Varaksin, Konstantin S.; Szatylowicz, Halina; Krygowski, Tadeusz M.
2017-06-01
Quantitative description of substituent effects is of a great importance especially in organic chemistry and QSAR-type treatments. The proposed approaches: substituent effect stabilization energy (SESE) and charge of the substituent active region (cSAR) provide substituent effect characteristics, physically independent of the Hammett's substituent constants, σ. To document abilities of these descriptors the B3LYP/6-311++G(d,p) method is employed to examine changes in properties of a reaction center Y (Y = COOH or COO- groups) and a transmitting moiety (benzene ring) due to substituent effects in a series of meta- and para-X-substituted benzoic acid and benzoate anion derivatives (X = NMe2, NH2, OH, OMe, CH3, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, NO). The transmitting moiety is described by aromaticity indices HOMA and NICS(1). Furthermore, an advantage of the cSAR characteristic is the ability to use it to describe both electron donating/accepting properties of a substituent as well as a reaction center. It allows demonstration of the reverse substituent effects of COOH and COO- groups on substituent X.
Relationship between electrophilicity index, Hammett constant and ...
Indian Academy of Sciences (India)
Unknown
Inter-relationships between the electrophilicity index (ω), Hammett constant (óp) and nucleus- independent chemical ... cess of DFT is that it provides simple working equa- tions to elucidate ... compasses both the ability of an electrophile to ac-.
Hu, Nvdan; Gong, Yulong; Wang, Xinchao; Lu, Yao; Peng, Guangyue; Yang, Long; Zhang, Shengtao; Luo, Ziping; Li, Hongru; Gao, Fang
2015-11-01
A series of new asymmetric chromophores containing aromatic substituents and possessing the excellent π-extension in space were prepared through multi-steps routes. One-photon and two-photon spectral properties of these new chromophores could be tuned by these substituents finely and simultaneously. The linear correlation of the wave numbers of the one-photon absorption and emission maxima to Hammett parameters of these substituents was presented. Near infrared two-photon absorption emission integrated areas of the target chromophores were correlated linearly to Hammett constants of these substituted groups.
Directory of Open Access Journals (Sweden)
Hicham Ben El Ayouchia
2016-10-01
Full Text Available The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.
Huang, Ying; Liu, Lianghong; Liu, Wanhui; Liu, Shaogang; Liu, Shubin
2011-12-29
Molecular acidity is an important physiochemical property essential in many fields of molecular studies, but an efficient and reliable computational approach to make accurate predictions is still missing. In this work, based on our previous studies to use gas phase electronic properties such as molecular electrostatic potential and valence natural atomic orbitals of the acidic atom and leaving proton, we demonstrate here that different approaches can be employed to tackle this problem. To that end, we employ 196 singly, doubly, and triply substituted benzoic acids for the study. We show that two different approaches are possible, one focusing on the carboxyl group through its localized electronic properties and the other on the substituting groups via Hammett constants and their additivity rule. Our present results clearly exhibit that with the linear models built from the singly substituted species, one can accurately predict the pK(a) values for the doubly and triply substituted species with both of these two approaches. The predictions from these approaches are consistent with each other and agree well with the experimental data. These intrinsically different approaches are the two manifestations of the same molecular acidity property, both valid and complementary to each other. © 2011 American Chemical Society
Expanding the Hammett Correlations for the Vinylheptafulvene Ring-Closure Reaction
DEFF Research Database (Denmark)
Kilde, Martin Drøhse; Hansen, Mia Harring; Broman, Søren Lindbæk
2017-01-01
of these reactions was studied at –20 °C for two series for which the substituent at the C-2 position (DHA numbering) was kept constant, and a linear free-energy relationship (Hammett correlation) was revealed in both cases. The relationships show that an electron-donating substituent at C-3 (the exocyclic VHF...
Molecular Quantum Similarity Measures from Fermi hole Densities: Modeling Hammett Sigma Constants
Czech Academy of Sciences Publication Activity Database
Girónes, X.; Ponec, Robert
2006-01-01
Roč. 46, č. 3 (2006), s. 1388-1393 ISSN 1549-9596 Grant - others:SMCT(ES) SAF2000/0223/C03/01 Institutional research plan: CEZ:AV0Z40720504 Keywords : molecula quantum similarity measures * fermi hole densities * substituent effect Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.423, year: 2006
International Nuclear Information System (INIS)
Echevarria, Aurea; Giesbrecht, Astrea
1999-01-01
A series of eleven Schiff Bases have been synthesized. They were obtained by condensation of piperonal (3,4-methylenedioxybenzaldehyde) with the corresponding aromatic primary amines. Their 1 H and 13 C-NMR spectra have been obtained and the Hammett correlations including chemical shifts and the substituent constants (σ p , σR e σI) were studied. Linear and bilinear significant correlations were observed for iminic carbon (C-α) and C-1 ' , showing a more significant resonance effect on chemical shifts. The chemical shifts for C-4 ' were highly affected by substituent effects, especially for halogens in the expected direction. Their biological activity against microorganisms has also been measured and significant activity was showed against Epidermophyton floccosum. The biological activity did not give a reasonable relationship with electronic effects. (author)
The substituent and solvent effects on the antioxidant activity of the ferulic acid derivations
International Nuclear Information System (INIS)
Najafi, M.; Bukhari, S.A.
2014-01-01
The antioxidant activity of ortho and meta substituted ferulic acid derivatives have been investigated in the gas phase and water. The reaction enthalpies of antioxidant activity of studied derivatives have been calculated and compared with corresponding values of ferulic acid. Results show that EWG substituents increase the BDE, IP, while EDG ones cause a rise in the PA. The ferulic acid derivatives with lowest BDE, IP and PA values were identified as the compounds with high antioxidant activity. Results show that the substituents at ortho position have high potential for synthesis of novel ferulic acid derivatives. Results show that ferulic acid derivatives can process their protective role via HAT and SPLET mechanism in gas phase and solvent, respectively. The calculated reaction enthalpies of the substituted ferulic acids have linear dependences with Hammett constants and EHOMO that can be utilized in the selection of suitable substituents for the synthesis of novel antioxidants based on ferulic acid. (author)
Kim; Zhu; Lee
2000-05-19
Rate constants (k(Y)) of the isomerizations of 11 diphenyl N-(substituted benzyl) ketenimines were measured at 40, 50, 60, and 70 degrees C. Activation parameters DeltaH()(Y) and DeltaS()(Y) were obtained using the Eyring equation. The relative rates (k(Y)/k(H)) were fitted into Hammett single correlations (log k(Y)/k(H) = rhosigma and log k(Y)/k(H) = rho(*)sigma(*)). The single correlations have been compared with Hammett dual correlations (log k(Y)/k(H) = rhosigma + rho(*)sigma(*) ). Separate treatments of para and meta substituents yielded even better correlations. Para substituents control the rates through spin-delocalizations and inductive effects. The former outweighs the latter when the latter exerts a modest but distinct influence on the rates. On the other hand, inductive effects are the "major" or the sole interactions triggered by meta substituents.
Czech Academy of Sciences Publication Activity Database
Zborowski, K. K.; Szatylowicz, H.; Stasyuk, Olga A.; Krygowski, T. M.
2017-01-01
Roč. 28, č. 4 (2017), s. 1223-1227 ISSN 1040-0400 Institutional support: RVO:61388963 Keywords : substituent effect * pyrrole derivatives * Hammett equation * charges of the substituent active region Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.582, year: 2016 https://link.springer.com/article/10.1007%2Fs11224-017-0938-7
International Nuclear Information System (INIS)
Seiceira, Rafael C.; Higa, Camila M.; Barreto, Amaro G.; Cajaiba da Silva, Joao F.
2005-01-01
Triaryl phosphites bearing electron donating and electron withdrawing substituents were prepared through the reaction of sodium phenoxides with phosphorus trichloride. The reactions were performed in a Mettler RC1 reaction calorimeter. The main purpose of this work was the determination of Hammett ρ from the synthesis of substituted triaryl phosphites through the interpretation of calorimetric data. The phenoxide bearing a methoxide group was the most reactive, and the one bearing the nitro group was the least reactive. It was demonstrated that the reaction rate depends mainly on the addition rate of phosphorus trichloride solution. A good correlation between the Hammet parameters (σ p + ) was obtained, indicating a reaction mechanism in which a decrease of the negative charge occurs in the transition state
Energy Technology Data Exchange (ETDEWEB)
Robert, J B [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires
1969-07-01
In order to investigate the influence of the configuration at the phosphorus atom and the influence of the substituents attached to the phosphorus atom on the J{sub PH} spin spin coupling constant, we have performed the NMR spectrum analysis of some three coordinated organo-phosphorus compounds. The studied coupling constants are {sup 3}J{sub PH} through P-O-C-H and P-C-C-H fragments and {sup 2}J{sub PH} through P-C-H fragment. The results clearly show that on the NMR time scale, in all the studied compounds (1,3,2-dioxaphospholanes, 1,3,2-dioxaphosphorinanes, 3-phospha-cyclopentene and 4-phosphorinanone) there is no inversion of the bonds around phosphorous. This conclusion held also for secondary phosphines. For a given geometry of the bonds joining the P and H atoms, and a given disposition of the bonds around the phosphorus atom, there is only a little influence of the nature of the substituents on the J{sub PH} spin coupling constants. The geometrical dependence of the {sup 3}J{sub PH} cannot be explained by a 'Karplus law'. There is an influence of the bond disposition around phosphorus. In the case of the {sup 2}J{sub P-C-H}, one can plot a curve {sup 2}J{sub P-C-H} = f({alpha}) (0{<=} {alpha} {<=} 180), {alpha} denote the dihedral angle of the two plane defined the first one by the P, C and H atoms, and the second one by the P-C bond together with the three-fold axis of the bond around phosphorus assuming a regular pyramidal arrangement. The function {sup 2}J{sub P-C-H} = f({alpha}) has two maxima, one for {alpha} = 0 degrees and the other for {alpha} = 180 degrees, and also a minimum for {alpha} = 110 degrees. (author) [French] Ce travail consiste en l'analyse par resonance magnetique nucleaire des constantes de couplage phosphore-proton dans des derives organo-phosphores tricoordines dans un double but: examen de la stabilite des liaisons au niveau du phosphore et etude de l'influence de la disposition des liaisons et de la nature de substituants au
Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei
2016-06-01
Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent
Infrared matrix isolation study of hydrogen bonds involving C-H bonds: Substituent effects
International Nuclear Information System (INIS)
Jeng, M.L.H.; Ault, B.S.
1989-01-01
The matrix isolation technique combined with infrared spectroscopy has been employed to isolate and characterize hydrogen-bonded complexes between a series of substituted alkynes and several oxygen and nitrogen bases. Distinct evidence for hydrogen bond formation was observed in each case, with a characteristic red shift of the hydrogen stretching motion ν r . Shifts between 100 and 300 cm -1 were observed, the largest being for the complex of CF 3 CCH with (CH 3 ) 3 N. The perturbed carbon-carbon triple bond stretching vibration was observed for most complexes, as was the alkynic hydrogen bending motion. Attempts were made to correlate the magnitude of the red shift of ν s with substituent constants for the different substituted alkynes; a roughly linear correlation was found with the Hammett σ parameter. Lack of correlation Δν s with either σ 1 or σ R alone suggests that both inductive and resonance contributions to the strength of the hydrogen-bonding interaction are important
Competitive/co-operative interactions in acid base sandwich: role of cation vs. substituents.
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.
Energy Technology Data Exchange (ETDEWEB)
Xiao, Jiadong [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Xie, Yongbing, E-mail: ybxie@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Han, Qingzhen [State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Cao, Hongbin [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Wang, Yujiao [Department of Chemical and Biomedical Engineering, University of Science and Technology Beijing (China); Nawaz, Faheem; Duan, Feng [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China)
2016-03-05
Highlights: • A weak EWG benefited photocatalytic oxidation of phenols the most. • Phenolic compounds were dominantly oxidized by ·O{sub 2}{sup −}, rather than ·OH, {sup 1}O{sub 2} or h{sup +}. • ·O{sub 2}{sup −} preferred to nucleophilically attack EDG substituted phenols. • ·O{sub 2}{sup −} more likely electrophilically attacked EWG substituted phenols. • ·O{sub 2}{sup −} simultaneously nucleophilically and electrophilically assaulted p-chlorophenol. - Abstract: A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag{sup +}/TiO{sub 2} suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (·O{sub 2}{sup −}) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between ·O{sub 2}{sup −} and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of ·O{sub 2}{sup −} and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by ·O{sub 2}{sup −}, while ·O{sub 2}{sup −} preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by ·O{sub 2}{sup −} could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate
International Nuclear Information System (INIS)
Xiao, Jiadong; Xie, Yongbing; Han, Qingzhen; Cao, Hongbin; Wang, Yujiao; Nawaz, Faheem; Duan, Feng
2016-01-01
Highlights: • A weak EWG benefited photocatalytic oxidation of phenols the most. • Phenolic compounds were dominantly oxidized by ·O_2"−, rather than ·OH, "1O_2 or h"+. • ·O_2"− preferred to nucleophilically attack EDG substituted phenols. • ·O_2"− more likely electrophilically attacked EWG substituted phenols. • ·O_2"− simultaneously nucleophilically and electrophilically assaulted p-chlorophenol. - Abstract: A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag"+/TiO_2 suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (·O_2"−) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between ·O_2"− and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of ·O_2"− and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by ·O_2"−, while ·O_2"− preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by ·O_2"− could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate constant. Possible reactive positions on the phenolic compounds were also detailedly uncovered.
Topological Substituent Descriptors
Directory of Open Access Journals (Sweden)
Mircea V. DIUDEA
2002-12-01
Full Text Available Motivation. Substituted 1,3,5-triazines are known as useful herbicidal substances. In view of reducing the cost of biological screening, computational methods are carried out for evaluating the biological activity of organic compounds. Often a class of bioactives differs only in the substituent attached to a basic skeleton. In such cases substituent descriptors will give the same prospecting results as in case of using the whole molecule description, but with significantly reduced computational time. Such descriptors are useful in describing steric effects involved in chemical reactions. Method. Molecular topology is the method used for substituent description and multi linear regression analysis as a statistical tool. Results. Novel topological descriptors, XLDS and Ws, based on the layer matrix of distance sums and walks in molecular graphs, respectively, are proposed for describing the topology of substituents linked on a chemical skeleton. They are tested for modeling the esterification reaction in the class of benzoic acids and herbicidal activity of 2-difluoromethylthio-4,6-bis(monoalkylamino-1,3,5-triazines. Conclusions. Ws substituent descriptor, based on walks in graph, satisfactorily describes the steric effect of alkyl substituents behaving in esterification reaction, with good correlations to the Taft and Charton steric parameters, respectively. Modeling the herbicidal activity of the seo of 1,3,5-triazines exceeded the models reported in literature, so far.
Kimura, Akifumi; Ishida, Takayuki
2018-01-01
Spin-crossover (SCO) is a reversible transition between low-spin (LS) and high-spin (HS) states by external stimuli like heat. The SCO behavior of [Fe(Ar-pybox)2](ClO4)2 was investigated, where Ar-pybox stands for 4-aryl-2,6-bis(oxazolin-2-yl)pyridine with Ar = 4-pyridyl (4Py), 3-thienyl (3Th), and phenyl (Ph). They were characterized by means of single-crystal X-ray diffraction study, being consistent with the results of the magnetic measurements. The SCO temperatures (T1/2) in the polycrystalline state were determined to be 360 and 230 K for Ar = 4Py and Ph, respectively. The 3Th derivative possessed a HS state in all the temperature range. The solution susceptometry was also performed to purge intermolecular interaction and rigid crystal lattice effects, affording T1/2 = 310, 240, and 240 K for Ar = 4Py, 3Th, and Ph, respectively, in acetone. The substituent effect analysis using the Hammett substituent constant (σp) clarified that electron-withdrawing groups raise T1/2. A plausible model describing the substituent effect on T1/2 is proposed based on d-π interaction. The present result is regarded as a successful example of crystal field engineering.
Energy Technology Data Exchange (ETDEWEB)
Robert, J.B. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires
1969-07-01
In order to investigate the influence of the configuration at the phosphorus atom and the influence of the substituents attached to the phosphorus atom on the J{sub PH} spin spin coupling constant, we have performed the NMR spectrum analysis of some three coordinated organo-phosphorus compounds. The studied coupling constants are {sup 3}J{sub PH} through P-O-C-H and P-C-C-H fragments and {sup 2}J{sub PH} through P-C-H fragment. The results clearly show that on the NMR time scale, in all the studied compounds (1,3,2-dioxaphospholanes, 1,3,2-dioxaphosphorinanes, 3-phospha-cyclopentene and 4-phosphorinanone) there is no inversion of the bonds around phosphorous. This conclusion held also for secondary phosphines. For a given geometry of the bonds joining the P and H atoms, and a given disposition of the bonds around the phosphorus atom, there is only a little influence of the nature of the substituents on the J{sub PH} spin coupling constants. The geometrical dependence of the {sup 3}J{sub PH} cannot be explained by a 'Karplus law'. There is an influence of the bond disposition around phosphorus. In the case of the {sup 2}J{sub P-C-H}, one can plot a curve {sup 2}J{sub P-C-H} = f({alpha}) (0{<=} {alpha} {<=} 180), {alpha} denote the dihedral angle of the two plane defined the first one by the P, C and H atoms, and the second one by the P-C bond together with the three-fold axis of the bond around phosphorus assuming a regular pyramidal arrangement. The function {sup 2}J{sub P-C-H} = f({alpha}) has two maxima, one for {alpha} = 0 degrees and the other for {alpha} = 180 degrees, and also a minimum for {alpha} = 110 degrees. (author) [French] Ce travail consiste en l'analyse par resonance magnetique nucleaire des constantes de couplage phosphore-proton dans des derives organo-phosphores tricoordines dans un double but: examen de la stabilite des liaisons au niveau du phosphore et etude de l'influence de la disposition des liaisons et de la nature de
Stereoelectronic Substituent Effects
DEFF Research Database (Denmark)
Bols, Mikael; Jensen, Henrik Helligsø
2006-01-01
An investigation was carried Out on the influence of the stereo-chemistry of substituents, particularly hydroxyl groups, on their electronic effects in piperidines, carbohydrates (pyranosides), and related compounds. Polar groups, such as OH, OR, and F, were found in the 3 and 4 position to be much...... more electron-withdrawing when positioned equatorially rather than axially. In contrast, little difference in electronic effects was observed from apolar groups as a result of epimerization. These observations were believed to be caused by differences in charge-dipole interactions and were used...... to explain why stereoisomeric glycosides hydrolyze with different rates. The conformational changes of hydroxylated piperidines and related compounds as a function of pH were likewise explained from the different substituent effects of axial and equatorial OH groups....
Bain, Ryan M.; Pulliam, Christopher J.; Yan, Xin; Moore, Kassandra F.; Mu¨ller, Thomas; Cooks, R. Graham
2014-01-01
Undergraduate laboratories generally teach an understanding of chemical reactivity using bulk or semimicroscale experiments with product isolation and subsequent chemical and spectroscopic analysis. In this study students were exposed to mass spectrometry as a means of chemical synthesis as well as analysis. The ionization method used, paper…
A 13C NMR Study of 7-Norbornadienyl Cation by Modified Hammett-Brown Equation
International Nuclear Information System (INIS)
Park, Jeong Kyu; Shin, Jung Hyu
1999-01-01
A series of the para-substituted 7-aryl-norbornadienyl cation (3) was prepared in FSO 3 H/SO 2 ClF solution at -100 .deg. C and their 13 C NMR shifts were measured at -80 .deg. C. The plots of the chemical shifts (changes in chemical shifts) of cationic carbon, Δδ C+ , against our calculated new substituent constant, σ c+ s, gave an excellent correlation (r = 0.994), with a p c+ value of 12.63. These results indicate that the new substituent onstants, σ c+ s, can be successfully employed to compare the relative charge demand of the carbonium ion by π- and πσ-participation
Pentafluorosulfanyl Substituents in Polymerization Catalysis.
Kenyon, Philip; Mecking, Stefan
2017-10-04
Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.
Reactivity and Regioselectivity in the Heck Reaction - A Hammett Study of 4-Substituted Styrenes
DEFF Research Database (Denmark)
Fristrup, Peter; Le Quement, Sebastian; Tanner, David Ackland
2004-01-01
The regioselectivity in the cationic Heck reaction of 4-substituted styrenes was addressed by a Hammett study. In this branching reaction, plots based on the substrate reactivity did not give meaningful data, whereas the product distribution was variable due to differing preferences for further...
International Nuclear Information System (INIS)
Zhang, Tingting; Lang, Qiaolin; Zeng, Lingxing; Li, Tie; Wei, Mingdeng; Liu, Aihua
2014-01-01
In this paper, the relationship between the electrochemical characteristics and the structure of a series of substituted phenol derivatives with electron-donating or electron-withdrawing groups were studied by voltammetry using ordered mesoporous carbons (OMCs) modified glassy carbon electrode (GCE) (OMCs/GCE). p-Nitrophenol (p-NP) and p-methylphenol were selected as models of electron-withdrawing and electron-donating groups, respectively, to illustrate the electrochemical behavior and reaction mechanism of substituted phenols. Voltammetric study showed that the oxidation peak potential (E pa ) of substituted phenols with an electron-withdrawing group was systematically higher than that of substituted phenols with an electron-donating group. That is, the direct electrochemical oxidation of substituted phenol with an electron-withdrawing group is more difficult than that of substituted phenol with an electron-donating group. The E pa value shifted negatively with the increase of pKa for both p-substituted phenols and o-substituted phenols with the equations of pKa = −6.986 E pa + 13.261 (for p-substituted phenols) and pKa = −7.929 E pa + 13.831 (for o-substituted phenols). Thus, a simple and novel method was proposed for the precise prediction of the pKa of substituted phenols by determining E pa values with voltammetry at OMCs/GCE, which matched fairly with the results calculated from Hammett's constants. Thus, the present work may provide additional strategy to determine pKa values and investigate possible mechanisms of some organic reactions. In addition, by making use of the substituent effect, different p-substituted phenols (or o-substituted phenols) can be well separated and identified at OMCs/GCE by voltametry, which may find possible applications in simultaneous detection of p-substituted phenols (or o-substituted phenols)
Winter, Gerhard; Steiner, Ulrich
1980-01-01
The influence of heavy atom substituents (Br, I) in the electron donor aniline on the electron transfer reaction with thiopyronine triplet is investigated by flash spectroscopy in solvents of different viscosity and polarity. Triplet quenching constants and radical yields are determined. The results are analysed in terms of decay constants of an intermediate triplet exciplex where the heavy atom substituents significantly enhance the intersystem crossing process leading to singlet ground stat...
