancer and many other environmentally-influenced skin disorders. However, UV also benefits human health by mediating natural synthesis of vitamin D and endorphins in the skin, therefore UV has complex and mixed effects on human health. Nonetheless, excessive exposure to UV carries profound health risks, including atrophy, pigmentary changes, wrinkling and malignancy. UV is epidemiologically and molecularly linked to the three most common types of skin cancer, basal cell carcinoma, squamous cell carcinoma and malignant melanoma, which together affect more than a million Americans annually. Genetic factors also influence risk of UV-mediated skin disease. Polymorphisms of the melanocortin 1 receptor (MC1R) gene, in particular, correlate with fairness of skin, UV sensitivity, and enhanced cancer risk. We are interested in developing UV-protective approaches based on a detailed understanding of molecular events that occur after UV exposure, focusing particularly on epidermal melanization and the role of the MC1R in genome maintenance.

UV sensing using film bulk acoustic resonators based on Au/n-ZnO/piezoelectric-ZnO/Al structure.

PubMed

Bian, Xiaolei; Jin, Hao; Wang, Xiaozhi; Dong, Shurong; Chen, Guohao; Luo, J K; Deen, M Jamal; Qi, Bensheng

2015-03-16

A new type of ultraviolet (UV) light sensor based on film bulk acoustic wave resonator (FBAR) is proposed. The new sensor uses gold and a thin n-type ZnO layer deposited on the top of piezoelectric layer of FBAR to form a Schottky barrier. The Schottky barrier's capacitance can be changed with UV light, resulting in an enhanced shift in the entire FBAR's resonant frequency. The fabricated UV sensor has a 50 nm thick n-ZnO semiconductor layer with a carrier concentration of ~ 10(17) cm(-3). A large frequency downshift is observed when UV light irradiates the FBAR. With 365 nm UV light of intensity 1.7 mW/cm(2), the FBAR with n-ZnO/Au Schottky diode has 250 kHz frequency downshift, much larger than the 60 kHz frequency downshift in a conventional FBAR without the n-ZnO layer. The shift in the new FBAR's resonant frequency is due to the junction formed between Au and n-ZnO semiconductor and its properties changes with UV light. The experimental results are in agreement with the theoretical analysis using an equivalent circuit model of the new FBAR structure.

Comparative experimental and simulation studies of high-power AlGaN-based 353 nm ultraviolet flip-chip and top-emitting LEDs

NASA Astrophysics Data System (ADS)

Liu, Mengling; Zhou, Shengjun; Liu, Xingtong; Gao, Yilin; Ding, Xinghuo

2018-03-01

Experimental and simulation studies of high-power AlGaN-based 353 nm ultraviolet (UV) flip-chip (FC) and top-emitting (TE) light-emitting diodes (LEDs) are performed here. To improve the optical and electrical properties of ultraviolet LEDs, we fabricate high-power FC-UV LEDs with Ta2O5/SiO2 distributed Bragg reflectors (DBRs) and a strip-shaped SiO2 current blocking layer (CBL). The reflectance of fourteen pairs of Ta2O5/SiO2 DBRs is 96.4% at 353 nm. The strip-shaped SiO2 CBL underneath the strip-shaped p-electrode can prevent the current concentrating in regions immediately adjacent to the p-electrode where the overlying opaque p-electrode metal layer absorbs the emitted UV light. Moreover, two-level metallization electrodes are used to improve current spreading. Our numerical results show that FC-UV LED has a more favorable current spreading uniformity than TE-UV LED. The light output power of 353 nm FC-UV LED was 23.22 mW at 350 mA, which is 24.7% higher than that of TE-UV LED.

A flexible UV nanosensor based on reduced graphene oxide decorated ZnO nanostructures

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Zhan, Xueying; Wang, Yajun; Muhammad, Safdar; Huang, Ying; He, Jun

2012-03-01

A low-cost, compatible with flexible electronics, high performance UV sensor has been achieved from a reduced graphene oxide (RGO) decorated hydrangea-like ZnO film on a PDMS substrate. The hydrangea-like ZnO UV sensor has the best UV sensing performance among devices made of three kinds of ZnO nanostructures synthesized by a hydrothermal method, and demonstrated a dramatic enhancement in on/off ratio and photoresponse current by introducing an appropriate weight ratio of RGO. The on/off ratio of the 0.05% RGO/ZnO sensor increases almost one order of magnitude compared to that of a pristine hydrangea-like ZnO UV sensor. While for the 5% RGO decorated ZnO sensor, the photoresponse current reaches as high as ~1 μA and exceeds 700 times that of a ZnO UV sensor. These results indicate that RGO is an appropriate material to enhance the performance of ZnO nanostructure UV sensors based on its unique features, especially the high optical transparency and excellent electronic conductivity. Our findings will make RGO/ZnO nanohybrids extraordinarily promising in optoelectronics, flexible electronics and sensor applications.