Radiation effects on polyacetylenes having substituents
International Nuclear Information System (INIS)
Higashimura, Toshinobu; Tang, Ben-Zhong; Masuda, Toshio; Yamaoka, Hitoshi; Matsuyama, Tomochika.
1985-01-01
Effects of γ-ray irradiation on high molecular weight polyacetylenes with various substituents were studied in air and in vacuum. The molecular weights of polymers from aliphatic disubstituted acetylenes (2-octyne and 2-decyne) remarkably reduced with irradiation in air. Their G values for chain scission in air were as high as 3 - 12, whereas no degradation occurred in vacuum. The degraded polymers contain carbonyl and hydroxyl groups, and are soluble in polar solvents such as methyl ethyl ketone and acetone. In contrast, polymers of aromatic disubstituted acetylenes (1-phenyl-1-propyne and 1-chloro-2-phenylacetylene) hardly degraded in air even with irradiation up to 40 Mrad. The degradation behavior of poly(t-butylacetylene) was intermediate between those of the above aliphatic and aromatic polymers. Thus the radiolysis of polyacetylenes was found to be greatly dependent on the kind of substituents. (author)
Ertl, P
1998-02-01
Easy to use, interactive, and platform-independent WWW-based tools are ideal for development of chemical applications. By using the newly emerging Web technologies such as Java applets and sophisticated scripting, it is possible to deliver powerful molecular processing capabilities directly to the desk of synthetic organic chemists. In Novartis Crop Protection in Basel, a Web-based molecular modelling system has been in use since 1995. In this article two new modules of this system are presented: a program for interactive calculation of important hydrophobic, electronic, and steric properties of organic substituents, and a module for substituent similarity searches enabling the identification of bioisosteric functional groups. Various possible applications of calculated substituent parameters are also discussed, including automatic design of molecules with the desired properties and creation of targeted virtual combinatorial libraries.
Directory of Open Access Journals (Sweden)
BRATISLAV Z. JOVANOVIC
2007-12-01
Full Text Available The rate constants for the reaction of twenty-two N-(substituted phenyl methylene-m- and -p-aminobenzoic acids with diazodiphenylmethane were determined in absolute ethanol at 30 °C. The effects of substituents on the reactivity of the investigated compounds were interpreted by correlation of the rate constants with LFER equations. The results of quantum mechanical calculations of the mole cular structure together with experimental results gave a better insight into the effects of structure on the transmission of electronic effects of the substituents. New σ constants for substituted benzylideneamino group were calculated.
Energy Technology Data Exchange (ETDEWEB)
Chihara, T; Tanaka, K
1979-02-01
The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation was demonstrated by the reactivities of 2-isopropyl and 2-tert.-butyl cyclohexanone relative to cyclohexanone in individual and competitive hydrogenation at 30/sup 0/C over alumina-supported ruthenium, rhodium, and platinum catalysts. The results indicate that the ketone adsorption onto the catalyst is sterically hindered by the alkyl substitution significantly more than the surface reaction which follows the adsorption.
Interaction of albumin with perylene-diimides with aromatic substituents
Farooqi, Mohammed; Penick, Mark; Burch, Jessica; Negrete, George; Brancaleon, Lorenzo
2015-03-01
Polyaromatic hydrocarbons (PAH) binding to proteins remains one of the fundamental aspects of research in biophysics. Ligand binding can regulate the function of proteins. Binding to small ligands remains a very important aspect in the study of the function of many proteins. Perylene diimide or PDI derivatives have attracted initial interest as industrial dyes and pigments. Recently, much attention has been focused on their strong π - π stacks resulting from the large PDI aromatic core. These PDI stacks have distinct optical properties, and provide informative models that mimic the light-harvesting system and initial charge separation and charge transfer in the photosynthetic system. The absorption property of PDI derivatives may be largely tuned from visible to near-infrared region by chemical modifications at the bay-positions. We are currently studying a new class of PDI derivatives with substituents made of the side chains of aromatic amino acids (Tyrosine, Tryptophan and Phenylalanine). We have looked at the fluorescence absorption and emission of these PDIs in water and other organic solvents. PDIs show evidence of dimerization and possible aggregation. We also present binding studies of these PDIs with Human Serum Albumin (HSA). The binding was studied using fluorescence emission quenching of the HSA Tryptophan residue. Stern-Volmer equation is used to derive the quenching constants. PDI binding to HSA also has an effect on the fluorescence emission of the PDIs themselves by red shifting the spectra. Funded by RCMI grant.
Smith, Caleb A; Gillespie, Blanton R; Heard, George L; Setser, D W; Holmes, Bert E
2017-11-22
The recombination of CF 3 and CHF 2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF 3 CHF 2 * molecules with 101 kcal mol -1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF 3 , CF 3 (F)C: and C 2 F 4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF 3 (F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 10 4 , 4.7 × 10 4 , and 1.1 × 10 4 s -1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E 0 ) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol -1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF 3 (F)C: and HF in the exit channel with a dissociation energy of ∼5 kcal mol -1 . Hydrogen-bonded complexes between HF and the H atom migration transition state of CH 3 (F)C: and the F atom migration transition state of CF 3 (F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed.
D'Anna, Francesca; Frenna, Vincenzo; Ghelfi, Franco; Marullo, Salvatore; Spinelli, Domenico
2011-04-15
The reaction rates for the rearrangement of eleven (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole 3a-k into the relevant (2-aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas 4a-k in the presence of trichloroacetic acid or of piperidine have been determined in toluene at 313.1 K. The results have been related to the effect of the aryl substituent by using Hammett and/or Ingold-Yukawa-Tsuno correlations and have been compared with those previously collected in a protic polar solvent (dioxane/water) as well as with those on the analogous rearrangement of the corresponding (Z)-arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole 1a-k in benzene. Some light can thus be shed on the general differences of chemical reactivity between protic polar (or dipolar aprotic) and apolar solvents.
Rationalizing substituent effects in 1-azathioxanthone photophysics
Junker, Anne Kathrine R.; Just Sørensen, Thomas
2018-01-01
The influence of an electron donating substituent on the photophysical properties of 1-azathioxanthone dyes has been investigated using optical spectroscopy and theoretical models. The motivation behind the study is based on the fact that thioxanthones are efficient triplet sensitizers, and thus promising sensitizers for lanthanide centered emission. By adding an aza group to one of the phenyl ring systems, direct coordination to a lanthanide center becomes possible, which makes azathoixanthones great candidates as antenna chromophores in lanthanide(III) based dyes. Here, three 1-azathioxanthone derivatives have been synthesized targeting efficient triplet formation following absorption in the visible range of the spectrum. This is achieved by adding methoxy groups to the 1-azathioxanthone core. The derivatives were characterized using absorption, emission, and time-gated emission spectroscopy, where fluorescent quantum yields, singlet and triplet excited states lifetimes were determined. The experimentally determined photophysical properties of the three 1-azathioxanthone compounds are contrasted to those of the parent thioxanthone and is rationalized using the Strickler-Berg equation, Hückel MO theory, and Dewar’s rules in combination with computational chemistry. We find that the transition energies follow predictions, but that the overall photophysical properties are determined by the relative energies as well as the nature of the involved states in both the singlet and the triplet excited state manifolds.
Darwish, Elham S.; Mosselhi, Mosselhi A.; Altalbawy, Farag M.; Saad, Hosam A.
2011-01-01
A series of new 8-arylhydrazono-2-(benzylsulfanyl)-7H-purin-6-ones 6 were synthesized, their electronic absorption spectra in different organic solvents of varying polarities were investigated and their acid dissociation constants in both the ground and excited states were determined spectrophotometrically. The tautomeric structures of such products were elucidated by spectral analyses and correlation of their acid dissociation constants with the Hammett equation. The results indicated that t...
International Nuclear Information System (INIS)
Foos, J.
1999-01-01
This paper is written in two tables. The first one describes the different particles (bosons and fermions). The second one gives the isotopes nuclear constants of the different elements, for Z = 1 to 56. (A.L.B.)
International Nuclear Information System (INIS)
Foos, J.
2000-01-01
This paper is written in two tables. The first one describes the different particles (bosons and fermions). The second one gives the isotopes nuclear constants of the different elements, for Z = 56 to 68. (A.L.B.)
International Nuclear Information System (INIS)
Foos, J.
1998-01-01
This paper is made of two tables. The first table describes the different particles (bosons and fermions) while the second one gives the nuclear constants of isotopes from the different elements with Z = 1 to 25. (J.S.)
International Nuclear Information System (INIS)
Foos, J.
1999-01-01
This paper is written in two tables. The first one describes the different particles (bosons and fermions). The second one gives the isotopes nuclear constants of the different elements, for Z = 56 to 68. (A.L.B.)
Are fundamental constants really constant
International Nuclear Information System (INIS)
Norman, E.B.
1986-01-01
Reasons for suspecting that fundamental constants might change with time are reviewed. Possible consequences of such variations are examined. The present status of experimental tests of these ideas is discussed
International Nuclear Information System (INIS)
Palusiak, Marcin; Simon, Silvia; Sola, Miquel
2007-01-01
The proton transfer in malonaldehyde and in some of its derivatives have been considered in order to study the interrelation between the reaction barrier and the π-delocalization in the quasi-ring. A set of simple and mostly common substituents having different properties in resonance effect according to values of substituents constants were chosen in order to simulate the influence of substitution in position 2 or in position 1 (or 3) of malonaldehyde on the quasi-aromaticity and H-bonding. The following substituents have been taken into consideration: NO, NO 2 , CN, CHO, F, H, CH 3 , OCH 3 , OH, and NH 2 . Our results show that when the substituent is attached at position 2 of the quasi-ring, the resonance effect predominates over the field/inductive effect which leads to changes in H-bonding and quasi-aromaticity of the ring motif, while in the case of 1(3) substitution the field/inductive effect is significantly more effective influencing the HB strength, and thus, the proton transfer barrier. Somehow counterintuitively, for the 1(3) substituted systems, the most stable isomer is the one having the weakest HB and lower aromaticity. The reason for this surprising behaviour is discussed
International Nuclear Information System (INIS)
Su, D.T.T.; Thornton, E.R.
1978-01-01
Intramolecular and intermolecular deuterium isotope effects have been measured for the thermal carbene H rearrangements of three substituted 1-phenyl-2-diazopropanes-1-d in hexane at 25 0 C. The isotope effects, k/sub H//k/sub D/, vary from ca. 1.2 to 1.5, increasing with electron-withdrawing substituents, for the formation of both cis- and trans-β-methylstyrenes. Product ratios were determined for these compounds as well as the corresponding undeuterated ones, permitting calculation of intermolecular primary and secondary isotope effects. In addition, the competition among the cis and trans products and the product of H migration from the terminal methyl group permitted determination of Hammett rho values of ca. -1 for the competition between benzylic and terminal migration. The results strongly indicate a ''pull-push'' mechanism, which can be pictured roughly as electrophilic attack on the C--H bond by the phantom p orbital of the carbene along with backside nucleophilic attack by the carbene unshared electron pair to push the H away and form the π bond. The data are believed to be consistent only with a nonzero barrier for the carbene hydrogen rearrangement
Effect of substituent structure on pyrimidine electrophilic substitution
CSIR Research Space (South Africa)
Van der Westhuyzen, CW
2007-01-01
Full Text Available In an investigation into the electrophilic nitrosation reactions of a series of 4,6-disubstituted pyrimidine derivatives, a subtle interplay between the electronic nature of the C-4 and C-6 substituents and reactivity was found where these were...
Organic Semiconductors and Conductors with tert-Butyl Substituents
Directory of Open Access Journals (Sweden)
Toshiki Higashino
2012-08-01
Full Text Available Tetrathiafulvalene (TTF, pentacene, and quarterthiophene with tert-butyl substituents are synthesized, and the crystal structures and the transistor properties are investigated. The tetracyanoquinodimethane (TCNQ complex of tert-butyl TTF constructs highly one-dimensional segregated columns with tetragonal crystal symmetry.
Effect of substituents on the reactivity of ninhydrin with urea
Jong, Jacobus A.W.; Moret, Marc Etienne; Verhaar, Marianne C.; Hennink, Wim E.; Gerritsen, Karin G.F.; Van Nostrum, Cornelus F.
2018-01-01
Ninhydrin, i. e. the stable hydrate of the reactive species indanetrione, is a well-known compound used for the quantification of ammonia and amino acids. However, substituent effects on the reactivity of ninhydrin with nucleophiles are not described. In this work, the kinetics of the reaction of
Energy Technology Data Exchange (ETDEWEB)
Chihara, T; Tanaka, K
1979-02-01
Adsorption estimations during competitive hydrogenation of cyclohexanone and its 2-alkyl derivatives alumina-supported ruthenium, rhodium, and platinum catalysts were obtained in a study to determine the relative contributions of the rate constants and the adsorption equilibrium constants to the substituent-dependent constant. The reaction rates obtained during competitive hydrogenation were in the order cyclohexanone (A) Vertical Bar3:Vertical Bar3: 2-methyl cyclohexanone (B) Vertical Bar3: 2-ethyl cyclohexanone (C) Vertical Bar3: 2-propyl cyclohexanone (D) for all catalysts, whereas the rates obtained during individual hydrogenation were in the order A Vertical Bar3: B approx. C approx. D. The adsorption equilibrium constants which were estimated by analyzing the kinetic data agreed well with the theoretical values derived from statistical mechanics by using a model in which the substrate ketones were immobilely adsorbed.
Energy Technology Data Exchange (ETDEWEB)
Jeon, Seong Hoon; Kim, Hyun Soo; Han, Young Joon [Sejong Science High School, Seoul (Korea, Republic of); Kim, Minyoung; Um, Ikhwan [Ewha Woman' s Univ., Seoul (Korea, Republic of)
2013-10-15
Second-order rate constants (k{sub N}) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % H{sub 2}O/20 mol % DMSO at 25.0 ± 0.1 .deg. C. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρ{sub X} = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Brφnsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with β{sub 2} = 0.85, β{sub 1} = 0.24, and pK{sub a}{sup o} = 10.5, implying that a change in RDS occurs from the k{sub 2} step to the k{sub 1} process as the pK{sub a} of the conjugate acid of the amine exceeds 10.5. Dissection of k{sub N} into the microscopic rate constants k{sub 1} and k{sub 2}/k{sub -1} ratio associated with the reaction of 1d reveals that k{sub 2} is dependent on the amine basicity, which is contrary to generally held views.
International Nuclear Information System (INIS)
Takayama, T.; Sekine, T.; Kudo, H.
2003-01-01
Theoretical calculations based on the density functional theory (DFT) were performed to understand the effect of substituents on the molecular and electronic structures of technetium nitrido complexes with salen type Schiff base ligands. Optimized structures of these complexes are square pyramidal. The electron density on a Tc atom of the complex with electron withdrawing substituents is lower than that of the complex with electron donating substituents. The HOMO energy is lower in the complex with electron withdrawing substituents than that in the complex with electron donating substituents. The charge on Tc atoms is a good measure that reflects the redox potential of [TcN(L)] complex. (author)
Shiraishi, Tomonari; Shiraki, Tomohiro; Nakashima, Naotoshi
2017-11-09
Single-walled carbon nanotubes (SWNTs) with local chemical modification have been recognized as a novel near infrared (NIR) photoluminescent nanomaterial due to the emergence of a new red-shifted photoluminescence (PL) with enhanced quantum yields. As a characteristic feature of the locally functionalized SWNTs (lf-SWNTs), PL wavelength changes occur with the structural dependence of the substituent structures in the modified aryl groups, showing up to a 60 nm peak shift according to an electronic property difference of the aryl groups. Up to now, however, the structural effect on the electronic states of the lf-SWNTs has been discussed only on the basis of theoretical calculations due to the very limited amount of modifications. Herein, we describe the successfully-determined electronic states of the aryl-modified lf-SWNTs with different substituents (Ar-X SWNTs) using an in situ PL spectroelectrochemical method based on electrochemical quenching of the PL intensities analyzed by the Nernst equation. In particular, we reveal that the local functionalization of (6,5)SWNTs induced potential changes in the energy levels of the HOMO and the LUMO by -23 to -38 meV and +20 to +22 meV, respectively, compared to those of the pristine SWNTs, which generates exciton trapping sites with narrower band gaps. Moreover, the HOMO levels of the Ar-X SWNTs specifically shift in a negative potential direction by 15 meV according to an enhancement of the electron-accepting property of the substituents in the aryl groups that corresponds to an increase in the Hammet substituent constants, suggesting the importance of the dipole effect from the aryl groups on the lf-SWNTs to the level shift of the frontier orbitals. Our method is a promising way to characterize the electronic features of the lf-SWNTs.
Energy Technology Data Exchange (ETDEWEB)
Krivdin, L.B.; Shcherbakov, V.V.; Kalabin, G.A.
1988-03-10
The direct spin-spin coupling constants in the vinyl group were measured in 100 mono-substituted ethylene derivatives. The inductive effect of the substituent was found to be the major factor in the variation of this constant and, in some cases, the stereospecific effect of the unshared electron pairs of heteratoms makes a significant contribution to the /sup 13/C-/sup 13/C coupling constants.
Correlating substituent parameter values to electron transport properties of molecules
International Nuclear Information System (INIS)
Vedova-Brook, Natalie; Matsunaga, Nikita; Sohlberg, Karl
2004-01-01
There are a vast number of organic compounds that could be considered for use in molecular electronics. Because of this, the need for efficient and economical screening tools has emerged. We demonstrate that the substituent parameter values (σ), commonly found in advanced organic chemistry textbooks, correlate strongly with features of the charge migration process, establishing them as useful indicators of electronic properties. Specifically, we report that ab initio derived electronic charge transfer values for 16 different substituted aromatic molecules for molecular junctions correlate to the σ values with a correlation coefficient squared (R 2 ) of 0.863
Directory of Open Access Journals (Sweden)
Hosam A. Saad
2011-10-01
Full Text Available A series of new 8-arylhydrazono-2-(benzylsulfanyl-7H-purin-6-ones 6 were synthesized, their electronic absorption spectra in different organic solvents of varying polarities were investigated and their acid dissociation constants in both the ground and excited states were determined spectrophotometrically. The tautomeric structures of such products were elucidated by spectral analyses and correlation of their acid dissociation constants with the Hammett equation. The results indicated that the studied compounds 6 exist predominantly in the hydrazone tautomeric form 6A in both the ground and excited states.
Long-range carbon-proton spin-spin coupling constants in conformational analysis
International Nuclear Information System (INIS)
Spoormaker, T.
1979-01-01
The author has collected a reliable set of data on long range 13 C- 1 H coupling constants in aliphatic compounds and developed the use of long range 13 C- 1 H coupling constants as a tool in the conformational analysis of aliphatic compounds. An empirical determination of the torsion angle dependence of the vicinal 13 C- 1 H coupling constant for model compounds is described and the dependence of long range 13 C- 1 H coupling constants on the electronegativity of substituents attached to the coupling pathway reported for the monohalogen substituted ethanes and propanes. The electronegativity dependence of the vicinal 13 C- 1 H coupling was studied in monosubstituted propanes whose substituents are elements from the first row of the periodic table and it is shown that the vicinal 13 C- 1 H coupling constant in aliphatic systems is a constitutive property. The geminal 13 C- 1 H coupling constants in ethyl, isopropyl and tert-butyl compounds, which have been substituted by an element of the first row of the periodic table or a haline atom, are reported and the influence of electronegative substituents on the vicinal 13 C- 1 H coupling constants in the individual rotamers of 13 CH 3 -C(X)H-C(Y)H- 1 H fragments discussed. The application of long range 13 C- 1 H coupling constants to the conformational analysis of CMP-N-Acetylneuraminic acid and 2,6-dichloro-1,4-oxathiane is described. (Auth.)
Zhao, J.; Schols, H.A.; Chen Zenghong,; Jin Zhengyu,; Buwalda, P.L.; Gruppen, H.
2012-01-01
Revealing the substituents distribution within starch can help to understand the changes of starch properties after modification. The distribution of substituents over cross-linked and hydroxypropylated sweet potato starch was investigated and compared with modified potato starch. The starches were
Shimizu, Akihiro; Ito, Akitaka; Teki, Yoshio
2016-02-18
Pentacene derivatives possessing nitronyl nitroxide radical substituents (1a and 1b) were synthesized, and their photochemical properties were evaluated. 1a with two radical substituents showed a remarkable enhancement of photostability compared with pentacene, 6,13-bis(triisopropylsilylethynyl)pentacene and the monoradical, 1b. This is understood due to the presence of the multiple deactivation pathways in the photoexcited states.
Constant physics and characteristics of fundamental constant
International Nuclear Information System (INIS)
Tarrach, R.
1998-01-01
We present some evidence which supports a surprising physical interpretation of the fundamental constants. First, we relate two of them through the renormalization group. This leaves as many fundamental constants as base units. Second, we introduce and a dimensional system of units without fundamental constants. Third, and most important, we find, while interpreting the units of the a dimensional system, that is all cases accessible to experimentation the fundamental constants indicate either discretization at small values or boundedness at large values of the corresponding physical quantity. (Author) 12 refs
Interchain interactions in charged diacetylenic oligomers carrying bulk substituents revisited
International Nuclear Information System (INIS)
Ottonelli, M.; Izzo, G.M.M.; Comoretto, D.; Musso, G.F.; Dellepiane, G.
2006-01-01
We are studying how the electronic properties of an aggregate, built with conjugated oligomers carrying bulk substituents, are affected by intermolecular interactions. In this paper we apply the CEO (Collective Electronic Oscillator) method, on the basis of the semiempirical INDO/S Hamiltonian, to compute the electronic density matrix modifications following the photon absorption in a doubly charged cluster of two units of a fully carbazolyl-substituted oligodiacetylene tetramer, taken as a model system. The picture that had emerged from our previous calculations based on the less sophisticated CIS (Configuration Interaction including Singles) approach is seen to be confirmed. Despite the large separation between the backbones, a through-space charge transfer occurs between the two oligomers due to the fact that the excess charge, contrary to what is generally believed, is not localized on the conjugated backbone, but is spread out over the carbazolyl moieties of the charged molecule. Consideration of this kind of interaction improves the theoretical results obtained for the isolated charged oligomer chain, and aids in better explaining some features of the experimental photoinduced spectra of the corresponding polymer
Cosmological Hubble constant and nuclear Hubble constant
International Nuclear Information System (INIS)
Horbuniev, Amelia; Besliu, Calin; Jipa, Alexandru
2005-01-01
The evolution of the Universe after the Big Bang and the evolution of the dense and highly excited nuclear matter formed by relativistic nuclear collisions are investigated and compared. Values of the Hubble constants for cosmological and nuclear processes are obtained. For nucleus-nucleus collisions at high energies the nuclear Hubble constant is obtained in the frame of different models involving the hydrodynamic flow of the nuclear matter. Significant difference in the values of the two Hubble constant - cosmological and nuclear - is observed
International Nuclear Information System (INIS)
Józefowicz, M.; Bajorek, A.; Pietrzak, M.; Heldt, J.R.; Heldt, J.
2014-01-01
In this article, we report the photophysical properties of six, newly synthesized donor-substituted 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene fluorophores. The steady-state and time-resolved spectroscopic experiments have been used to investigate the substituent and solvent effects on the locally excited (LE) and intramolecular charge transfer (ICT) emission. We demonstrate that the spectroscopic characteristics (fluorescence quantum yields, fluorescence decay times, radiative rate constants, and ground and excited state dipole moments) of the studied D–A dyes, as well as the reorganization energies characterizing the solute–solvent interactions and intramolecular torsion motions greatly depend on different substituents and microenvironment. On the basis of the experimental results and our previous quantum-chemical calculations, it was shown that two emitting charge transfer states: non-relaxed (ICT) NR and relaxed (ICT) R exist in six biphenyl derivatives dissolved in polar solvents (e.g., THF), whereas in non-polar medium (MCH) the existence of two emissive states have been attributed to non-relaxed and relaxed, locally excited state ((LE) NR , (LE) R ). - Highlights: • Spectroscopic properties greatly depend on different substituents and microenvironment. • Investigated dyes form a typically spectrally inhomogeneous system. • Two emitting charge transfer states (ICT) NR and (ICT) R exist in polar solvents. • In non-polar medium locally excited fluorescence is possible from (LE) NR and (LE) R states
Cui, Xiaoyan; Sun, Can; Zhao, Pei; Wang, Yanyan; Guo, Yanchun; Zhao, Yufen; Cao, Shuxia
2018-04-01
The fragmentation pathways of pentacoordinated phenoxyspirophosphoranes were investigated in the positive mode by electrospray ionization multistage mass spectrometry. The results demonstrate that the sodium adducts of the title compounds undergo two competitive fragmentation pathways, and the fragmentation patterns are heavily dependent on the various substituent patterns at the phenolic group. An electron-withdrawing substituent at the ortho-position always results in the removal of a corresponding phenol analogue, while cleavage by spiroring opening becomes the predominant fragmentation pathway if an electron-donating substituent is at the phenolic group. The substituent effects on the competitive fragmentation pathways were further elucidated by theoretical calculations, single crystal structure analysis, and high-resolution mass spectrometry. The results contribute to the understanding of the gas-phase fragmentation reactions and the structure identification of spirophosphorane analogues by electrospray ionization multistage mass spectrometry. Copyright © 2018 John Wiley & Sons, Ltd.
Effects of the Substituents of Boron Atoms on Conjugated Polymers Containing B←N Units.
Liu, Jun; Wang, Tao; Dou, Chuandong; Wang, Lixiang
2018-06-15
Organoboron chemistry is a new tool to tune the electronic structures and properties of conjugated polymers, which are important for applications in organic opto-electronic devices. To investigate the effects of substituents of boron atoms on conjugated polymers, we synthesized three conjugated polymers based on double B←N bridged bipyridine (BNBP) with various substituents on the boron atoms. By changing the substituents from four phenyl groups and two phenyl groups/two fluorine atoms to four fluorine atoms, the BNBP-based polymers show the blue-shifted absorption spectra, decreased LUMO/HOMO energy levels and enhanced electron affinities, as well as the increased electron mobilities. Moreover, these BNBP-based polymers can be used as electron acceptors for all-polymer solar cells. These results demonstrate that the substituents of boron atoms can effectively modulate the electronic properties and applications of conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
FORMATION CONSTANTS AND THERMODYNAMIC ...
African Journals Online (AJOL)
KEY WORDS: Metal complexes, Schiff base ligand, Formation constant, DFT calculation ... best values for the formation constants of the proposed equilibrium model by .... to its positive charge distribution and the ligand deformation geometry.
Ion exchange equilibrium constants
Marcus, Y
2013-01-01
Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and
Wei, Lu; She, Yuanbin; Yu, Yanmin; Yao, Xiaoqian; Zhang, Suojiang
2012-06-01
To investigate the effects of the substituents, substituent positions and axial chloride ligand on the geometric and electronic properties of the iron tetraphenylporphyrin (FeTPP), a series of the substituented iron tetraphenylporphyrins and their chlorides, FeT(o/p-R)PP and FeT(o/p-R)PPCl (R = -H, -Cl, -NO(2), -OH, -OCH(3)), were systematically calculated without any symmetry constraint by using DFT method. For geometric structure, the substituent position and axial Cl ligand change the configuration of the iron porphyrin obviously. The ortho-substituents prefer making the phenyls perpendicular to the porphyrin ring; the axial chloride draws the central Fe ion ~0.500 Å out of the porphyrin plane toward the ligand. With regard to electronic properties, it is found that E(LUMO) could be related to the catalytic activity. The electron-withdrawing group always lowers the energies of both frontier orbitals, while the electron-donating one heightens them simultaneously, but they affect the E(HOMO) and E(LUMO) in the same sequence, -NO(2) < -Cl < -H < -OH < -OCH(3). The substituent effects on the central Fe ion were explored by calculating NBO charge distribution, spin density and natural electron configuration.
Energy Technology Data Exchange (ETDEWEB)
Basso, Ernani A [Universidade Estadual de Maringa, PR (Brazil); Trevisan, Paulo S [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica; Lambert, Joseph B [Northwestern Univ. (United States)
1992-12-31
This work re-evaluates, using a high-field device (400 MHz) and the Eliel method, the 2-halo substituted cyclohexanone conformational equilibrium, which applies the chemical shift values ({delta}) and the {alpha} proton coupling constants (J). {sup 13} C NMR spectra were also obtained for investigation of the substituent effects on the cyclohexanone ring carbons chemical shift, since the few works treating the subject are at most incomplete. The results are compared with those obtained for the 2-methoxy cyclohexanone previously described, and reproduced in this work 12 refs., 4 figs., 3 tabs.
Indian Academy of Sciences (India)
IAS Admin
The article discusses the importance of the fine structure constant in quantum mechanics, along with the brief history of how it emerged. Al- though Sommerfelds idea of elliptical orbits has been replaced by wave mechanics, the fine struc- ture constant he introduced has remained as an important parameter in the field of ...
The effects of characteristics of substituents on toxicity of the nitroaromatics: HiT QSAR study
Kuz'min, Victor E.; Muratov, Eugene N.; Artemenko, Anatoly G.; Gorb, Leonid; Qasim, Mohammad; Leszczynski, Jerzy
2008-10-01
The present study applies the Hierarchical Technology for Quantitative Structure-Activity Relationships (HiT QSAR) for (i) evaluation of the influence of the characteristics of 28 nitroaromatic compounds (some of which belong to a widely known class of explosives) as to their toxicity; (ii) prediction of toxicity for new nitroaromatic derivatives; (iii) analysis of the effects of substituents in nitroaromatic compounds on their toxicity in vivo. The 50% lethal dose concentration for rats (LD50) was used to develop the QSAR models based on simplex representation of molecular structure. The preliminary 1D QSAR results show that even the information on the composition of molecules reveals the main tendencies of changes in toxicity. The statistic characteristics for partial least squares 2D QSAR models are quite satisfactory ( R 2 = 0.96-0.98; Q 2 = 0.91-0.93; R 2 test = 0.89-0.92), which allows us to carry out the prediction of activity for 41 novel compounds designed by the application of new combinations of substituents represented in the training set. The comprehensive analysis of toxicity changes as a function of substituent position and nature was carried out. Molecular fragments that promote and interfere with toxicity were defined on the basis of the obtained models. It was shown that the mutual influence of substituents in the benzene ring plays a crucial role regarding toxicity. The influence of different substituents on toxicity can be mediated via different C-H fragments of the aromatic ring.
Energy Technology Data Exchange (ETDEWEB)
Stefan, L.S. [Ain Shams Univ., Cairo (Egypt)
1995-09-01
Chelate stability constants of aryl bis(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)methane (ABPM) derivatives with thorium(IV) ion were determined by the potentiometric method at 30 C and 0.1 mol dm{sup -3} (KNO{sub 3}) in 75% (v/v) dioxane-water solvent. The computation of the titration data indicated that four kinds of complexes [ThL]{sup 2+}, [ThL(OH)]{sup +}, [ThL{sub 2}] and [ThL(OH){sub 2}] were formed. The appropriate formation constants for all of the 1:1 species and 2:1 complexes have been calculated are probable ligand-banding sites of the complexes were proposed. In addition, the applicability of the Hammett equation for correlation of the stability constants of [Th(IV)-ABPM] complexes was discussed. (author). 19 refs, 5 figs, 1 tab.
International Nuclear Information System (INIS)
Stefan, L.S.
1995-01-01
Chelate stability constants of aryl bis(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)methane (ABPM) derivatives with thorium(IV) ion were determined by the potentiometric method at 30 C and 0.1 mol dm -3 (KNO 3 ) in 75% (v/v) dioxane-water solvent. The computation of the titration data indicated that four kinds of complexes [ThL] 2+ , [ThL(OH)] + , [ThL 2 ] and [ThL(OH) 2 ] were formed. The appropriate formation constants for all of the 1:1 species and 2:1 complexes have been calculated are probable ligand-banding sites of the complexes were proposed. In addition, the applicability of the Hammett equation for correlation of the stability constants of [Th(IV)-ABPM] complexes was discussed. (author). 19 refs, 5 figs, 1 tab
Semi-empirical proton binding constants for natural organic matter
Matynia, Anthony; Lenoir, Thomas; Causse, Benjamin; Spadini, Lorenzo; Jacquet, Thierry; Manceau, Alain
2010-03-01
Average proton binding constants ( KH,i) for structure models of humic (HA) and fulvic (FA) acids were estimated semi-empirically by breaking down the macromolecules into reactive structural units (RSUs), and calculating KH,i values of the RSUs using linear free energy relationships (LFER) of Hammett. Predicted log KH,COOH and log KH,Ph-OH are 3.73 ± 0.13 and 9.83 ± 0.23 for HA, and 3.80 ± 0.20 and 9.87 ± 0.31 for FA. The predicted constants for phenolic-type sites (Ph-OH) are generally higher than those derived from potentiometric titrations, but the difference may not be significant in view of the considerable uncertainty of the acidity constants determined from acid-base measurements at high pH. The predicted constants for carboxylic-type sites agree well with titration data analyzed with Model VI (4.10 ± 0.16 for HA, 3.20 ± 0.13 for FA; Tipping, 1998), the Impermeable Sphere model (3.50-4.50 for HA; Avena et al., 1999), and the Stockholm Humic Model (4.10 ± 0.20 for HA, 3.50 ± 0.40 for FA; Gustafsson, 2001), but differ by about one log unit from those obtained by Milne et al. (2001) with the NICA-Donnan model (3.09 ± 0.51 for HA, 2.65 ± 0.43 for FA), and used to derive recommended generic values. To clarify this ambiguity, 10 high-quality titration data from Milne et al. (2001) were re-analyzed with the new predicted equilibrium constants. The data are described equally well with the previous and new sets of values ( R2 ⩾ 0.98), not necessarily because the NICA-Donnan model is overparametrized, but because titration lacks the sensitivity needed to quantify the full binding properties of humic substances. Correlations between NICA-Donnan parameters are discussed, but general progress is impeded by the unknown number of independent parameters that can be varied during regression of a model fit to titration data. The high consistency between predicted and experimental KH,COOH values, excluding those of Milne et al. (2001), gives faith in the proposed
Indian Academy of Sciences (India)
IAS Admin
Here, we intend to provide a qualitative ... She works as. CSIR Senior Research Fellow. (Ext). ... conformational analysis, Pollak and Curtin put forward the fun- ..... A common question to the students in their practical classes is: how can the ...
Substituent Effects on the Hydrogen Bonding Between Phenolate and HF, H2O and NH3
Institute of Scientific and Technical Information of China (English)
无
2002-01-01
B3LYP/6-31+g(d) calculations were performed on the hydrogen bonded complexes between substituted phenolates and HF, H2O as well as NH3. It was found that some properties of the non-covalent complexes, including the interaction energies, donor-acceptor (host-guest) distances, bond lengths, and vibration frequencies, could show well-defined substituent effects. Thus, from the substituent studies we can not only understand the mechanism of a particular non-covalent interaction better, but also easily predict the interaction energies and structures of a particular non-covalent complex, which might otherwise be very hard or resource-consuming to be known. This means that substituent effect is indeed a useful tool to be used in supramolecular chemistry and therefore, many valuable studies remain to be carried out.
Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.
Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki
2010-08-21
Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.
Energy Technology Data Exchange (ETDEWEB)
Praveen, P. A.; Babu, R. Ramesh, E-mail: rampap2k@yahoo.co.in [Crystal Growth and Thin films Laboratory, Department of Physics, Bharathidasan University, Tiruchirappalli - 620 024, Tamilnadu (India)
2016-05-23
In this report, the polarizability and first and second order hyperpolarizability values of bis benzimidazole Zn(II)-2R and bis benzimidazole Cd(II)-2R complexes, with different electron donating moieties R (R= Cl, Br, I, Acetate) were calculated using time dependent Hartree-Fock (TDHF) formalism embedded in MOPAC2012 package. Further the role of substituents on polarizability and hyperpolarizability values is investigated for the first time by analyzing the frontier molecular orbitals of the complexes with respect to the electronegativity of the substituents. It is found that the increase in electronegativity of the substituents correspondingly increases the energy gap of the molecules, which in turn reduces the polarizability values of both Zn and Cd benzimidazole complexes. Similarly, increase in electronegativity reduces the electric quadrupole moments of both the metal complexes, which in turn reduces the hyperpolarizability values.
Energy Technology Data Exchange (ETDEWEB)
Krivdin, L.B.; Proidakov, A.G.; Bazhenov, B.N.; Zinchenko, S.V.; Kalabin, G.A.
1989-01-10
The effects of substitution on the direct /sup 13/C-/sup 13/C spin-spin coupling constants of the triple bond were studied in 100 derivatives of acetylene. It was established that these parameters exhibit increased sensitivity to the effect of substituents compared with other types of compounds. The main factor which determines their variation is the electronegativity of the substituting groups, and in individual cases the /pi/-electronic effects are appreciable. The effect of the substituents with an element of the silicon subgroup at the /alpha/ position simultaneously at the triple bond or substituent of the above-mentioned type and a halogen atom.
Cosmological constants and variations
International Nuclear Information System (INIS)
Barrow, John D
2005-01-01
We review properties of theories for the variation of the gravitation and fine structure 'constants'. We highlight some general features of the cosmological models that exist in these theories with reference to recent quasar data that is consistent with time-variation in the fine structure 'constant' since a redshift of 3.5. The behaviour of a simple class of varying alpha cosmologies is outlined in the light of all the observational constraints. We also discuss some of the consequences of varying 'constants' for oscillating universes and show by means of exact solutions that they appear to evolve monotonically in time even though the scale factor of the universe oscillates
The cosmological constant problem
International Nuclear Information System (INIS)
Dolgov, A.D.
1989-05-01
A review of the cosmological term problem is presented. Baby universe model and the compensating field model are discussed. The importance of more accurate data on the Hubble constant and the Universe age is stressed. 18 refs
Alem, van K.; Lodder, G.; Zuilhof, H.
2002-01-01
The effects of -substituents on alkyl and vinyl cations are studied using high-level ab initio calculations. The geometries, stabilities, and electronic properties of 27 alkyl cations and 27 vinyl cations with -substituents are computed at the B3LYP/6-311 G(d,p), MP2/6-311 G(d,p), and CBS-Q levels.
野本, 健雄; Nomoto, Takeo
1986-01-01
Six monosubstituted diphenylacetylenes, p-X-C6H4-C≡C-C6H5 1 (Ⅹ=NMe2, NH2, OMe, Cl, and NO2), were synthesized, and 13C-NMR spectra of their acetylenic carbons were measured. Hammett plots of the chemical shifts of the acetylenic α-13C and β-13C (against substituent constants σ) respectively showed a linear relationship, eXCept for β-13C on NMe2 and NH2 groups. The effects of substituents on 13C-Chemical shifts of diphenylacetylenes and effeciency of the C≡C bonds in transmitting the substitue...
Emission color tuning in AlQ3 complexes with extended conjugated chromophores.
Pohl, Radek; Anzenbacher, Pavel
2003-08-07
[reaction: see text] A new method for the synthesis of 5-arylethynyl-8-hydroxyquinoline ligands using Sonogashira-Hagihara coupling was developed. The electronic nature of arylethynyl substituents affects the emission color and quantum yield of the resulting Al(III) complex. Photophysical properties of the metallocomplexes correspond to the electron-withdrawing/-donating character of the arylethynyl substituents. Optical properties of such Al(III) complexes correlate with the Hammett constant values of the respective substituents. This strategy offers a powerful tool for the preparation of electroluminophores with predictable photophysical properties.
Xu, Linxiang; Cheng, Rui; Li, Jing; Wang, Yang; Zhu, Bin; Ma, Shihong; Zhang, Weiming; Dong, Wei; Wang, Shiming; Zhang, Jianfa
2017-01-01
Salecan, a soluble β-1,3-D-glucan produced by a salt-tolerant strain Agrobacterium sp. ZX09, has been the subject of considerable interest in recent years because of its multiple bioactivities and unusual rheological properties in solution. In this study, both succinyl and pyruvyl substituent groups on salecan were identified by an enzymatic hydrolysis following nuclear magnetic resonance (NMR), HPLC, and MS analysis. The putative succinyltransferase gene (sleA) and pyruvyltransferase gene (sleV) were determined and cloned. Disruption of the sleA gene resulted in the absence of succinyl substituent groups on salecan. This defect could be complemented by expressing the sleA cloned in a plasmid. Thus, the sleA and sleV genes located in a 19.6-kb gene cluster may be involved in salecan biosynthesis. Despite the lack of succinyl substituents, the molecular mass of salecan generated by the sleA mutant did not substantially differ from that generated by the wild-type strain. Loss of succinyl substituents on salecan changed its rheological characteristics, especially a decrease in intrinsic viscosity.
Molecules with Linear π-Conjugated Pathways between All Substituents : Omniconjugation
Veen, Marleen H. van der; Rispens, Minze T.; Jonkman, Harry T.; Hummelen, Jan C.
2004-01-01
In this paper, omniconjugation is introduced as a topological phenomenon in π-conjugated systems. Omniconjugated molecules are defined by the fact that they provide direct and fully π-conjugated pathways between all substituents attached to them. Surprisingly, until now such topologies have never
DEFF Research Database (Denmark)
Guo, Zheng; Chen, Biqiang; Murillo, Rafael López
2006-01-01
hydrophobic substituents and hydrophilic ethoxyl or hydroxyl moieties is found, respectively, to be essential for triglycerides (TG) dissolving and equilibrium shifting. The reactions in the ILs with cations consisting of long chain and free hydroxyl groups gave markedly higher conversion of TG and better...
Substituent effif ects on hydrogen bonding in Watson-Crick base pairs. A theoretical study
Fonseca Guerra, C.; van der Wijst, T.; Bickelhaupt, F.M.
2005-01-01
We have theoretically analyzed Watson-Crick AT and GC base pairs in which purine C8 and/or pyrimidine C6 positions carry a substituent X = H, F, Cl or Br, using the generalized gradient approximation (GGA) of density functional theory at BP86/TZ2P. The purpose is to study the effects on structure
Adachi, Shinya; Takeda, Norihiko; Sibi, Mukund P
2014-12-19
Enantioselective conjugate addition of malononitrile to pyrazolidinone-derived enoates proceeds in excellent yields and high enantioselectivities. A comparison of fluxional substituents with and without a Brønsted basic site and their impact on selectivity is detailed. Molecular sieves as an additive were found to be essential to achieve high enantioselectivity.
Role of substituents on the reactivity and electron density profile of ...
Indian Academy of Sciences (India)
Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. Role of substituents on the reactivity and electron density profile of diimine ligands: A density functional theory based study. Bhakti S Kulkarni Deepti Mishra Sourav Pal. Volume 125 Issue 5 September 2013 pp 1247-1258 ...
Substituent effects on the excited states of phenyl-capped phenylene vinylene tetramers
Candeias, L.P.; Gelinck, G.H.; Piet, J.J.; Piris, J.; Wegewijs, B.; Peeters, E.; Wildeman, J.; Hadziioannou, G.; Müllen, K.
2001-01-01
The singlet and triplet excited states of phenyl-capped tetramers of phenylene vinylene with different alkyl, alkoxy or cyano substituents, were investigated in benzene solution. The lowest singlet states were studied by laser flash-photolysis with time-resolved microwave conductivity and
Substituent effects in the ortho position: Model compounds with a removed reaction centre
Czech Academy of Sciences Publication Activity Database
Böhm, S.; Exner, Otto
2007-01-01
Roč. 81, 5/6 (2007), s. 993-1006 ISSN 0137- 5083 Institutional research plan: CEZ:AV0Z40550506 Keywords : substituent effect * density functional theory * ortho effect * steric effect Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.483, year: 2007
Radiographic constant exposure technique
DEFF Research Database (Denmark)
Domanus, Joseph Czeslaw
1985-01-01
The constant exposure technique has been applied to assess various industrial radiographic systems. Different X-ray films and radiographic papers of two producers were compared. Special attention was given to fast film and paper used with fluorometallic screens. Radiographic image quality...... was tested by the use of ISO wire IQI's and ASTM penetrameters used on Al and Fe test plates. Relative speed and reduction of kilovoltage obtained with the constant exposure technique were calculated. The advantages of fast radiographic systems are pointed out...
International Nuclear Information System (INIS)
Chandra, R.
1977-01-01
On the grounds of the two correspondence limits, the Newtonian limit and the special theory limit of Einstein field equations, a modification of the cosmical constant has been proposed which gives realistic results in the case of a homogeneous universe. Also, according to this modification an explanation for the negative pressure in the steady-state model of the universe has been given. (author)
International Nuclear Information System (INIS)
Weinberg, S.
1989-01-01
Cosmological constant problem is discussed. History of the problem is briefly considered. Five different approaches to solution of the problem are described: supersymmetry, supergravity, superstring; anthropic approach; mechamism of lagrangian alignment; modification of gravitation theory and quantum cosmology. It is noted that approach, based on quantum cosmology is the most promising one
International Nuclear Information System (INIS)
O Murchadha, N.
1991-01-01
The set of riemannian three-metrics with positive Yamabe constant defines the space of independent data for the gravitational field. The boundary of this set is investigated, and it is shown that metrics close to the boundary satisfy the positive-energy theorem. (Author) 18 refs
Energy Technology Data Exchange (ETDEWEB)
Li, Xiangcheng; Zhao, Zhang; Zhu, Boquan [Wuhan Univ. of Science and Technology (China). State Key Lab. of Refractories and Metallurgy
2015-01-15
In this study, La-Zn-substituted SrFe{sub 12}O{sub 19} ferrites were synthesized using the traditional ceramic process. The by-products of iron oxide scales from a steel plant were used as the main raw materials. The influence of the La-Zn substituent and the calcination temperature on the microstructure and magnetic properties of Sr{sub 1-x}La{sub x}Fe{sub 12-x}Zn{sub x}O{sub 19} ferrites was investigated. The results showed that with the increase in the x value, the crystalline lattice constant of the a- and c-axes and the cell volume decreased. There was no α-Fe{sub 2}O{sub 3} phase in the ferrites when the value of x was 0.3. The corresponding saturation magnetization (M{sub s}) and remnant magnetization (M{sub r}) values were, respectively, about 65 emu g{sup -1} and 39.5 emu g{sup -1}. Both values of M{sub s} and M{sub r} rise to the maximum value. When the calcination temperature was reduced from 1200 C to 1150 C, the average particle size decreased from 0.9 μm to 0.7 μm and M{sub s} remained at 65 emu g{sup -1}. However, the coercivity increased from 2690 Oe to 3100 Oe.
Production in constant evolution
International Nuclear Information System (INIS)
Lozano, T.
2009-01-01
The Cofrentes Nuclear Power Plant now has 25 years of operation behind it: a quarter century adding value and demonstrating the reasons why it is one of the most important energy producing facilities in the Spanish power market. Particularly noteworthy is the enterprising spirit of the plant, which has strived to continuously improve with the large number of modernization projects that it has undertaken over the past 25 years. The plant has constantly evolved thanks to the amount of investments made to improve safety and reliability and the perseverance to stay technologically up to date. Efficiency, training and teamwork have been key to the success of the plant over these 25 years of constant change and progress. (Author)
International Nuclear Information System (INIS)
Blake, J.B.; Dearborn, D.S.P.
1979-01-01
Small fluctuations in the solar constant can occur on timescales much shorter than the Kelvin time. Changes in the ability of convection to transmit energy through the superadiabatic and transition regions of the convection zone cause structure adjustments which can occur on a time scale of days. The bulk of the convection zone reacts to maintain hydrostatic equilibrium (though not thermal equilibrium) and causes a luminosity change. While small radius variations will occur, most of the change will be seen in temperature
Stabilized power constant alimentation
International Nuclear Information System (INIS)
Roussel, L.
1968-06-01
The study and realization of a stabilized power alimentation variable from 5 to 100 watts are described. In order to realize a constant power drift of Lithium compensated diodes, we have searched a 1 per cent precision of regulation and a response time minus than 1 sec. Recent components like Hall multiplicator and integrated amplifiers give this possibility and it is easy to use permutable circuits. (author) [fr
Yongquan, Han
2016-10-01
The ideal gas state equation is not applicable to ordinary gas, it should be applied to the Electromagnetic ``gas'' that is applied to the radiation, the radiation should be the ultimate state of matter changes or initial state, the universe is filled with radiation. That is, the ideal gas equation of state is suitable for the Singular point and the universe. Maybe someone consider that, there is no vessel can accommodate radiation, it is because the Ordinary container is too small to accommodate, if the radius of your container is the distance that Light through an hour, would you still think it can't accommodates radiation? Modern scientific determinate that the radius of the universe now is about 1027 m, assuming that the universe is a sphere whose volume is approximately: V = 4.19 × 1081 cubic meters, the temperature radiation of the universe (cosmic microwave background radiation temperature of the universe, should be the closest the average temperature of the universe) T = 3.15k, radiation pressure P = 5 × 10-6 N / m 2, according to the law of ideal gas state equation, PV / T = constant = 6 × 1075, the value of this constant is the universe, The singular point should also equal to the constant Author: hanyongquan
Connecting Fundamental Constants
International Nuclear Information System (INIS)
Di Mario, D.
2008-01-01
A model for a black hole electron is built from three basic constants only: h, c and G. The result is a description of the electron with its mass and charge. The nature of this black hole seems to fit the properties of the Planck particle and new relationships among basic constants are possible. The time dilation factor in a black hole associated with a variable gravitational field would appear to us as a charge; on the other hand the Planck time is acting as a time gap drastically limiting what we are able to measure and its dimension will appear in some quantities. This is why the Planck time is numerically very close to the gravitational/electric force ratio in an electron: its difference, disregarding a π√(2) factor, is only 0.2%. This is not a coincidence, it is always the same particle and the small difference is between a rotating and a non-rotating particle. The determination of its rotational speed yields accurate numbers for many quantities, including the fine structure constant and the electron magnetic moment
Kumar, Ashish; Singh, Roop Shikha; Kumar, Amit; Ali, Afsar; Biswas, Arnab; Pandey, Daya Shankar
2016-09-19
A pioneering approach towards controlling the efficiency of saponification assisted gelation in ethyl ester based Zn II -complexes have been described. Using four new ester containing bis-salen Zn II complexes (C1-C4) involving different para-azo phenyl substituted ligands it has been clearly shown that gelation efficiency is greatly influenced by the electronic effects of the substituents (-H (C1), -CH 3 (C2), -NO 2 (C3), and -OCH 3 (C4)). Morphological, photophysical, and rheological investigations corroborated the experimental observations well and established that gelation efficiency was enhanced with electron-withdrawing characteristics of substituents (C4
Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch
DEFF Research Database (Denmark)
Hansen, Mia Harring; Elm, Jonas; Olsen, Stine Tetzschner
2016-01-01
We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazu......We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent...... on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption...
Directory of Open Access Journals (Sweden)
Neal Jackson
2015-09-01
Full Text Available I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. There are two broad categories of measurements. The first uses individual astrophysical objects which have some property that allows their intrinsic luminosity or size to be determined, or allows the determination of their distance by geometric means. The second category comprises the use of all-sky cosmic microwave background, or correlations between large samples of galaxies, to determine information about the geometry of the Universe and hence the Hubble constant, typically in a combination with other cosmological parameters. Many, but not all, object-based measurements give H_0 values of around 72–74 km s^–1 Mpc^–1, with typical errors of 2–3 km s^–1 Mpc^–1. This is in mild discrepancy with CMB-based measurements, in particular those from the Planck satellite, which give values of 67–68 km s^–1 Mpc^–1 and typical errors of 1–2 km s^–1 Mpc^–1. The size of the remaining systematics indicate that accuracy rather than precision is the remaining problem in a good determination of the Hubble constant. Whether a discrepancy exists, and whether new physics is needed to resolve it, depends on details of the systematics of the object-based methods, and also on the assumptions about other cosmological parameters and which datasets are combined in the case of the all-sky methods.
International Nuclear Information System (INIS)
Willson, R.C.; Hudson, H.
1984-01-01
The Active Cavity Radiometer Irradiance Monitor (ACRIM) of the Solar Maximum Mission satellite measures the radiant power emitted by the sun in the direction of the earth and has worked flawlessly since 1980. The main motivation for ACRIM's use to measure the solar constant is the determination of the extent to which this quantity's variations affect earth weather and climate. Data from the solar minimum of 1986-1987 is eagerly anticipated, with a view to the possible presence of a solar cycle variation in addition to that caused directly by sunspots
Anaerobic C1 metabolism of the O-methyl-14C-labeled substituent of vanillate
International Nuclear Information System (INIS)
Frazer, A.C.; Young, L.Y.
1986-01-01
The O-methyl substituents of aromatic compounds constitute a C 1 growth substrate for a number of taxonomically diverse anaerobic acetogens. In this study, strain TH-001, an O-demethylating obligate anaerobe, was chosen to represent this physiological group, and the carbon flow when cells were grown on O-methyl substituents as a C 1 substrate was determined by 14 C radiotracer techniques. O-[methyl- 14 C]vanillate (4-hydroxy-3-methoxy-benzoate) was used as the labeled C 1 substrate. The data showed that for every O-methyl carbon converted to [ 14 C]acetate, two were oxidized to 14 CO 2 . Quantitation of the carbon recovered in the two products, acetate and CO 2 , indicated that acetate was formed in part by the fixation of unlabeled CO 2 . The specific activity of 14 C in acetate was 70% of that in the O-methyl substrate, suggesting that only one carbon of acetate was derived from the O-methyl group. Thus, it is postulated that the carboxyl carbon of the product acetate is derived from CO 2 and the methyl carbon is derived from the O-methyl substituent of vanillate
Potential constants and centrifugal distortion constants of octahedral hexafluoride molecules
Energy Technology Data Exchange (ETDEWEB)
Manivannan, G [Government Thirumagal Mill' s Coll., Gudiyattam, Tamil Nadu (India)
1981-04-01
The kinetic constants method outlined by Thirugnanasambandham (1964) based on Wilson's (1955) group theory has been adapted in evaluating the potential constants for SF/sub 6/, SeF/sub 6/, WF/sub 6/, IrF/sub 6/, UF/sub 6/, NpF/sub 6/, and PuF/sub 6/ using the experimentally observed vibrational frequency data. These constants are used to calculate the centrifugal distortion constants for the first time.
1995-08-01
about the distances to galaxies and thereby about the expansion rate of the Universe. A simple way to determine the distance to a remote galaxy is by measuring its redshift, calculate its velocity from the redshift and divide this by the Hubble constant, H0. For instance, the measured redshift of the parent galaxy of SN 1995K (0.478) yields a velocity of 116,000 km/sec, somewhat more than one-third of the speed of light (300,000 km/sec). From the universal expansion rate, described by the Hubble constant (H0 = 20 km/sec per million lightyears as found by some studies), this velocity would indicate a distance to the supernova and its parent galaxy of about 5,800 million lightyears. The explosion of the supernova would thus have taken place 5,800 million years ago, i.e. about 1,000 million years before the solar system was formed. However, such a simple calculation works only for relatively ``nearby'' objects, perhaps out to some hundred million lightyears. When we look much further into space, we also look far back in time and it is not excluded that the universal expansion rate, i.e. the Hubble constant, may have been different at earlier epochs. This means that unless we know the change of the Hubble constant with time, we cannot determine reliable distances of distant galaxies from their measured redshifts and velocities. At the same time, knowledge about such change or lack of the same will provide unique information about the time elapsed since the Universe began to expand (the ``Big Bang''), that is, the age of the Universe and also its ultimate fate. The Deceleration Parameter q0 Cosmologists are therefore eager to determine not only the current expansion rate (i.e., the Hubble constant, H0) but also its possible change with time (known as the deceleration parameter, q0). Although a highly accurate value of H0 has still not become available, increasing attention is now given to the observational determination of the second parameter, cf. also the Appendix at the
Lu, Jia-Syun; Yang, Ming-Chung; Su, Ming-Der
2017-07-05
Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH₃, SiH₃, SiMe(Si t Bu₃)₂, Si i PrDis₂, Tbt (=C₆H₂-2,4,6-(CH(SiMe₃)₂)₃), and Ar* (=C₆H₃-2,6-(C₆H₂-2, 4,6- i -Pr₃)₂)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.
Mulder, Joshua R; Guerra, Célia Fonseca; Slootweg, J Chris; Lammertsma, Koop; Bickelhaupt, F Matthias
2016-01-15
A comprehensive theoretical treatment is presented for the electronic excitation spectra of ca. 50 different mono-, di-, and tetrasubstituted naphthalenediimides (NDI) using time-dependent density functional theory (TDDFT) at ZORA-CAM-B3LYP/TZ2P//ZORA-BP86/TZ2P with COSMO for simulating the effect of dichloromethane (DCM) solution. The substituents -XHn are from groups 14-17 and rows 2-5 of the periodic table. The lowest dipole-allowed singlet excitation (S0 -S1 ) of the monosubstituted NDIs can be tuned from 3.39 eV for -F to 2.42 eV for -TeH, while the S0 -S2 transition is less sensitive to substitution with energies ranging between 3.67 eV for -CH3 and 3.44 eV for -SbH2 . In the case of NDIs with group-15 and -16 substituents, the optical transitions strongly depend on the extent to which -XHn is planar or pyramidal as well as on the possible formation of intramolecular hydrogen bonds. The accumulative effect of double and quadruple substitution leads in general to increasing bathochromic shifts, but the increased steric hindrance in tetrasubstituted NDIs can lead to deformations that diminish the effectiveness of the substituents. Detailed analyses of the Kohn-Sham orbital electronic structure in monosubstituted NDIs reveal the mesomeric destabilization of the HOMO as the primary cause of the bathochromic shift of the S0-S1 transition. © 2015 Wiley Periodicals, Inc.
2013-01-01
reactivated than AChE conjugates inhibited by the corresponding Rp enantiomers and this effect is enhanced as the size of the O-alkyl substituents of OP...Organophosphates and Carbamates, Butterworth & Heinemann , Oxford, 1992. pp. 555–577. [2] P. Taylor, Anticholinesterase agents, in: L.L. Brunton, J.S...application of the Hammett equation with the constants rph in the chemistry of organophosphorus compounds, Russ. Chem. Rev. 38 (1969) 795–811. [13
Association constants of telluronium salts
International Nuclear Information System (INIS)
Kovach, N.A.; Rivkin, B.B.; Sadekov, T.D.; Shvajka, O.P.
1996-01-01
Association constants in acetonitrile of triphenyl telluronium salts, which are dilute electrolytes, are determined through the conductometry method. Satisfactory correlation dependence of constants of interion association and threshold molar electroconductivity on the Litvinenko-Popov constants for depositing groups is identified. 6 refs
Anisotropic constant-roll inflation
Energy Technology Data Exchange (ETDEWEB)
Ito, Asuka; Soda, Jiro [Kobe University, Department of Physics, Kobe (Japan)
2018-01-15
We study constant-roll inflation in the presence of a gauge field coupled to an inflaton. By imposing the constant anisotropy condition, we find new exact anisotropic constant-roll inflationary solutions which include anisotropic power-law inflation as a special case. We also numerically show that the new anisotropic solutions are attractors in the phase space. (orig.)
Quintessence and the cosmological constant
International Nuclear Information System (INIS)
Doran, M.; Wetterich, C.
2003-01-01
Quintessence -- the energy density of a slowly evolving scalar field -- may constitute a dynamical form of the homogeneous dark energy in the universe. We review the basic idea in the light of the cosmological constant problem. Cosmological observations or a time variation of fundamental 'constants' can distinguish quintessence from a cosmological constant
Ferrer-Ugalde, A; Cabrera-González, J; Juárez-Pérez, E J; Teixidor, F; Pérez-Inestrosa, E; Montenegro, J M; Sillanpää, R; Haukka, M; Núñez, R
2017-02-14
Two novel styrene-containing meta-carborane derivatives substituted at the second carbon cluster atom (C c ) with either a methyl (Me) or a phenyl (Ph) group are introduced herein along with a new set of stilbene-containing ortho- (o-) and meta- (m-) carborane dyads. The latter set of compounds have been prepared from styrene-containing carborane derivatives via a Heck coupling reaction. High regioselectivity has been achieved for these compounds by using a combination of palladium complexes [Pd 2 (dba) 3 ]/[Pd(t-Bu 3 P) 2 ] as a catalytic system, yielding exclusively E isomers. All compounds have been fully characterised and the crystal structures of seven of them were analysed by X-ray diffraction. The absorption spectra of these compounds are similar to those of their respective fluorophore groups (styrene or stilbene), showing a very small influence of the substituent (Me or Ph) linked to the second C c atom or the cluster isomer (o- or m-). On the other hand, fluorescence spectroscopy revealed high emission intensities for Me-o-carborane derivatives, whereas their Ph-o-carborane analogues evidenced an almost total lack of fluorescence, confirming the significant role of the substituent bound to the adjacent C c in o-carboranes. In contrast, all the m-carborane derivatives display similar photoluminescence (PL) behavior regardless of the substituent attached to the second C c , demonstrating its small influence on emission properties. Additionally, m-carborane derivatives are significantly more fluorescent than their o-counterparts, reaching quantum yield values as high as 30.2%. Regarding solid state emission, only stilbene-containing Ph-o-carborane derivatives, which showed very low fluorescence in solution, exhibited notable PL emission in films attributed to aggregation-induced emission. DFT calculations were performed to successfully complement the photoluminescence studies, supporting the experimentally observed photophysical behavior of the styrene and
Directory of Open Access Journals (Sweden)
Dall'Oglio Evandro
2002-01-01
Full Text Available The tautomerism of five symmetrically substituted 2,2'-bis-benzimidazoles [5(6,5'(6'-tetramethyl- (1; 5(6,5'(6'-dimethyl-(2; 5(6,5'(6'-dichloro- (3; 5(6,5'(6'-dimethoxy- (4 and 4(7,4'(7'-dimethyl-2,2'-bis-benzimidazole (5], was studied by means of ¹H NMR spectroscopy at variable temperatures, and the influence of the substituents on the energy barriers for tautomeric interconversion was interpreted with the aid of theoretical calculations.
Excited-state dynamics of pentacene derivatives with stable radical substituents.
Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio
2014-06-23
The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Electronic effects of substituents in o-hydroxyazo compounds and azoquinone-hydrazone tautomerism
International Nuclear Information System (INIS)
Raikhshtat, M.M.; Zhogina, V.V.; Savvin, S.B.
1987-01-01
The authors have investigated the electronic structure of p-substituted phenylazonaphthol and some o-hydroxyazo compounds of the general structure X-N=N-Y. The influence of structural changes of the X and Y radicals on the electronic structure of the o-hydroxyazo group was studied. The results are compared with experimental data, obtained by NMR 13 C, by tautomerism of these compounds in solution in CDCl 3 . The electronic structure of o-hydroxyazo compounds was calculated by the PPDP/2 method. This method satisfactorily describes the electronic structure of organic compounds and correctly reproduces electronic effects of the substituents
Hemmateenejad, Bahram; Emami, Leila; Sharghi, Hashem
2010-01-01
The acidity constants of some newly synthesized Schiff base derivatives were determined by hard-model based multivariate data analysis of the spectrophotometric data in the course of pH-metric titration in 50% (v/v) methanol-water binary solvent. The employed data analysis method was also able to extract the pure spectra and pH-dependent concentration profiles of the acid-base species. The molecules that possess different substituents (both electron donating and withdrawing) on the ortho-, meta- and para-positions of one of the phenyl ring showed variable acidity constants ranging from 8.77 to 11.07 whereas the parent molecule had an acidity constant of 10.25. To investigate the quantitative effects of changing of substitution pattern on the acidity constant, a quantitative structure-property relation analysis was conducted using substituent constants and molecular descriptor. Some models with high statistical quality (measured by cross-validation Q2) were obtained. It was found that the acidity constant of the studied molecules in the methanol-water mixed solvent not only is affected by electronic features of the solutes but also by the lipophilic interaction between methanol part of solvent and the deprotonated solutes.
Directory of Open Access Journals (Sweden)
Maximiliano Martínez-Cifuentes
2016-12-01
Full Text Available In this work, a computational study of a series of N-substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N-substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA and vertical electron affinities (VEA, as well as vertical detachment energy (VDE. To study electrophilic properties of these structures, local reactivity indices, such as Fukui (f+ and Parr (P+ functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity.
Energy Technology Data Exchange (ETDEWEB)
Tikhonov, Sergey A., E-mail: allser@bk.ru [Far Eastern Federal University, 8 Sukhanova St., Vladivostok, 690950 (Russian Federation); Vovna, Vitaliy I. [Far Eastern Federal University, 8 Sukhanova St., Vladivostok, 690950 (Russian Federation); Borisenko, Aleksandr V. [Vladivostok Branch of Russian Customs Academy, 16v Strelkovaya St., Vladivostok, 690034 (Russian Federation)
2016-11-15
Highlights: • The electronic structures of three nitrogen analogues of boron β-diketonates have been investigated. • UV photoelectron spectra have been interpreted. • The structure of the UV photoelectron spectra is in good agreement with the energies and compositions of Kohn-Sham orbitals. - Abstract: The electronic structure of three nitrogen analogoues of boron β-diketonates containing aromatic substituents was studied by the ultraviolet photoelectron spectroscopy and within the density functional theory. In order to determine effects of heteroatom substitution in the chelate ligand, a comparative analysis was carried out for the electronic structure of three model compounds. In a range of model compounds, the HOMO's nature was revealed to be the same. The HOMO-1 orbital of nitrogen containing compounds is determined by the presence of lone electron pairs of nitrogen. In a range of the complexes under study, the influence of aromatic substituents on the electronic structure was defined. In the imidoylamidinate complex, in contrast to formazanates and β-diketonates, it was found the absence of any noticeable mixing of π-orbitals of the chelate and benzene rings. It was shown that within energy range to 11 eV, the calculated results reproduce well the energy differences between the ionized states of complexes.
Tejerina, Lara; Martínez-Díaz, M Victoria; Nazeeruddin, Mohammad Khaja; Torres, Tomas
2016-03-18
Phthalocyanines (Pcs) are used as sensitizers in dye-sensitized solar cells (DSSCs) because of their stability and intense absorption in the red and near-IR regions. Impressive progress has been made in photovoltaic efficiencies by introduction of bulky peripheral substituents to help suppress macrocycle aggregation. To reach benchmark efficiencies reported for other related dyes, new designs need to be explored. Single carboxy-ZnPc regioisomers substituted at the non-peripheral positions by rigid aryl groups have now been studied, which has shed light on the influence of steric hindrance and/or orientation of the substituent around the anchoring group on the photovoltaic response. The regioisomer bearing the aryl group far away from the anchoring group produces a more effective sensitization of the TiO2 films and higher short-circuit photocurrent density (Jsc). Taking advantage of the good photovoltaic performance in the near-IR region of this ZnPc, it was combined with another appropriate dye for panchromatic sensitization of the mesoporous photoelectrode and an increase of the overall device efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DFT study on the effect of exocyclic substituents on the proton affinity of 1-methylimidazole
International Nuclear Information System (INIS)
Liu, Haining; Bara, Jason E.; Turner, C. Heath
2013-01-01
Highlights: • DFT calculations are used to predict the proton affinity of 1-methylimidazoles. • The electron-withdrawing groups dominate the predicted proton affinity. • The effects of multiple substituents on the proton affinity can be accurately predicted. • Large compound libraries can be screened for imidazoles with tailored reactivity. - Abstract: A deeper understanding of the acid/base properties of imidazole derivatives will aid the development of solvents, polymer membranes and other materials that can be used for CO 2 capture and acid gas removal. In this study, we employ density functional theory calculations to investigate the effect of various electron-donating and electron-withdrawing groups on the proton affinity of 1-methylimidazole. We find that electron-donating groups are able to increase the proton affinity relative to 1-methylimidazole, i.e., making the molecule more basic. In contrast, electron-withdrawing groups cause a decrease of the proton affinity. When multiple substituents are present, their effects on the proton affinity were found to be additive. This finding offers a quick approach for predicting and targeting the proton affinities of this series of molecules, and we show the strong correlation between the calculated proton affinities and experimental pK a values
International Nuclear Information System (INIS)
Zhang Shiming; Guo Yunlong; Xi Hongxia; Di Chongan; Yu Jian; Zheng Kai; Liu Ruigang; Zhan Xiaowei; Liu Yunqi
2009-01-01
Dithienothiophene-phenylene cooligomers with n-hexyloxy or n-dodecyloxy substituents have been synthesized and compared to the previously reported unsubstituted parent compound. The effect of substituents on the thermal, electronic, optical, thin film structure and field-effect transistor (OFET) properties was investigated. Structural phase transitions from highly-ordered nanocrystalline to liquid crystalline were observed at 241 and 213 deg. C for n-hexyloxy- and n-dodecyloxy-substituted compounds respectively, different from the parent compound. For the alkoxy-substituted compounds, the absorption spectra in thin film blue shift 50 nm, while the fluorescence spectra in thin film red shift 88-100 nm compared to those in solution. The OFET devices based on the alkoxy-substituted compounds exhibit mobilities as high as ca 0.02 cm 2 V -1 s -1 and their performance is sensitive to the alkoxy substituents and substrate temperatures
Elongational flow of polymer melts at constant strain rate, constant stress and constant force
Wagner, Manfred H.; Rolón-Garrido, Víctor H.
2013-04-01
Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.
DEFF Research Database (Denmark)
Dahlstrand, Christian; Yamazaki, Kaoru; Kilså, Kristine
2010-01-01
(TCNQ) and tetrathiafulvalene (TTF) as representing strong electron-acceptor and -donor compounds, respectively. The substituents X at the exocyclic positions of the fulvenes were either NH(2), H, or CN, while the substituents Y at the ring positions were H, Cl, F, CN, or NH(2). The variations...... of bis(fulvene)s, i.e., compounds composed of a donor-type heptafulvene fused with an acceptor-type pentafulvene, and it was revealed that these bis(fulvene)s can be designed so that the IE and EA of the two separate fulvene segments are retained, potentially allowing for the design of compact donor...
Spectrophotometric determination of association constant
DEFF Research Database (Denmark)
2016-01-01
Least-squares 'Systematic Trial-and-Error Procedure' (STEP) for spectrophotometric evaluation of association constant (equilibrium constant) K and molar absorption coefficient E for a 1:1 molecular complex, A + B = C, with error analysis according to Conrow et al. (1964). An analysis of the Charge...
Directory of Open Access Journals (Sweden)
Lingjia Xu
2007-04-01
Full Text Available Semiempirical AM1 and INDO/CIS methods were used to study the structures and spectroscopy of hydrogen bonded complexes formed by the oligophenyleneethynylene (monomer A with isophthalic acid (monomer B. The binding energies of the complexes are lowered by increasing electron-donating abilities of the substituents near the hydrogen bonds on monomer A. The first absorptions in the electronic spectra and the vibration frequencies of the N-H bonds in the IR spectra for the complexes are both red-shifted compared with those of the monomers. The presence of dimethylsulfoxide (DMSO can reduce the binding energy of the complex through hydrogen bonding. This results in a blue-shift for the first absorption in the electronic spectrum and red-shift for the vibration frequencies of the N-H bonds in the IR spectrum of the complex.
Asgharzadeh, Somaie; Vahedpour, Morteza
2018-06-01
Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.
Jia, Yu-Hui; Yang, Kai-Xiang; Chen, Shi-Lu; Huang, Mu-Hua
2018-01-11
Nitrogen-rich compounds such as tetrazoles are widely used as candidates in gas-generating agents. However, the details of the differentiation of the two isomers of disubstituted tetrazoles are rarely studied, which is very important information for designing advanced materials based on tetrazoles. In this article, pairs of 2,5- and 1,5-disubstituted tetrazoles were carefully designed and prepared for study on their thermal decomposition behavior. Also, the substitution fashion of 2,5- and 1,5- and the substituents at C-5 position were found to affect the endothermic or exothermic properties. This is for the first time to the best of our knowledge that the thermal decomposition properties of different tetrazoles could be tuned by substitution ways and substitute groups, which could be used as a useful platform to design advanced materials for temperature-dependent rockets. The aza-Claisen rearrangement was proposed to understand the endothermic decomposition behavior.
Energy Technology Data Exchange (ETDEWEB)
Tang, Gui-Mei, E-mail: meiguit@163.com; Chi, Rui-Hai; Wan, Wen-Zhu; Chen, Zhi-Qiang; Yan, Ting-Xiang; Dong, Yan-Ping; Wang, Yong-Tao, E-mail: ceswyt@qlu.edu.cn; Cui, Yue-Zhi
2017-05-15
Two phenylcarbazole-based dimers, namely, 9,9'-diphenyl-9H,9'H−3,3'-bicarbazole (1) and 9,9'-bis(4-bromophenyl)−9H,9'H−3,3'-bicarbazole (2), have been obtained through the oxidation of 9-phenylcarbazole and 9-(4’-bromophenyl) in the presence of FeCl{sub 3}, respectively, which show strong photoluminescent properties with the fluorescence quantum yields of 0.2 and 0.21 based on the reference of Quinin sulfate, respectively. The maximal emission peak of compounds 1 and 2 were observed at 465 and 413 nm in the solid state, respectively, revealing that the luminescent properties were tuned by the substituent group. The title compounds were characterized by FI-IR, UV–vis, {sup 1}H-NMR, {sup 13}C-NMR, {sup 1}H−{sup 13}C NMR, mass spectra, elemental analysis (EA) and single-crystal X-ray diffraction. Both compounds 1 and 2 crystallize in space group P-1, and supramolecular hydrogen bondings and stacking interactions between aromatic rings are observed. Compounds 1 and 2 display trans- and cis-formation structures, respectively. Two compounds show high thermal stabilities, in which the decomposition temperature is 414 and 363 °C for 1 and 2, respectively. - Graphical abstract: Two phenylcarbazole-based dimers have been obtained through the oxidation of 9-phenylcarbazole and 9-(4’-bromophenyl) in the presence of FeCl{sub 3}, respectively. The maximal emission peaks of compounds 1 and 2 were observed at 465 and 413 nm, respectively, revealing that the luminescent properties were tuned by the substituent group. Compounds 1 and 2 display trans- and cis-formation structures, respectively, and they show high thermal stabilities.
Ring substituents mediate the morphology of PBDTTPD-PCBM bulk-heterojunction solar cells
Warnan, Julien
2014-04-08
Among π-conjugated polymer donors for efficient bulk-heterojunction (BHJ) solar cell applications, poly(benzo[1,2-b:4,5-b′]dithiophene- thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill-factors (FF, ca. 70%) in conventional (single-cell) BHJ devices with PCBM acceptors. In PBDTTPD, side chains of varying size and branching affect polymer self-assembly, nanostructural order, and impact material performance. However, the role of the polymer side-chain pattern in the intimate mixing between polymer donors and PCBM acceptors, and on the development of the BHJ morphology is in general less understood. In this contribution, we show that ring substituents such as furan (F), thiophene (T) and selenophene (S)-incorporated into the side chains of PBDTTPD polymers-can induce significant and, of importance, very different morphological effects in BHJs with PCBM. A combination of experimental and theoretical (via density functional theory) characterizations sheds light on how varying the heteroatom of the ring substituents impacts (i) the preferred side-chain configurations and (ii) the ionization, electronic, and optical properties of the PBDTTPD polymers. In parallel, we find that the PBDT(X)TPD analogs (with X = F, T, or S) span a broad range of power conversion efficiencies (PCEs, 3-6.5%) in optimized devices with improved thin-film morphologies via the use of 1,8-diiodooctane (DIO), and discuss that persistent morphological impediments at the nanoscale can be at the origin of the spread in PCE across optimized PBDT(X)TPD-based devices. With their high VOC ∼1 V, PBDT(X)TPD polymers are promising candidates for use in the high-band gap cell of tandem solar cells. © 2014 American Chemical Society.
Ring substituents mediate the morphology of PBDTTPD-PCBM bulk-heterojunction solar cells
Warnan, Julien; El Labban, Abdulrahman; Cabanetos, Clement; Hoke, Eric T.; Shukla, Pradeep Kumar; Risko, Chad; Bré das, Jean Luc; McGehee, Michael D.; Beaujuge, Pierre
2014-01-01
Among π-conjugated polymer donors for efficient bulk-heterojunction (BHJ) solar cell applications, poly(benzo[1,2-b:4,5-b′]dithiophene- thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill-factors (FF, ca. 70%) in conventional (single-cell) BHJ devices with PCBM acceptors. In PBDTTPD, side chains of varying size and branching affect polymer self-assembly, nanostructural order, and impact material performance. However, the role of the polymer side-chain pattern in the intimate mixing between polymer donors and PCBM acceptors, and on the development of the BHJ morphology is in general less understood. In this contribution, we show that ring substituents such as furan (F), thiophene (T) and selenophene (S)-incorporated into the side chains of PBDTTPD polymers-can induce significant and, of importance, very different morphological effects in BHJs with PCBM. A combination of experimental and theoretical (via density functional theory) characterizations sheds light on how varying the heteroatom of the ring substituents impacts (i) the preferred side-chain configurations and (ii) the ionization, electronic, and optical properties of the PBDTTPD polymers. In parallel, we find that the PBDT(X)TPD analogs (with X = F, T, or S) span a broad range of power conversion efficiencies (PCEs, 3-6.5%) in optimized devices with improved thin-film morphologies via the use of 1,8-diiodooctane (DIO), and discuss that persistent morphological impediments at the nanoscale can be at the origin of the spread in PCE across optimized PBDT(X)TPD-based devices. With their high VOC ∼1 V, PBDT(X)TPD polymers are promising candidates for use in the high-band gap cell of tandem solar cells. © 2014 American Chemical Society.
International Nuclear Information System (INIS)
Cuillerdier, C.; Musikas, C.
1993-01-01
Present invention is concerned with new amides with nitrogenous heterocyclic substituent utilizable to separate trivalent actinium series from trivalent lanthanides. In these molecules, it is possible to obtain particularly covalent liaison which has more affinity with 5f series, that is to say actinium series; included a manufacturing process for these amides with nitrogenous heterocyclic substituent
Haitjema, HJ; Buruma, R; VanEkenstein, GORA; Tan, YY; Challa, G
1996-01-01
New azobenzene-based (az.b.) monomers with CO2H (acid) or N(CH3)(2) (basic) substituents were synthesized. For some of these compounds new synthetic routes had to be developed, especially for the az.b. monomers with a CO2H substituent (azoacids) where their synthesis, purification and (thermal)
International Nuclear Information System (INIS)
Luo Jianxin; Lu Mangeng; Yang Chaolong; Tong Bihai; Liang Liyan
2012-01-01
Two bipolar Alq 3 -based complexes, tris{5-[(carbazole-9'-yl)methyl]-8-hydroxyquinoline} aluminum (Al(CzHQ) 3 ) and tris{5-[(phenothiazine-9'-yl)methyl]-8-hydroxyquinoline} aluminum (Al(PHQ) 3 ), involving an Alq 3 -center and three hole-transporting substituents (carbazole or phenothiazine), were prepared and characterized. Effects of hole-transporting substituent on the properties of Alq 3 -center were investigated in detail. It is found that the two complexes have improved hole-transporting performance and appropriate thermal stability (the 5%-weight-loss temperatures T 5% >260 °C). Photoluminescence (PL) spectra indicate that both energy transfer and electron transfer can take place simultaneously in the PL process of these complexes. Both thermodynamics and dynamics of the electron transfer were studied and corresponding parameters were calculated. Energy transfer is favorable for the PL of Alq 3 -center, while electron transfer is unfavorable for the PL of Alq 3 -center. These results will be useful to explore novel OLEDs material with increased efficiency. - Highlights: ► Effects of substituent on the properties of Alq 3 -center were investigated. ► Energy transfer and electron transfer can transfer from substituent to Alq 3 -center. ► The thermodynamics and dynamics of electron transfer were studied. ► The mechanisms of PL and EL of Al(CzHQ) 3 were studied and compared with each other.
Guerra, C.F.; van der Wijst, T.; Bickelhaupt, F.M.
2006-01-01
We have theoretically analyzed Watson–Crick guanine–cytosine (GC) base pairs in which purine-C8 and/or pyrimidine-C6 positions carry a substituent X = NH−, NH2, NH3+ (N series), O−, OH, or OH2+ (O series), using the generalized gradient approximation (GGA) of density functional theory at the
Substituent Effects Dehalogenation of Aryl Bromides with NaAlH2(OCH2CH2OCH3)2
Czech Academy of Sciences Publication Activity Database
Czakoová, Marie; Hetflejš, Jiří; Včelák, Jaroslav
2001-01-01
Roč. 72, č. 2 (2001), s. 277-287 ISSN 0133-1736 R&D Projects: GA ČR GA203/97/1173 Institutional research plan: CEZ:AV0Z4072921 Keywords : substituent effects * aryl bromides * Co-assisted debromination Subject RIV: CC - Organic Chemistry Impact factor: 0.475, year: 2001
Czech Academy of Sciences Publication Activity Database
Zemánek, Jaroslav; Štěpnička, P.; Fejfarová, K.; Gyepes, R.; Císařová, I.; Horáček, Michal; Kubišta, Jiří; Varga, V.; Mach, Karel
2001-01-01
Roč. 66, č. 4 (2001), s. 605-620 ISSN 0010-0765 R&D Projects: GA AV ČR IBS4040017 Institutional research plan: CEZ:AV0Z4040901 Keywords : titanium * (amidocyclopentadienyl)dichlorotitanium(IV) complexes * substituent effects Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.778, year: 2001
2008-10-27
was repeated twice, dissolving the product in chloroform and diethyl ether, respectively. The polymer was dried at 60 °C under vacuum overnight...the Tg of the i Bu remains the same. Table 1. Tg for Butyl Methacrylate-co- Propyl Methacryl POSS Polymers with Various POSS Substituents
Varying Constants, Gravitation and Cosmology
Directory of Open Access Journals (Sweden)
Jean-Philippe Uzan
2011-03-01
Full Text Available Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.
Stabilized power constant alimentation; Alimentation regulee a puissance constante
Energy Technology Data Exchange (ETDEWEB)
Roussel, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires
1968-06-01
The study and realization of a stabilized power alimentation variable from 5 to 100 watts are described. In order to realize a constant power drift of Lithium compensated diodes, we have searched a 1 per cent precision of regulation and a response time minus than 1 sec. Recent components like Hall multiplicator and integrated amplifiers give this possibility and it is easy to use permutable circuits. (author) [French] On decrit l'etude et la realisation d'une alimentation a puissance constante reglable dans une gamme de 5 a 100 watts. Prevue pour le drift a puissance constante des diodes compensees au lithium, l'etude a ete menee en vue d'obtenir une precision de regulation de 1 pour cent et un temps de reponse inferieur a la seconde. Des systemes recents tels que multiplicateurs a effet Hall et circuits integres ont permis d'atteindre ce but tout en facilitant l'emploi de modules interchangeables. (auteur)
From the Rydberg constant to the fundamental constants metrology
International Nuclear Information System (INIS)
Nez, F.
2005-06-01
This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)
Learning Read-constant Polynomials of Constant Degree modulo Composites
DEFF Research Database (Denmark)
Chattopadhyay, Arkadev; Gavaldá, Richard; Hansen, Kristoffer Arnsfelt
2011-01-01
Boolean functions that have constant degree polynomial representation over a fixed finite ring form a natural and strict subclass of the complexity class \\textACC0ACC0. They are also precisely the functions computable efficiently by programs over fixed and finite nilpotent groups. This class...... is not known to be learnable in any reasonable learning model. In this paper, we provide a deterministic polynomial time algorithm for learning Boolean functions represented by polynomials of constant degree over arbitrary finite rings from membership queries, with the additional constraint that each variable...
Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2 H-azirines
Gómez-Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana L.; Pinho e Melo, Teresa M. V. D.; Fausto, Rui
2007-05-01
In this study, the UV induced photochemical reactions of two 2 H-azirines - methyl 2-chloro-3-methyl-2 H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2 H-azirine-2-carboxylate (MMAC) - isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) C sbnd C bond cleavage, with production of nitrile ylides (P1-type products), and (b) C sbnd N bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a C dbnd N +dbnd C - group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC. The C sbnd N photochemical cleavage is an unusual process in aliphatic 2 H-azirines. In the studied compounds, its preference over the commonly observed C sbnd C azirine-ring bond photocleavage is attributed to the presence of electron withdrawing substituents (methylcarboxy group in both azirines and also the chlorine atom in MCMAC), which accelerates intersystem crossing towards the triplet state from where the cleavage of the C sbnd N bond takes place. The lack of the chlorine atom in MMAC may be partially compensated by the significantly higher stabilization of the P2-type photoproduct derived from this molecule ( ca. -52 kJ mol -1) relatively to the reactant, when
Energy Technology Data Exchange (ETDEWEB)
Nez, F
2005-06-15
This document reviews the theoretical and experimental achievements of the author since the beginning of his scientific career. This document is dedicated to the spectroscopy of hydrogen, deuterium and helium atoms. The first part is divided into 6 sub-sections: 1) the principles of hydrogen spectroscopy, 2) the measurement of the 2S-nS/nD transitions, 3) other optical frequency measurements, 4) our contribution to the determination of the Rydberg constant, 5) our current experiment on the 1S-3S transition, 6) the spectroscopy of the muonic hydrogen. Our experiments have improved the accuracy of the Rydberg Constant by a factor 25 in 15 years and we have achieved the first absolute optical frequency measurement of a transition in hydrogen. The second part is dedicated to the measurement of the fine structure constant and the last part deals with helium spectroscopy and the search for optical references in the near infrared range. (A.C.)
Systematics of constant roll inflation
Anguelova, Lilia; Suranyi, Peter; Wijewardhana, L. C. R.
2018-02-01
We study constant roll inflation systematically. This is a regime, in which the slow roll approximation can be violated. It has long been thought that this approximation is necessary for agreement with observations. However, recently it was understood that there can be inflationary models with a constant, and not necessarily small, rate of roll that are both stable and compatible with the observational constraint ns ≈ 1. We investigate systematically the condition for such a constant-roll regime. In the process, we find a whole new class of inflationary models, in addition to the known solutions. We show that the new models are stable under scalar perturbations. Finally, we find a part of their parameter space, in which they produce a nearly scale-invariant scalar power spectrum, as needed for observational viability.
Strain fluctuations and elastic constants
Energy Technology Data Exchange (ETDEWEB)
Parrinello, M.; Rahman, A.
1982-03-01
It is shown that the elastic strain fluctuations are a direct measure of elastic compliances in a general anisotropic medium; depending on the ensemble in which the fluctuation is measured either the isothermal or the adiabatic compliances are obtained. These fluctuations can now be calculated in a constant enthalpy and pressure, and hence, constant entropy, ensemble due to recent develpments in the molecular dynamics techniques. A calculation for a Ni single crystal under uniform uniaxial 100 tensile or compressive load is presented as an illustration of the relationships derived between various strain fluctuations and the elastic modulii. The Born stability criteria and the behavior of strain fluctuations are shown to be related.
Energy Technology Data Exchange (ETDEWEB)
Li, Nan; Chen, Yong; Zhang, Ying-Ming; Wang, Li-Hua; Mao, Wen-Zhao; Liu, Yu, E-mail: yuliu@nankai.edu.cn
2014-01-20
Graphical abstract: - Highlights: • Different conformation of β-CD derivatives. • Enthalpy gain. • High binding ability. - Abstract: The molecular binding behaviors of two β-cyclodextrin (β-CD) derivatives bearing 1,2,3-triazole moieties, i.e. mono-6-deoxy-6-{4-(8-oxymethylquinolino)[1,2,3]triazolyl}-β-CD (1) and mono-6-deoxy-6-{4-(8-oxymethylnaphthol)[1,2,3]triazolyl}-β-CD (3), and their analogs without 1,2,3-triazole moieties, i.e. mono-6-deoxy-6-(8-oxymethylquinolino)-β-CD (2) and mono-6-deoxy-6-(8-oxymethylnaphthol)-β-CD (4) toward spherical guests (±)-borneol and (±)-camphor were investigated to elucidate how substituent moiety of host affects the binding abilities by 2D NMR as well as microcalorimetric titrations in aqueous phosphate buffer solution (pH 7.20) at 298.15 K. The binding modes of host–guest interactions obtained from 2D NMR displayed that host CDs without triazole moieties gave better induce-fit efficiency between hosts and guests, leading to stronger binding abilities. Thermodynamically, the inclusion complexation was driven by enthalpy with the stoichiometry of 1:1. Another factor contributed to the enhanced binding abilities was the enthalpy gain with the smaller entropy loss.
Influence of substituents in vinyl groups on reactivity of parylene during polymerization process
International Nuclear Information System (INIS)
Freza, Sylwia; Skurski, Piotr; Bobrowski, Maciej
2010-01-01
The MCSCF calculations indicate that both triplet and singlet state of biradical di-para-xylylene can exist during polymerization of parylene in gas phase and both can potentially react with vinyl molecules. The singlet-state open-shell dimer turned out to exhibit multiconfigurational character. In the case of triplet state of the dimer two mechanisms of the reactions with various species containing vinyl groups have been examined at the B3LYP/6-31G level. The kinetic and thermodynamical barriers have been estimated for the reaction path involving the π-bond cleavage as well as for the route describing the hydrogen atom transfer. It was found that the overall reactions are thermodynamically favorable, whereas appropriate kinetic barriers for certain derivatives are very small (close to 0 kcal/mol) which in turn makes allowances for easy reactivity under accessible conditions. The calculated mechanisms indicate the influence of substituents in vinyl groups for reactivity of parylene during LPCVD process.
Janprapa, Nuttaporn; Vchirawongkwin, Viwat; Kritayakornupong, Chinapong
2018-06-01
The structural, electronic and photovoltaic properties of furan-phenylene copolymer ((Fu-co-Ph)4) and its derivatives were evaluated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The calculated band gaps of pristine furan and phenylene are in good agreement with the available experimental data. The lower band gap value of 2.72 eV was obtained from -NO2 and -NHCH3 substituents, leading to broader solar absorption range. With respected to the reorganization energy, -OCH3, -NHCH3, -OH, -SCH3, -CH3, -CF3, -NO2, and -F substituted (Fu-co-Ph)4 structures were classified as better electron donor materials. For combination with PC61BM, -NO2, -CN, -CF3 and -F functionalized copolymers demonstrated significantly higher open circuit voltage (Voc) values ranging from 1.07 to 2.10 eV. Our results revealed that electron withdrawing group substitution on furan-phenylene copolymers was an effective way for improving electronic and optical properties of donor materials used in photovoltaic applications.
Influence of Introduced Substituents on the Anion-selectivity of [14]Tetraazaannulene Complexes.
Moriuchi-Kawakami, Takayo; Obita, Minako; Tsujinaka, Toshiki; Shibutani, Yasuhiko
2015-01-01
Nickel(II) complexes of [14]tetraazaannulene derivatives incorporating aromatic rings into their azaannulene framework were synthesized, and the anion-selectivity of the [14]tetraazaannulene nickel complexes 1 - 4 was evaluated by potentiometric measurements with solvent polymeric membrane electrodes. All of the [14]Tetraazaannulene nickel complexes, except 3, were found to exhibit high selectivity for the I(-) ion over the SCN(-) ion, although considerable interference of the ClO4(-) ion was observed in all 1 - 4 complexes. Concerning the anion-selectivities of 1 and 4, the incorporation of naphthalene rings into the azaannulene framework decreased not only the interference of the ClO4(-) ion but also the I(-) ion-selectivity over the SCN(-) ion. Comparison studies between the dibenzotetraaza[14]annulene nickel complexes 1 - 3 indicated that differences in the attached substituents of the [14]tetraazaannulene nickel complexes greatly influenced the ion-selectivity as ionophores. According to our computational results, the ionophoric properties of [14]tetraazaannulene nickel complexes 1 - 4 were influenced by their electrostatic properties rather than their topological properties.
International Nuclear Information System (INIS)
Popelis, Yu.Yu.; Liepin'sh, E.E.; Lukevits, E.Ya.
1986-01-01
The 1 H, 13 C, and 15 N NMR spectra of 15 N-enriched 5-substituted furfural oximes were investigated. It was shown that the chemical shifts of the ring atoms and the oxime group correlate satisfactorily with the F and R substituent constants, whereas their sensitivity to the effect of the substituents is lower than in monosubstituted furan derivatives. The constants of spin-spin coupling between the ring protons and the oxime group were determined. An analysis of the 1 H- 1 H spin-spin coupling constants (SSCC) on the basis of their stereospecificity indicates that the E isomers have primarily an s-trans conformation in polar dimethyl sulfoxide, whereas the Z isomers, on the other hand, have an s-cis conformation. The signs of the direct and geminal 13 C- 15 N SSCC were determined for 5-trimethylsilylfurfural oxime
International Nuclear Information System (INIS)
Adhikary, Keshab Kumar; Lee, Hai Whang
2011-01-01
Kinetic studies of the reactions of N-methyl-Y-α-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at 25.0 .deg. C. The Hammett plots for substituent X variations in the nucleophiles (log k N vs σ X ) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log k N vs pK a ) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log k N vs σ Y ) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant ρ XY values are all negative: ρ XY = -0.32 for X = Y = electron-donating: -0.22 for X = electron-withdrawing and Y = electron-donating: -1.80 for X = electron-donating and Y = electronwithdrawing: -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal (k H /k D > 1) for Y = electron-donating, while secondary inverse (k H /k D < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-α-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the α-carbon for Y = electronwithdrawing substituents
Universal relation between spectroscopic constants
Indian Academy of Sciences (India)
(3) The author has used eq. (6) of his paper to calculate De. This relation leads to a large deviation from the correct value depending upon the extent to which experimental values are known. Guided by this fact, in our work, we used experimentally observed De values to derive the relation between spectroscopic constants.
Tachyon constant-roll inflation
Mohammadi, A.; Saaidi, Kh.; Golanbari, T.
2018-04-01
The constant-roll inflation is studied where the inflaton is taken as a tachyon field. Based on this approach, the second slow-roll parameter is taken as a constant which leads to a differential equation for the Hubble parameter. Finding an exact solution for the Hubble parameter is difficult and leads us to a numerical solution for the Hubble parameter. On the other hand, since in this formalism the slow-roll parameter η is constant and could not be assumed to be necessarily small, the perturbation parameters should be reconsidered again which, in turn, results in new terms appearing in the amplitude of scalar perturbations and the scalar spectral index. Utilizing the numerical solution for the Hubble parameter, we estimate the perturbation parameter at the horizon exit time and compare it with observational data. The results show that, for specific values of the constant parameter η , we could have an almost scale-invariant amplitude of scalar perturbations. Finally, the attractor behavior for the solution of the model is presented, and we determine that the feature could be properly satisfied.
International Nuclear Information System (INIS)
Nadvornik, M.; Lycka, A.; Gee, A.; Popkov, A.
1999-01-01
The aim of this work was to study of influence of substituents on benzophenone substituent on thermodynamic controlled induction of complexes as well as influence of substituents on benzyl group and on benzophenone on kinetically controlled asymmetric induction of complexes. [ 13 C]methyl iodide was used in the synthesis. Replace of benzyl group by 2,4,6-trimethylbenzyl group increase kinetically controlled asymmetric induction of synthesis of (S)-α-[ 13 C]methylalanine from 43% d.e. to 66% d.e
International Nuclear Information System (INIS)
Vitullo, V.P.; Grabowski, J.; Sridharan, S.
1980-01-01
Rates and α-D isotope effects have been determined for the following substrates and nucleophiles: p-methoxybenzyl bromide (Et 3 N, SCN - , N 3 - , OH - , S 2 O 3 2- ), benzyl bromide (Et 3 N, SCN - , N 3 - , OH - , S 2 O 3 2- ), and p-nitrobenzyl bromide (Et 3 N, SCN - , N 3 - , S 2 O 3 2- ). In nearly all cases the second-order rate constant for each nucleophile goes through a minimum for the unsubstituted compound while the α-D isotope increases monotonically in the squence p-NO 2 > p-H > p-OCH 3 . These results are consistent with an increasing looseness of the S/sub N/2 transition state as the substituent on the aromatic ring becomes more electron donating. 4 figures, 3 tables
Substituent Effects on the Hydrogen Bonding between 4-Substituted Phenols and HF, H2O, NH3
Institute of Scientific and Technical Information of China (English)
程宇辉; 傅尧; 刘磊; 郭庆祥
2003-01-01
Density function theory UB3LYP/6-31+g(d) calculations were performed to study the hydrogen bonds between para-substituted phenols and HF, H2O, or NH3. It revealed that many properties of the non-covalent complexes, such as the interaction energies, donor-acceptor distances, bond lengths and vibration frequencies, showed well-defined substituent effects. Therefore, from the substituent effects not only the mechanism of a certain non-covalent interaction can be better understood, but also the interaction energies and structures of a certain non-covalent complex, which otherwise might be very hard or resource-consuming to estimate, can be easily predicted.
Stabilized power constant alimentation; Alimentation regulee a puissance constante
Energy Technology Data Exchange (ETDEWEB)
Roussel, L. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires
1968-06-01
The study and realization of a stabilized power alimentation variable from 5 to 100 watts are described. In order to realize a constant power drift of Lithium compensated diodes, we have searched a 1 per cent precision of regulation and a response time minus than 1 sec. Recent components like Hall multiplicator and integrated amplifiers give this possibility and it is easy to use permutable circuits. (author) [French] On decrit l'etude et la realisation d'une alimentation a puissance constante reglable dans une gamme de 5 a 100 watts. Prevue pour le drift a puissance constante des diodes compensees au lithium, l'etude a ete menee en vue d'obtenir une precision de regulation de 1 pour cent et un temps de reponse inferieur a la seconde. Des systemes recents tels que multiplicateurs a effet Hall et circuits integres ont permis d'atteindre ce but tout en facilitant l'emploi de modules interchangeables. (auteur)
Directory of Open Access Journals (Sweden)
Bruno Commare
2017-06-01
Full Text Available Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS onto heterocycles. In this context, fluoroalkyl amino reagents (FARs—a class of chemicals that was slightly forgotten over the last decades—has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (heteroaromatic derivatives.
Commare, Bruno; Schmitt, Etienne; Aribi, Fallia; Panossian, Armen; Vors, Jean-Pierre; Pazenok, Sergiy; Leroux, Frédéric R
2017-06-12
Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS) onto heterocycles. In this context, fluoroalkyl amino reagents (FARs)-a class of chemicals that was slightly forgotten over the last decades-has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (hetero)aromatic derivatives.
Arroyo-Currás, Netzahualcóyotl; Rosas-García, Víctor M; Videa, Marcelo
2016-10-27
Flavonoids are natural products commonly found in the human diet that show antioxidant, anti-inflammatory and anti-hepatotoxic activities. These nutraceutical properties may relate to the electrochemical activity of flavonoids. To increase the understanding of structure-electrochemical activity relations and the inductive effects that OH substituents have on the redox potential of flavonoids, we carried out square-wave voltammetry experiments and ab initio calculations of eight flavonoids selected following a systematic variation in the number of hydroxyl substituents and their location on the flavan backbone: three flavonols, three anthocyanidins, one anthocyanin and the flavonoid backbone flavone. We compared the effect that the number of -OH groups in the ring B of flavan has on the oxidation potential of the flavonoids considered, finding linear correlations for both flavonols and anthocyanidins ( R 2 = 0.98 ). We analyzed the effects that position and number of -OH substituents have on electron density distributions via ab initio quantum chemical calculations. We present direct correlations between structural features and oxidation potentials that provide a deeper insight into the redox chemistry of these molecules.
International Nuclear Information System (INIS)
Xia, Hong-qi; Hibino, Yuya; Kitazumi, Yuki; Shirai, Osamu; Kano, Kenji
2016-01-01
Highlights: • Methoxy-functionalized surface improves the DET-type bioelectrocatalysis of FDH. • Methoxy-functionalized surface increases productive orientations. • The total catalytic activity of FDH is almost independent of the modification. • High current density as well as good stability is useful for biofuel cells. - Abstract: D-Fructose dehydrogenase (FDH) from Gluconobacter japonicus NBRC3260 catalyzes the two-electron oxidation of D-fructose to 5-keto-D-fructose, and it is widely used in biofuel cells and biosensors. In this study, methoxy-substituent-functionalized carbon electrodes are constructed by electrochemical oxidation of methoxy-aniline derivatives on Ketjen Black (KB)-modified electrodes to improve the immobilization and bioelectrocatalysis of FDH. It is proposed that the specific interaction between FDH, especially the heme c moiety, and methoxy substituent(s) of amines on carbon electrode increases the proportion of the productively oriented FDH molecules to the total FDHs. Consequently, the limiting catalytic current density of the D-fructose oxidation increases to as much as 23 ± 2 mA cm −2 in FDH/2,4-dimethoxyaniline/KB/glassy carbon electrode, for example.
Evolution of the solar constant
International Nuclear Information System (INIS)
Newman, M.J.
1978-01-01
The ultimate source of the energy utilized by life on Earth is the Sun, and the behavior of the Sun determines to a large extent the conditions under which life originated and continues to thrive. What can be said about the history of the Sun. Has the solar constant, the rate at which energy is received by the Earth from the Sun per unit area per unit time, been constant at its present level since Archean times. Three mechanisms by which it has been suggested that the solar energy output can vary with time are discussed, characterized by long (approx. 10 9 years), intermediate (approx. 10 8 years), and short (approx. years to decades) time scales
Calculation of magnetic hyperfine constants
International Nuclear Information System (INIS)
Bufaical, R.F.; Maffeo, B.; Brandi, H.S.
1975-01-01
The magnetic hyperfine constants of the V sub(K) center in CaF 2 , SrF 2 and BaF 2 have been calculated assuming a phenomenological model, based on the F 2 - 'central molucule', to describe the wavefunction of the defect. Calculations have shown that introduction of a small degree of covalence, between this central molecule and neighboring ions, is necessary to improve the electronic structure description of the defect. It was also shown that the results for the hyperfine constants are strongly dependent on the relaxations of the ions neighboring the central molecule; these relaxations have been determined by fitting the experimental data. The present results are compared with other previous calculations where similar and different theoretical methods have been used
On the gravitational constant change
International Nuclear Information System (INIS)
Milyukov, V.K.
1986-01-01
The nowadays viewpoint on the problem of G gravitational constant invariability is presented in brief. The methods and results of checking of the G dependence on the nature of substance (checking of the equivalence principle), G dependepce on distance (checking of Newton gravity law) and time (cosmological experiments) are presented. It is pointed out that all performed experiments don't give any reasons to have doubts in G constancy in space and time and G independence on the nature of the substance
Photodissociation constant of NO2
International Nuclear Information System (INIS)
Nootebos, M.A.; Bange, P.
1992-01-01
The velocity of the dissociation of NO 2 into ozone and NO mainly depends on the ultraviolet sunlight quantity, and with that the cloudiness. A correct value for this reaction constant is important for the accurate modelling of O 3 - and NO 2 -concentrations in plumes of electric power plants, in particular in the case of determination of the amount of photochemical summer smog. An advanced signal processing method (deconvolution, correlation) was applied on the measurements. The measurements were carried out from aeroplanes
The unique role of halogen substituents in the design of modern agrochemicals.
Jeschke, Peter
2010-01-01
The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.
Pentiptycene-derived light-driven molecular brakes: substituent effects of the brake component.
Sun, Wei-Ting; Huang, Yau-Ting; Huang, Guan-Jhih; Lu, Hsiu-Feng; Chao, Ito; Huang, Shou-Ling; Huang, Shing-Jong; Lin, Ying-Chih; Ho, Jinn-Hsuan; Yang, Jye-Shane
2010-10-11
Five pentiptycene-derived stilbene systems (1 R; R = H, OM, NO, Pr, and Bu) have been prepared and investigated as light-driven molecular brakes that have different-sized brake components (1 Hbrake component in the trans form ((E)-1 R), which corresponds to the brake-off state. When the brake is turned on by photoisomerization to the cis form ((Z)-1 R), the pentiptycene rotation can be arrested on the NMR spectroscopic timescale at temperatures that depend on the brake component. In the cases of (Z)-1 NO, (Z)-1 Pr, and (Z)-1 Bu, the rotation is nearly blocked (k(rot)=2-6 s(-1)) at 298 K. It is also demonstrated that the rotation is slower in [D(6)]DMSO than in CD(2)Cl(2). A linear relationship between the free energies of the rotational barrier and the steric parameter A values is present only for (Z)-1 H, (Z)-1 OM, and (Z)-1 NO, and it levels off on going from (Z)-1 NO to (Z)-1 Pr and (Z)-1 Bu. DFT calculations provide insights into the substituent effects in the rotational ground and transition states. The molar reversibility of the E-Z photoswitching is up to 46%, and both the E and Z isomers are stable under the irradiation conditions. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Directory of Open Access Journals (Sweden)
Gholamreza Karimipour
2015-06-01
Full Text Available This work studied the synthesis of 5,10,15-tris(4-aminophenyl-20-(N,N-dialkyl/diaryl-N-phenylurea porphyrins (P1-P4 with alkyl or aryl groups of Ph, iPr, Et and Me, respectively and also the preparation of their manganese (III and cobalt (II complexes (MnP and CoP. The P1-P4 ligands were characterized by different spectroscopic techniques (1H NMR, FTIR, UV-Vis and elemental analysis, and metalated with Mn and Co acetate salts. The antibacterial and antifungal activities of these compounds in vitro were investigated by agar-disc diffusion method against Escherichia coli (-, Pseudomonas aeruginosa (-, Staphylococcus aureus(+, Bacillus subtilis (+ and Aspergillus oryzae and Candida albicans. Results showed that antibacterial and antifungal activity of the test samples increased with increase of their concentrations and the highest activity was obtained when the concentration of porphyrin compounds was 100 µg/mL. The activity for the porphyrin ligands depended on the nature of the urea derivative substituents and increased in the order P1 > P2 > P3 >P4, which was consistent with the order of their liposolubility. MnP and CoP complexes exhibited much higher antibacterial and antifungal activity than P1-P4ligands. Further, the growth inhibitory effects of these compounds was generally in the order CoP complexes > MnP complexes > P1-P4 ligands. Among these porphyrin compounds, CoP1displayed the highest antibacterial and antifungal activity, especially with a concentration of 100 µg/mL, against all the four tested bacteria and two fungi, and therefore it could be potential to be used as drug.
Gieseking, Rebecca L.
2014-11-25
Polymethine dyes in dilute solutions display many of the optical properties required for all-optical switching applications. However, in thin films, aggregation and polymethine-counterion interactions can substantially modify their properties and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum-chemical calculations. Importantly, it is found that the positions of the substituents near the center and/or ends of the dye determine the extent to which aggregation is reduced; in particular, substituents near the polymethine center primarily modify the type of aggregation that is observed, while substituents near the polymethine ends reduce aggregation and aid in maintaining solution-like properties in the solid state. Our theoretical study elucidates relationships between molecular structure and bulk optical properties and provides design guidelines for all-optical switching materials.
Gieseking, Rebecca L.; Mukhopadhyay, Sukrit; Risko, Chad; Marder, Seth R.; Bredas, Jean-Luc
2014-01-01
and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum
Directory of Open Access Journals (Sweden)
Volodymyr V. Tkachenko
2014-12-01
Full Text Available The switchable three-component reactions of 5-amino-3-methylisoxazole, salicylaldehyde and N-aryl-3-oxobutanamides under different conditions were studied and discussed. The unexpected influence of the aryl substituent in N-aryl-3-oxobutanamides on the behavior of the reaction was discovered. The key influence of ultrasonication and Lewis acid catalysts led to an established protocol to selectively obtain two or three types of heterocyclic scaffolds depending on the substituent in the N-aryl moiety.
Fine-structure constant: Is it really a constant
International Nuclear Information System (INIS)
Bekenstein, J.D.
1982-01-01
It is often claimed that the fine-structure ''constant'' α is shown to be strictly constant in time by a variety of astronomical and geophysical results. These constrain its fractional rate of change alpha-dot/α to at least some orders of magnitude below the Hubble rate H 0 . We argue that the conclusion is not as straightforward as claimed since there are good physical reasons to expect alpha-dot/α 0 . We propose to decide the issue by constructing a framework for a variability based on very general assumptions: covariance, gauge invariance, causality, and time-reversal invariance of electromagnetism, as well as the idea that the Planck-Wheeler length (10 -33 cm) is the shortest scale allowable in any theory. The framework endows α with well-defined dynamics, and entails a modification of Maxwell electrodynamics. It proves very difficult to rule it out with purely electromagnetic experiments. In a cosmological setting, the framework predicts an alpha-dot/α which can be compatible with the astronomical constraints; hence, these are too insensitive to rule out α variability. There is marginal conflict with the geophysical constraints: however, no firm decision is possible because of uncertainty about various cosmological parameters. By contrast the framework's predictions for spatial gradients of α are in fatal conflict with the results of the Eoetvoes-Dicke-Braginsky experiments. Hence these tests of the equivalence principle rule out with confidence spacetime variability of α at any level
Chandra Independently Determines Hubble Constant
2006-08-01
A critically important number that specifies the expansion rate of the Universe, the so-called Hubble constant, has been independently determined using NASA's Chandra X-ray Observatory. This new value matches recent measurements using other methods and extends their validity to greater distances, thus allowing astronomers to probe earlier epochs in the evolution of the Universe. "The reason this result is so significant is that we need the Hubble constant to tell us the size of the Universe, its age, and how much matter it contains," said Max Bonamente from the University of Alabama in Huntsville and NASA's Marshall Space Flight Center (MSFC) in Huntsville, Ala., lead author on the paper describing the results. "Astronomers absolutely need to trust this number because we use it for countless calculations." Illustration of Sunyaev-Zeldovich Effect Illustration of Sunyaev-Zeldovich Effect The Hubble constant is calculated by measuring the speed at which objects are moving away from us and dividing by their distance. Most of the previous attempts to determine the Hubble constant have involved using a multi-step, or distance ladder, approach in which the distance to nearby galaxies is used as the basis for determining greater distances. The most common approach has been to use a well-studied type of pulsating star known as a Cepheid variable, in conjunction with more distant supernovae to trace distances across the Universe. Scientists using this method and observations from the Hubble Space Telescope were able to measure the Hubble constant to within 10%. However, only independent checks would give them the confidence they desired, considering that much of our understanding of the Universe hangs in the balance. Chandra X-ray Image of MACS J1149.5+223 Chandra X-ray Image of MACS J1149.5+223 By combining X-ray data from Chandra with radio observations of galaxy clusters, the team determined the distances to 38 galaxy clusters ranging from 1.4 billion to 9.3 billion
Cryptography in constant parallel time
Applebaum, Benny
2013-01-01
Locally computable (NC0) functions are 'simple' functions for which every bit of the output can be computed by reading a small number of bits of their input. The study of locally computable cryptography attempts to construct cryptographic functions that achieve this strong notion of simplicity and simultaneously provide a high level of security. Such constructions are highly parallelizable and they can be realized by Boolean circuits of constant depth.This book establishes, for the first time, the possibility of local implementations for many basic cryptographic primitives such as one-way func
Low power constant fraction discriminator
International Nuclear Information System (INIS)
Krishnan, Shanti; Raut, S.M.; Mukhopadhyay, P.K.
2001-01-01
This paper describes the design of a low power ultrafast constant fraction discriminator, which significantly reduces the power consumption. A conventional fast discriminator consumes about 1250 MW of power whereas this low power version consumes about 440 MW. In a multi detector system, where the number of discriminators is very large, reduction of power is of utmost importance. This low power discriminator is being designed for GRACE (Gamma Ray Atmospheric Cerenkov Experiments) telescope where 1000 channels of discriminators are required. A novel method of decreasing power consumption has been described. (author)
Can coupling constants be related
International Nuclear Information System (INIS)
Nandi, Satyanarayan; Ng, Wing-Chiu.
1978-06-01
We analyze the conditions under which several coupling constants in field theory can be related to each other. When the relation is independent of the renormalization point, the relation between any g and g' must satisfy a differential equation as follows from the renormalization group equations. Using this differential equation, we investigate the criteria for the feasibility of a power-series relation for various theories, especially the Weinberg-Salam type (including Higgs bosons) with an arbitrary number of quark and lepton flavors. (orig./WL) [de
Exact constants in approximation theory
Korneichuk, N
1991-01-01
This book is intended as a self-contained introduction for non-specialists, or as a reference work for experts, to the particular area of approximation theory that is concerned with exact constants. The results apply mainly to extremal problems in approximation theory, which in turn are closely related to numerical analysis and optimization. The book encompasses a wide range of questions and problems: best approximation by polynomials and splines; linear approximation methods, such as spline-approximation; optimal reconstruction of functions and linear functionals. Many of the results are base
Hydrodynamic constants from cosmic censorship
International Nuclear Information System (INIS)
Nakamura, Shin
2008-01-01
We study a gravity dual of Bjorken flow of N=4 SYM-theory plasma. We point out that the cosmic censorship hypothesis may explain why the regularity of the dual geometry constrains the hydrodynamic constants. We also investigate the apparent horizon of the dual geometry. We find that the dual geometry constructed on Fefferman-Graham (FG) coordinates is not appropriate for examination of the apparent horizon since the coordinates do not cover the trapped region. However, the preliminary analysis on FG coordinates suggests that the location of the apparent horizon is very sensitive to the hydrodynamic parameters. (author)
Energy Technology Data Exchange (ETDEWEB)
Dostanić, J., E-mail: jasmina@nanosys.ihtm.bg.ac.rs [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and Chemical Engineering, Njegoševa 12, 11000 Belgrade (Serbia); Lončarević, D. [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and Chemical Engineering, Njegoševa 12, 11000 Belgrade (Serbia); Zlatar, M. [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Department of Chemistry, Njegoševa 12, 11000 Belgrade (Serbia); Vlahović, F. [University of Belgrade, Innovation center of the Faculty of Chemistry, 11000 Belgrade (Serbia); Jovanović, D.M. [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and Chemical Engineering, Njegoševa 12, 11000 Belgrade (Serbia)
2016-10-05
Highlights: • Electronic effects of para substituted arylazo pyridone dyes. • Linear relationship between Hammett σ{sub p} constants and dyes photoreactivity. • The photocatalytic reactions facilitated by el.-acceptors and retarded by el.-donors. • Fukui functions to analyze the reactivity on concurrent sites within a molecule. • Hydroxyl radicals sustain attack from two reaction sites, depending on a substituent type. - Abstract: A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31 + G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σ{sub p} constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO{sub 2} photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups.
International Nuclear Information System (INIS)
Dostanić, J.; Lončarević, D.; Zlatar, M.; Vlahović, F.; Jovanović, D.M.
2016-01-01
Highlights: • Electronic effects of para substituted arylazo pyridone dyes. • Linear relationship between Hammett σ_p constants and dyes photoreactivity. • The photocatalytic reactions facilitated by el.-acceptors and retarded by el.-donors. • Fukui functions to analyze the reactivity on concurrent sites within a molecule. • Hydroxyl radicals sustain attack from two reaction sites, depending on a substituent type. - Abstract: A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31 + G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σ_p constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO_2 photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups.
Relaxing a large cosmological constant
International Nuclear Information System (INIS)
Bauer, Florian; Sola, Joan; Stefancic, Hrvoje
2009-01-01
The cosmological constant (CC) problem is the biggest enigma of theoretical physics ever. In recent times, it has been rephrased as the dark energy (DE) problem in order to encompass a wider spectrum of possibilities. It is, in any case, a polyhedric puzzle with many faces, including the cosmic coincidence problem, i.e. why the density of matter ρ m is presently so close to the CC density ρ Λ . However, the oldest, toughest and most intriguing face of this polyhedron is the big CC problem, namely why the measured value of ρ Λ at present is so small as compared to any typical density scale existing in high energy physics, especially taking into account the many phase transitions that our Universe has undergone since the early times, including inflation. In this Letter, we propose to extend the field equations of General Relativity by including a class of invariant terms that automatically relax the value of the CC irrespective of the initial size of the vacuum energy in the early epochs. We show that, at late times, the Universe enters an eternal de Sitter stage mimicking a tiny positive cosmological constant. Thus, these models could be able to solve the big CC problem without fine-tuning and have also a bearing on the cosmic coincidence problem. Remarkably, they mimic the ΛCDM model to a large extent, but they still leave some characteristic imprints that should be testable in the next generation of experiments.
Formas estructurales de fuerza constante
Directory of Open Access Journals (Sweden)
Zalewski, Waclaw
1963-05-01
Full Text Available The author seeks to prove the need to obtain the most essential form in the various types of structures by applying a number of rational principles, of which the constant stress principle is one of the most decisive. The structural form should be a logical consequence of all its functional circumstances, and this requires a clear understanding of the general behaviour of each part of the structure, and also of the main stresses which operate on it, considered as a unitary whole. To complete his theoretical argument, the author gives some examples, in the design of which the criterion of constant stress has been adopted. The author considers the various aspects which are involved in obtaining a structural design that satisfies given functional and aesthetic requirements. In doing so he refers to his personal experience within Poland, and infers technical principles of general validity which should determine the rational design of the form, as an integrated aspect of the structural pattern. The projects which illustrate this paper are Polish designs of undoubted constructive significance, in which the principle of constant stress has been applied. Finally the author condenses his whole theory in a simple and straightforward practical formula, which should be followed if a truly rational form is to be achieved: the constancy of stress in the various structural elements.El autor se esfuerza en mostrar la necesidad de llegar a la forma real en las distintas estructuras siguiendo una serie de principios racionales, entre los que domina el criterio de la fuerza constante. La forma ha de ser una consecuencia lógica en todos sus aspectos, y esto exige un claro conocimiento del comportamiento general de cada una de las partes de la estructura, y de los esfuerzos generales que dominan en la misma al considerarla como un todo. Para completar la exposición de orden teórico, el autor presenta algunos ejemplos en cuyo proyecto se ha seguido el criterio de
Constant Proportion Debt Obligations (CPDOs)
DEFF Research Database (Denmark)
Cont, Rama; Jessen, Cathrine
2012-01-01
be made arbitrarily small—and thus the credit rating arbitrarily high—by increasing leverage, but the ratings obtained strongly depend on assumptions on the credit environment (high spread or low spread). More importantly, CPDO loss distributions are found to exhibit a wide range of tail risk measures......Constant Proportion Debt Obligations (CPDOs) are structured credit derivatives that generate high coupon payments by dynamically leveraging a position in an underlying portfolio of investment-grade index default swaps. CPDO coupons and principal notes received high initial credit ratings from...... the major rating agencies, based on complex models for the joint transition of ratings and spreads for all names in the underlying portfolio. We propose a parsimonious model for analysing the performance of CPDO strategies using a top-down approach that captures the essential risk factors of the CPDO. Our...
Energy, stability and cosmological constant
International Nuclear Information System (INIS)
Deser, S.
1982-01-01
The definition of energy and its use in studying stability in general relativity are extended to the case when there is a nonvanishing cosmological constant Λ. Existence of energy is first demonstrated for any model (with arbitrary Λ). It is defined with respect to sets of solutions tending asymptotically to any background space possessing timelike Killing symmetry, and is both conserved and of flux integral form. When Λ O, small excitations about De Sitter space are stable inside the event horizon. Outside excitations can contribute negatively due to the Killing vector's flip at the horizon. This is a universal phenomenon associated with the possibility of Hawking radiation. Apart from this effect, the Λ>O theory appears to be stable, also at the semi-classical level. (author)
Filament instability under constant loads
Monastra, A. G.; Carusela, M. F.; D’Angelo, M. V.; Bruno, L.
2018-04-01
Buckling of semi-flexible filaments appears in different systems and scales. Some examples are: fibers in geophysical applications, microtubules in the cytoplasm of eukaryotic cells and deformation of polymers freely suspended in a flow. In these examples, instabilities arise when a system’s parameter exceeds a critical value, being the Euler force the most known. However, the complete time evolution and wavelength of buckling processes are not fully understood. In this work we solve analytically the time evolution of a filament under a constant compressive force in the small amplitude approximation. This gives an insight into the variable force scenario in terms of normal modes. The evolution is highly sensitive to the initial configuration and to the magnitude of the compressive load. This model can be a suitable approach to many different real situations.
Evolution of the solar 'constant'
Energy Technology Data Exchange (ETDEWEB)
Newman, M J
1980-06-01
Variations in solar luminosity over geological time are discussed in light of the effect of the solar constant on the evolution of life on earth. Consideration is given to long-term (5 - 7% in a billion years) increases in luminosity due to the conversion of hydrogen into helium in the solar interior, temporary enhancements to solar luminosity due to the accretion of matter from the interstellar medium at intervals on the order of 100 million years, and small-amplitude rapid fluctuations of luminosity due to the stochastic nature of convection on the solar surface. It is noted that encounters with dense interstellar clouds could have had serious consequences for life on earth due to the peaking of the accretion-induced luminosity variation at short wavelengths.
Asympotics with positive cosmological constant
Bonga, Beatrice; Ashtekar, Abhay; Kesavan, Aruna
2014-03-01
Since observations to date imply that our universe has a positive cosmological constant, one needs an extension of the theory of isolated systems and gravitational radiation in full general relativity from the asymptotically flat to asymptotically de Sitter space-times. In current definitions, one mimics the boundary conditions used in asymptotically AdS context to conclude that the asymptotic symmetry group is the de Sitter group. However, these conditions severely restricts radiation and in fact rules out non-zero flux of energy, momentum and angular momentum carried by gravitational waves. Therefore, these formulations of asymptotically de Sitter space-times are uninteresting beyond non-radiative spacetimes. The situation is compared and contrasted with conserved charges and fluxes at null infinity in asymptotically flat space-times.
The fundamental constants a mystery of physics
Fritzsch, Harald
2009-01-01
The speed of light, the fine structure constant, and Newton's constant of gravity — these are just three among the many physical constants that define our picture of the world. Where do they come from? Are they constant in time and across space? In this book, physicist and author Harald Fritzsch invites the reader to explore the mystery of the fundamental constants of physics in the company of Isaac Newton, Albert Einstein, and a modern-day physicist
Study on effect of substituents in α positron of N,N-diethylamides by nuclear magnetic resonance
International Nuclear Information System (INIS)
Martins, M.A.P.
1982-01-01
The effect of a substituent in the α position of some N,N-diethylamides, through the 1 H and 13 C n.m.r. spectroscopy is studied. Eight N,N-diethylamides having the structure: Y-CH 2 -C(O) - NEt 2 , where Y=H, Me, Cl, Br, I, OMe, SMe, and NMe 2 were prepared by usual procedures; all these compounds were characterized by their 1 H and 13 C n.m.r. and infrared spectra, as well as by their elementary analysis. (M.J.C.) [pt
Directory of Open Access Journals (Sweden)
Qingqiang Tian
2017-11-01
Full Text Available A selective and practical bromine–metal exchange on bromoheterocyclics bearing substituents with an acidic proton under non-cryogenic conditions was developed by a simple modification of an existing protocol. Our protocol of using a combination of i-PrMgCl and n-BuLi has not only solved the problem of intermolecular quenching that often occurred when using alkyl lithium alone as the reagent for halogen–lithium exchange, but also offered a highly selective method for performing bromo–metal exchange on dibrominated arene compounds through chelation effect.
Directory of Open Access Journals (Sweden)
Seiya Nagao
2011-12-01
Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.
Eseola, Abiodun O.; Obi-Egbedi, Nelson O.
2010-02-01
New 2-(1H-imidazol-2-yl)phenols ( L1Et- L8tBuPt) bearing a phenolic proton in the vicinity of the imidazole base were prepared and characterized. Experimental studies of the dependence of their protonation/deprotonation equilibrium on substituent identities and intramolecular hydrogen bonding tendencies were carried out using electronic absorption spectroscopy at varying pH values. In order to make comparison, 2-(anthracen-10-yl)-4,5-diphenyl-1H-imidazole ( L9Anthr) bearing no phenolic proton and 4,5-diphenyl-2-(4,5-diphenyl-1H-imidazol-2-yl)-1H-imidazole ( L10BisIm) bearing two symmetrical imidazole base fragments were also prepared and experimentally investigated. DFT calculations were carried out to study frontier orbitals of the investigated molecules. While electron-releasing substituents produced increase in protonation-deprotonation p Kas for the hydroxyl group, values for the imidazole base were mainly affected by polarization of the imidazole ring aromaticity across the 2-imidazole carbon and the 4,5-imidazole carbons axis of the imidazole ring. It was concluded that electron-releasing substituents on the phenol ring and/or electron-withdrawing substituents on 4,5-imidazole carbons negatively affects donor strengths/coordination chemistries of 2-(1H-imidazol-2-yl)phenols, and vice versa. Change of substituents on the phenol ring significantly altered the donor strength of the imidazole base. The understanding of p Ka variation on account of electronic effects of substituents in this work should aid the understanding of biochemical properties and substituent environments of imidazole-containing biomacromolecules.
Effect of Cl substituent in the aromatic tetracycline ring on its reactivity with solvated electrons
Energy Technology Data Exchange (ETDEWEB)
Dziegielewski, J O; Glowacki, P [Universytet Slaski, Katowice (Poland). Inst. Chemii; Goracy, J; Orlowska-Dudek, D; Sloma, E [Wroclaw Univ. (Poland) Inst. Chemii
1984-09-18
Decomposition yields of tetracycline hydrochloride (TC.HCl) and chlorotetracycline hydrochloride (ClTC.HCl) in methanol solution saturated with Ar or N/sub 2/O were determined. Rate constants of the reaction esub(s)/sup -/ with some antibiotics were obtained. It was demonstrated by /sup 1/H NMR that the radical formed by degradation of 7-C-Cl group is recombined with the H atoms leading to ClTC.HCl being converted into tetracycline hydrochloride (TC.HCl).
International Nuclear Information System (INIS)
Kim, Young Cheul; Lim, Jong Wan; Choi, Sung Yong; Kim, Se Kyong
1999-01-01
The reaction rates of substituted quinolines(6-CH 3 C 9 H 7 N, C 9 H 7 N) with p-substituted benzoylchlorides(p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15, 20, 25 .deg. C) and pressures(1, 200, 500, 1000bar). From the values of rate constants, the activation parameters(Ea, ΔV ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increase as a function of temperatures and pressures, and are further increase by introduction the electron donor substituents in nucleophile(p-CH 3 ) or electron acceptor(p-NO 2 ) substituents in substrate. The activation volume, and the activation entropy are all negative. Hammett ρ values are also negative for nucleophile (ρ X ) and positive for the substrate (ρ Y ) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in which bond formation favored with increasing pressures
Arrhenius Rate: constant volume burn
Energy Technology Data Exchange (ETDEWEB)
Menikoff, Ralph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2017-12-06
A constant volume burn occurs for an idealized initial state in which a large volume of reactants at rest is suddenly raised to a high temperature and begins to burn. Due to the uniform spatial state, there is no fluid motion and no heat conduction. This reduces the time evolu tion to an ODE for the reaction progress variable. With an Arrhenius reaction rate, two characteristics of thermal ignition are illustrated: induction time and thermal runaway. The Frank-Kamenetskii approximation then leads to a simple expression for the adiabatic induction time. For a first order reaction, the analytic solution is derived and used to illustrate the effect of varying the activation temperature; in particular, on the induction time. In general, the ODE can be solved numerically. This is used to illustrate the effect of varying the reaction order. We note that for a first order reaction, the time evolution of the reaction progress variable has an exponential tail. In contrast, for a reaction order less than one, the reaction completes in a nite time. The reaction order also affects the induction time.
Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu
2005-05-30
A family of diruthenium complexes with ligand-unsupported Ru-Ru bonds has been systematically synthesized, and their crystal structures and physical properties have been examined. A simple, useful reaction between Ru2(OAc)4Cl (OAc- = acetate) and catechol derivatives in the presence of bases afforded a variety of diruthenium complexes, generally formulated as [Na(n){Ru2(R4Cat)4}] (n = 2 or 3; R4 = -F4, -Cl4, -Br4, -H4, -3,5-di-t-Bu, and -3,6-di-t-Bu; Cat(2-) = catecholate). The most characteristic feature of the complexes is the formation of short ligand-unsupported Ru-Ru bonds (2.140-2.273 A). These comprehensive studies were carried out to evaluate the effects of the oxidation states and the substituents governing the molecular structures and physicochemical properties. The Ru-Ru bond distances, rotational conformations, and bending structures of the complexes were successfully varied. The results presented in this manuscript clearly demonstrate that the complexes with ligand-unsupported Ru-Ru bonds can sensitively respond to redox reactions and ligand substituents on the basis of the greater degree of freedom in their molecular structures.
Yang, Wenjing; Chen, Xuebo
2014-03-07
A combined approach of the multiconfigurational perturbation theory with the Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of excited state intra-molecular proton transfer (ESIPT) for the WOLED material molecule of HBFO and its four meta- or para-substituted compounds in gas phase, acetonitrile and cyclohexane solvents. The kinetic control for these reactions is quantitatively determined and extensively studied on the basis of the accurate potential energy surfaces when the thermodynamic factor associated with the free energy change becomes negligible in the case of the existence of a significant barrier in the ESIPT process. These computational efforts contribute to a deep understanding of the ESIPT mechanism, dual emission characteristics, kinetic controlling factor, substituent and solvent effects for these material molecules. The white light emission is generated by the establishment of dynamic equilibrium between enol and keto forms in the charge transfer excited SCT((1)ππ*) state. The performance of white light emission is quantitatively demonstrated to be mainly sensitive to the molecular tailoring approach of the electronic properties of meta- or para- substituents by the modulation of the forward/backward ESIPT rate ratio. The quality of white light emission is slightly tunable through its surrounding solvent environment. These computational results will provide a useful strategy for the molecular design of OLED and WOLED materials.
Capacitive Cells for Dielectric Constant Measurement
Aguilar, Horacio Munguía; Maldonado, Rigoberto Franco
2015-01-01
A simple capacitive cell for dielectric constant measurement in liquids is presented. As an illustrative application, the cell is used for measuring the degradation of overheated edible oil through the evaluation of their dielectric constant.
The Dielectric Constant of Lubrication Oils
National Research Council Canada - National Science Library
Carey, A
1998-01-01
The values of the dielectric constant of simple molecules is discussed first, along with the relationship between the dielectric constant and other physical properties such as boiling point, melting...
Globally Coupled Chaotic Maps with Constant Force
International Nuclear Information System (INIS)
Li Jinghui
2008-01-01
We investigate the motion of the globally coupled maps (logistic map) with a constant force. It is shown that the constant force can cause multi-synchronization for the globally coupled chaotic maps studied by us.
STABILITY CONSTANT OF THE TRISGLYCINATO METAL ...
African Journals Online (AJOL)
DR. AMINU
overall stability constants of the complexes were found to be similar. Keywords: Glycinato, titration ... +. −. = 1 where Ka = dissociation constant of the amino acid. [ ]+. H = concentration of the .... Synthesis and techniques in inorganic chemistry.
Influence of fluorine substituents on the NMR properties of phenylboronic acids.
Gierczyk, Błażej; Kaźmierczak, Marcin; Popenda, Łukasz; Sporzyński, Andrzej; Schroeder, Grzegorz; Jurga, Stefan
2014-05-01
The paper presents results of a systematic NMR studies on fluorinated phenylboronic acids. All possible derivatives were studied. The experimental (1)H, (13)C, (19)F, (11)B, and (17)O spectral data were compared with the results of theoretical calculations. The relation between the calculated natural bond orbital parameters and spectral data (chemical shifts and coupling constants) is discussed. The first examples of (10)B/(11)B isotopic effect on the (19)F spectra and (4)JFO scalar coupling in organic compounds are reported. Copyright © 2014 John Wiley & Sons, Ltd.
Directory of Open Access Journals (Sweden)
I. JURANIC
2000-11-01
Full Text Available The pKa values for a series of eight p-substituted trans-2,3-epoxy-4-phenyl butanoic acids (p-substituted trans-b-aroylepoxyacrylic acids have been determined potentiometrically in aqueous media at 25°C at an ionic strength of 0.1 mol/dm3 (NaCl. The transmission of polar effects from the substituents on the phenyl nucleus to the carboxylic group through the side chain involving a carbonyl group and an epoxide ring was investigated. The pKa values were correlated with structure using the Hammett, Taft and Yukawa-Tsuno approaches. The Hammett r constant (0.34 was compared with analogue values for structurally similar acids.
Mojica, Martha; Méndez, Francisco; Alonso, Julio A
2016-02-12
The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.
Directory of Open Access Journals (Sweden)
Matthias Zeller
2014-09-01
Full Text Available The structure of the title compound, C14H15ClN2O4, prepared by reaction of a methacryloyl dimer with nitroaniline, was determined to establish the relative substituent orientation on the cyclopentanone ring. In agreement with an earlier proposed reaction mechanism, the amide group and the methyl group adjacent to the chloro substituent adopt equatorial positions and relative cis orientation, whereas the Cl substituent itself and the methyl group adjacent to the amide have axial orientations relative to the mean plane of the five-membered ring. The conformation of the molecule is stabilized by one classical N—H...O (2.18 Å and one non-classical C—H...O (2.23 Å hydrogen bond, each possessing an S(6 graph-set motif. The crystal packing is defined by several non-classical intramolecular hydrogen bonds, as well as by partial stacking of the aromatic rings.
Tam, Annie; Gotoh, Hiroaki; Robertson, William M.; Boger, Dale L.
2010-01-01
The examination of the catharanthine C16 substituent effects on the Fe(III)-promoted biomimetic coupling reaction with vindoline is detailed, confirming the importance of the presence of a C16 electron-withdrawing substituent, and establishing an unanticipated unique role (>10-fold) that the C16 methyl ester plays in the expression of the natural product properties. Thus, replacement of the vinblastine C16′ methyl ester with an ethyl ester (10-fold), a cyano group (100-fold), an aldehyde (100-fold), a hydroxymethyl group (1000-fold), or a primary carboxamide (>1000-fold) led to surprisingly large reductions in cytotoxic activity. PMID:20932748
Directory of Open Access Journals (Sweden)
Tatiana S. Chmilenko
2014-03-01
Full Text Available The interaction of 5 anionic xanthene dyes – 9-R-2,3,7-trihydroxy-6-fluorones (ТОF with cationic polyelectrolyte (PE – polyhexamethyleneguanidine chloride (PHMG has been studied by the optical spectroscopy in a concentration range where PHMG has a polyelectrolyte effect. Hammet σ-constants were calculated. The correlations between structure of ТОF and shift of protolytic equilibrium in aqueous-polyelectrolyte solutions were established. Influence of рН, concentration of the ethanol, components ratio in the system PHMG-TOF on the character of the interaction of cationic PE with ТОF and value of the analytical signal were studied based on absorption spectra. The results were compared to those obtained in water solutions.
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.
La Regina, Giuseppe; Coluccia, Antonio; Brancale, Andrea; Piscitelli, Francesco; Gatti, Valerio; Maga, Giovanni; Samuele, Alberta; Pannecouque, Christophe; Schols, Dominique; Balzarini, Jan; Novellino, Ettore; Silvestri, Romano
2011-03-24
New indolylarylsulfone derivatives bearing cyclic substituents at indole-2-carboxamide linked through a methylene/ethylene spacer were potent inhibitors of the WT HIV-1 replication in CEM and PBMC cells with inhibitory concentrations in the low nanomolar range. Against the mutant L100I and K103N RT HIV-1 strains in MT-4 cells, compounds 20, 24-26, 36, and 40 showed antiviral potency superior to that of NVP and EFV. Against these mutant strains, derivatives 20, 24-26, and 40 were equipotent to ETV. Molecular docking experiments on this novel series of IAS analogues have also suggested that the H-bond interaction between the nitrogen atom in the carboxamide chain of IAS and Glu138:B is important in the binding of these compounds. These results are in accordance with the experimental data obtained on the WT and on the mutant HIV-1 strains tested.
CODATA recommended values of the fundamental constants
International Nuclear Information System (INIS)
Mohr, Peter J.; Taylor, Barry N.
2000-01-01
A review is given of the latest Committee on Data for Science and Technology (CODATA) adjustment of the values of the fundamental constants. The new set of constants, referred to as the 1998 values, replaces the values recommended for international use by CODATA in 1986. The values of the constants, and particularly the Rydberg constant, are of relevance to the calculation of precise atomic spectra. The standard uncertainty (estimated standard deviation) of the new recommended value of the Rydberg constant, which is based on precision frequency metrology and a detailed analysis of the theory, is approximately 1/160 times the uncertainty of the 1986 value. The new set of recommended values as well as a searchable bibliographic database that gives citations to the relevant literature is available on the World Wide Web at physics.nist.gov/constants and physics.nist.gov/constantsbib, respectively
Substituent effects on dynamics at conical intersections: Allene and methyl allenes
Energy Technology Data Exchange (ETDEWEB)
Neville, Simon P. [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Wang, Yanmei [State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China); Boguslavskiy, Andrey E.; Stolow, Albert, E-mail: albert.stolow@nrc-cnrc.gc.ca [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa ON K1N 6N5 (Canada); Schuurman, Michael S., E-mail: michael.schuurman@nrc-cnrc.gc.ca [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada)
2016-01-07
We report a joint experimental and theoretical study on the ultrafast excited state dynamics of allene and a series of its methylated analogues (1,2-butadiene, 1,1-dimethylallene, and tetramethylallene) in order to elucidate the conical intersection mediated dynamics that give rise to ultrafast relaxation to the ground electronic state. We use femtosecond time-resolved photoelectron spectroscopy (TRPES) to probe the coupled electronic-vibrational dynamics following UV excitation at 200 nm (6.2 eV). Ab initio multiple spawning (AIMS) simulations are employed to determine the mechanistic details of two competing dynamical pathways to the ground electronic state. In all molecules, these pathways are found to involve as follows: (i) twisting about the central allenic C–C–C axis followed by pyramidalization at one of the terminal carbon atoms and (ii) bending of allene moiety. Importantly, the AIMS trajectory data were used for ab initio simulations of the TRPES, permitting direct comparison with experiment. For each molecule, the decay of the TRPES signal is characterized by short (30 fs, 52 fs, 23 fs) and long (1.8 ps, 3.5 ps, [306 fs, 18 ps]) time constants for 1,2-butadiene, 1,1-dimethylallene, and tetramethylallene, respectively. However, AIMS simulations show that these time constants are only loosely related to the evolution of electronic character and actually more closely correlate to large amplitude motions on the electronic excited state, modulating the instantaneous vertical ionization potentials. Furthermore, the fully substituted tetramethylallene is observed to undergo qualitatively different dynamics, as displacements involving the relatively massive methyl groups impede direct access to the conical intersections which give rise to the ultrafast relaxation dynamics observed in the other species. These results show that the branching between the “twisting” and “bending” pathways can be modified via the selective methylation of the terminal
Structural, magnetic and electrical properties of Zr-substitued NiZnCo ferrite nanopowders
Energy Technology Data Exchange (ETDEWEB)
Li, Le-Zhong, E-mail: lezhongli@cuit.edu.cn; Zhong, Xiao-Xi; Wang, Rui; Tu, Xiao-Qiang
2017-08-01
Highlights: • The static magnetic properties of NiZnCoZr ferrite nanopowders have been investigated. • The dielectric constant increases with the increase of Zr substitution. • The relaxation peak of tan δ ∼ T curves is observed for x ≥ 0.10. • Electrical transport behavior is found to follow the impurity semiconductor. • The dc resistivity increases at transition temperature with Zr substitution. - Abstract: Zr-substituted NiZnCo ferrite nanopowders, Ni{sub 0.4−x}Zn{sub 0.5}Zr{sub x}Co{sub 0.1}Fe{sub 2.0}O{sub 4} (0 ≤ x ≤ 0.20), were synthesized by the sol-gel auto-combustion method. The effects of Zr substitution on the structural, magnetic and electrical properties have been investigated. The DTA and TG results indicate that there are three steps of combustion process. The X-ray diffraction patterns show that the lattice parameter and the average crystallite size increase with the increase of Zr substitution. The saturation magnetization increases with the increase of Zr substitution when x ≤ 0.05, and then decreases when x > 0.05. Meanwhile, the coercivity initially decreases with the increase of Zr substitution when x ≤ 0.05, and then increases when x > 0.05. The polarization behavior for all the samples in the test frequency range from100 Hz to10 MHz obeys the charge polarization mechanism, which happens since the frequency of the hopping of electron exchange between Fe{sup 2+} and Fe{sup 3+} ions are far from the frequency of alternating-current field. And the dielectric constant increases with the increase of Zr substitution. The relaxation peak of the frequency dependence of dielectric loss is observed for x ≥ 0.10, which is due to the frequency of charge hopping between the Fe{sup 2+} and Fe{sup 3+} exactly matches with the frequency of the external applied field. Electrical transport behavior of the ferrite nanopowders is found to follow the impurity semiconductor, and the effect of Zr substitution on the temperature dependence
Stability constants of scandium complexes, 1
International Nuclear Information System (INIS)
Itoh, Hisako; Itoh, Naomi; Suzuki, Yasuo
1984-01-01
The stability constants of scandium complexes with some carboxylate ligands were determined potentiometrically at 25.0 and 40.0 0 C and at an ionic strength of 0.10 with potassium nitrate as supporting electrolyte. The constants of the scandium complexes were appreciably greater than those of the corresponding lanthanoid complexes, as expected. The changes in free energy, enthalpy, and entropy for the formation of the scandium complexes were calculated from the stability constants at two temperatures. (author)
Constant exposure technique in industrial radiography
International Nuclear Information System (INIS)
Domanus, J.C.
1983-08-01
The principles and advantages of the constant exposure technique are explained. Choice of exposure factors is analyzed. Film, paper and intensifying screens used throughout the investigation and film and paper processing are described. Exposure technique and the use of image quality indicators are given. Methods of determining of radiographic image quality are presented. Conclusions about the use of constant exposure vs. constant kilovoltage technique are formulated. (author)
Dose rate constants for new dose quantities
International Nuclear Information System (INIS)
Tschurlovits, M.; Daverda, G.; Leitner, A.
1992-01-01
Conceptual changes and new quantities made is necessary to reassess dose rate quantities. Calculations of the dose rate constant were done for air kerma, ambient dose equivalent and directional dose equivalent. The number of radionuclides is more than 200. The threshold energy is selected as 20 keV for the dose equivalent constants. The dose rate constant for the photon equivalent dose as used mainly in German speaking countries as a temporary quantity is also included. (Author)
Dias, Jerry Ray; Gao, Hongwu
2009-12-01
The 13C NMR spectra of over 24 tetracyclic triterpenoid derivatives have been structurally analyzed. The 13C NMR chemical shifts allow one to probe the steric topology of the rigid steroid skeleton and inductive effects of its substituents. Use of deuterium labeling in chemical shift assignment and B-ring aromatic terpenoids are also featured.
Alem, van K.; Belder, G.; Lodder, G.; Zuilhof, H.
2005-01-01
The photochemical reactions in methanol of the vinylic halides 1-4, halostyrenes with a methyl or a trifluoromethyl substituent at the - or -position, have been investigated quantitatively. Next to E/Z isomerization, the reactions are formation of vinyl radicals, leading to reductive dehalogenation
International Nuclear Information System (INIS)
Dubonosov, A.D.; Rybalkin, V.P.; Tsukanov, A.V.; Minkin, V.I.; Popova, L.L.; Revinsky, Y.V.; Bren, V.A.; Minkin, V.I.
2009-01-01
Synthesis and properties of photo chromic acylated 2-(N-arylaminomethylene)benzo[b]thiophene-3(2H)-ones are described. Their structure largely depends on the nature of acyl migrant and in a less degree on N-aryl substituent.
A natural cosmological constant from chameleons
International Nuclear Information System (INIS)
Nastase, Horatiu; Weltman, Amanda
2015-01-01
We present a simple model where the effective cosmological constant appears from chameleon scalar fields. For a Kachru–Kallosh–Linde–Trivedi (KKLT)-inspired form of the potential and a particular chameleon coupling to the local density, patches of approximately constant scalar field potential cluster around regions of matter with density above a certain value, generating the effect of a cosmological constant on large scales. This construction addresses both the cosmological constant problem (why Λ is so small, yet nonzero) and the coincidence problem (why Λ is comparable to the matter density now)
A natural cosmological constant from chameleons
Directory of Open Access Journals (Sweden)
Horatiu Nastase
2015-07-01
Full Text Available We present a simple model where the effective cosmological constant appears from chameleon scalar fields. For a Kachru–Kallosh–Linde–Trivedi (KKLT-inspired form of the potential and a particular chameleon coupling to the local density, patches of approximately constant scalar field potential cluster around regions of matter with density above a certain value, generating the effect of a cosmological constant on large scales. This construction addresses both the cosmological constant problem (why Λ is so small, yet nonzero and the coincidence problem (why Λ is comparable to the matter density now.
A natural cosmological constant from chameleons
Energy Technology Data Exchange (ETDEWEB)
Nastase, Horatiu, E-mail: nastase@ift.unesp.br [Instituto de Física Teórica, UNESP-Universidade Estadual Paulista, R. Dr. Bento T. Ferraz 271, Bl. II, Sao Paulo 01140-070, SP (Brazil); Weltman, Amanda, E-mail: amanda.weltman@uct.ac.za [Astrophysics, Cosmology & Gravity Center, Department of Mathematics and Applied Mathematics, University of Cape Town, Private Bag, Rondebosch 7700 (South Africa)
2015-07-30
We present a simple model where the effective cosmological constant appears from chameleon scalar fields. For a Kachru–Kallosh–Linde–Trivedi (KKLT)-inspired form of the potential and a particular chameleon coupling to the local density, patches of approximately constant scalar field potential cluster around regions of matter with density above a certain value, generating the effect of a cosmological constant on large scales. This construction addresses both the cosmological constant problem (why Λ is so small, yet nonzero) and the coincidence problem (why Λ is comparable to the matter density now)
Sarangapani, Radhakrishnan; Reddy, Sreekantha T; Sikder, Arun K
2015-04-01
Molecular dynamics simulations studies are carried out on hydroxyl terminated polyethers that are useful in energetic polymeric binder applications. Energetic polymers derived from oxetanes with heterocyclic side chains with different energetic substituents are designed and simulated under the ensembles of constant particle number, pressure, temperature (NPT) and constant particle number, volume, temperature (NVT). Specific volume of different amorphous polymeric models is predicted using NPT-MD simulations as a function of temperature. Plots of specific volume versus temperature exhibited a characteristic change in slope when amorphous systems change from glassy to rubbery state. Several material properties such as Young's, shear, and bulk modulus, Poisson's ratio, etc. are predicted from equilibrated structures and established the structure-property relations among designed polymers. Energetic performance parameters of these polymers are calculated and results reveal that the performance of the designed polymers is comparable to the benchmark energetic polymers like polyNIMMO, polyAMMO and polyBAMO. Overall, it is worthy remark that this molecular simulations study on novel energetic polyethers provides a good guidance on mastering the design principles and allows us to design novel polymers of tailored properties. Copyright © 2015 Elsevier Inc. All rights reserved.
Directory of Open Access Journals (Sweden)
Andreas Gansäuer
2013-08-01
Full Text Available The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and that a combination of electrophilic radicals with preferably nucleophilic arenes results in the highest rate constants. This is opposite to the Minisci reaction where the radical acts as nucleophile and the arene as electrophile. The substitution at the N-atom of the aniline is crucial. Methyl substitution leads to slower addition than phenyl substitution. Carbamates as substituents are suitable only when the radical center is not too electrophilic. No correlations between free reaction barriers and energies (ΔG‡ and ΔGR are found. Addition reactions leading to indanes or dihydrobenzofurans are too slow to be useful synthetically.
Accurate core-electron binding energy shifts from density functional theory
International Nuclear Information System (INIS)
Takahata, Yuji; Marques, Alberto Dos Santos
2010-01-01
Current review covers description of density functional methods of calculation of accurate core-electron binding energy (CEBE) of second and third row atoms; applications of calculated CEBEs and CEBE shifts (ΔCEBEs) in elucidation of topics such as: hydrogen-bonding, peptide bond, polymers, DNA bases, Hammett substituent (σ) constants, inductive and resonance effects, quantitative structure activity relationship (QSAR), and solid state effect (WD). This review limits itself to works of mainly Chong and his coworkers for the period post-2002. It is not a fully comprehensive account of the current state of the art.
Equilibrium-constant expressions for aqueous plutonium
International Nuclear Information System (INIS)
Silver, G.L.
2010-01-01
Equilibrium-constant expressions for Pu disproportionation reactions traditionally contain three or four terms representing the concentrations or fractions of the oxidation states. The expressions can be rewritten so that one of the oxidation states is replaced by a term containing the oxidation number of the plutonium. Experimental estimations of the numerical values of the constants can then be checked in several ways. (author)
A null test of the cosmological constant
International Nuclear Information System (INIS)
Chiba, Takeshi; Nakamura, Takashi
2007-01-01
We provide a consistency relation between cosmological observables in general relativity with the cosmological constant. Breaking of this relation at any redshift would imply the breakdown of the hypothesis of the cosmological constant as an explanation of the current acceleration of the universe. (author)
A stringy nature needs just two constants
International Nuclear Information System (INIS)
Veneziano, G.
1986-01-01
Dual string theories of everything, being purely geometrical, contain only two fundamental constants: c, for relativistic invariance, and a length lambda, for quantization. Planck's and Newton's constants appear only through Planck's length, a ''calculable'' fraction of lambda. Only the existence of a light sector breaks a ''reciprocity'' principle and unification at lambda, which is also the theory's cut-off
On special relativity with cosmological constant
International Nuclear Information System (INIS)
Guo Hanying; Huang Chaoguang; Xu Zhan; Zhou Bin
2004-01-01
Based on the principle of relativity and the postulate of invariant speed and length, we propose the theory of special relativity with cosmological constant SRc,R, in which the cosmological constant is linked with the invariant length. Its relation with the doubly special relativity is briefly mentioned
DETERMINATION OF STABILITY CONSTANTS OF MANGANESE (II ...
African Journals Online (AJOL)
DR. AMINU
Keywords: Amino acids, dissociation constant, potentiometry, stability constant. INTRODUCTION. Acids – base titration involves the gradual addition or removal of protons for example using the deprotic form of glycine. The plot has two distinct stages corresponding to the deprotonation of the two different groups on glycine.
Shapley Value for Constant-sum Games
Khmelnitskaya, A.B.
2002-01-01
It is proved that Young's axiomatization for the Shapley value by marginalism, efficiency, and symmetry is still valid for the Shapley value defined on the class of nonnegative constant-sum games and on the entire class of constant-sum games as well. To support an interest to study the class of
Constant Width Planar Computation Characterizes ACC0
DEFF Research Database (Denmark)
Hansen, Kristoffer Arnsfelt
2006-01-01
We obtain a characterization of ACC0 in terms of a natural class of constant width circuits, namely in terms of constant width polynomial size planar circuits. This is shown via a characterization of the class of acyclic digraphs which can be embedded on a cylinder surface in such a way that all...
Experimental Determination of the Avogadro Constant
Indian Academy of Sciences (India)
mental physical constant such as charge of an electron or the. Boltzmann constant ... ideas was that the number of particles or molecules in a gas of given volume could not ... knowledge of at least one property of a single molecule. Loschmidt ...
The time constant of the somatogravic illusion.
Correia Grácio, B J; de Winkel, K N; Groen, E L; Wentink, M; Bos, J E
2013-02-01
Without visual feedback, humans perceive tilt when experiencing a sustained linear acceleration. This tilt illusion is commonly referred to as the somatogravic illusion. Although the physiological basis of the illusion seems to be well understood, the dynamic behavior is still subject to discussion. In this study, the dynamic behavior of the illusion was measured experimentally for three motion profiles with different frequency content. Subjects were exposed to pure centripetal accelerations in the lateral direction and were asked to indicate their tilt percept by means of a joystick. Variable-radius centrifugation during constant angular rotation was used to generate these motion profiles. Two self-motion perception models were fitted to the experimental data and were used to obtain the time constant of the somatogravic illusion. Results showed that the time constant of the somatogravic illusion was on the order of two seconds, in contrast to the higher time constant found in fixed-radius centrifugation studies. Furthermore, the time constant was significantly affected by the frequency content of the motion profiles. Motion profiles with higher frequency content revealed shorter time constants which cannot be explained by self-motion perception models that assume a fixed time constant. Therefore, these models need to be improved with a mechanism that deals with this variable time constant. Apart from the fundamental importance, these results also have practical consequences for the simulation of sustained accelerations in motion simulators.
Zero cosmological constant from normalized general relativity
International Nuclear Information System (INIS)
Davidson, Aharon; Rubin, Shimon
2009-01-01
Normalizing the Einstein-Hilbert action by the volume functional makes the theory invariant under constant shifts in the Lagrangian. The associated field equations then resemble unimodular gravity whose otherwise arbitrary cosmological constant is now determined as a Machian universal average. We prove that an empty space-time is necessarily Ricci tensor flat, and demonstrate the vanishing of the cosmological constant within the scalar field paradigm. The cosmological analysis, carried out at the mini-superspace level, reveals a vanishing cosmological constant for a universe which cannot be closed as long as gravity is attractive. Finally, we give an example of a normalized theory of gravity which does give rise to a non-zero cosmological constant.
Graviton fluctuations erase the cosmological constant
Wetterich, C.
2017-10-01
Graviton fluctuations induce strong non-perturbative infrared renormalization effects for the cosmological constant. The functional renormalization flow drives a positive cosmological constant towards zero, solving the cosmological constant problem without the need to tune parameters. We propose a simple computation of the graviton contribution to the flow of the effective potential for scalar fields. Within variable gravity, with effective Planck mass proportional to the scalar field, we find that the potential increases asymptotically at most quadratically with the scalar field. The solutions of the derived cosmological equations lead to an asymptotically vanishing cosmological "constant" in the infinite future, providing for dynamical dark energy in the present cosmological epoch. Beyond a solution of the cosmological constant problem, our simplified computation also entails a sizeable positive graviton-induced anomalous dimension for the quartic Higgs coupling in the ultraviolet regime, substantiating the successful prediction of the Higgs boson mass within the asymptotic safety scenario for quantum gravity.
Solar constant values for estimating solar radiation
International Nuclear Information System (INIS)
Li, Huashan; Lian, Yongwang; Wang, Xianlong; Ma, Weibin; Zhao, Liang
2011-01-01
There are many solar constant values given and adopted by researchers, leading to confusion in estimating solar radiation. In this study, some solar constant values collected from literature for estimating solar radiation with the Angstroem-Prescott correlation are tested in China using the measured data between 1971 and 2000. According to the ranking method based on the t-statistic, a strategy to select the best solar constant value for estimating the monthly average daily global solar radiation with the Angstroem-Prescott correlation is proposed. -- Research highlights: → The effect of the solar constant on estimating solar radiation is investigated. → The investigation covers a diverse range of climate and geography in China. → A strategy to select the best solar constant for estimating radiation is proposed.
Găină, Luiza; Csámpai, Antal; Túrós, György; Lovász, Tamás; Zsoldos-Mády, Virág; Silberg, Ioan A; Sohár, Pál
2006-12-07
A series of novel 3(5)-aryl/ferrocenyl-5(3)-phenothiazinylpyrazoles and pyrazolines were obtained by substituent-dependent regioselective condensation of the corresponding (E)-3-(2-alkyl-10H-phenothiazin-3-yl)-1-aryl/ferrocenylprop-2-en-1-one with hydrazine or methylhydrazine in acetic acid. The different propensity of the primary formed beta-hydrazino adducts to undergo competitive retro-Mannich reaction was interpreted in terms of tautomerisation equilibrium constants calculated by DFT using a solvent model. The regioselectivity of the cyclisation reactions with methylhydrazine and the substituent-dependent redox properties of pyrazolines were also rationalized by comparative DFT calculations performed for simplified model molecules. On the effect of ultrasound-promoted oxidation with copper(II)nitrate phenothiazine-containing pyrazolines, enones and oxo-compounds were selectively transformed into sulfoxides. Only one sulfoxide enone was partially converted into an oxirane derivative. The structure of the novel products was determined by IR and NMR spectroscopy including COSY, HSQC, HMBC and DNOE measurements.
Directory of Open Access Journals (Sweden)
K. Ranganathan
2014-05-01
Full Text Available Some aryl-aryl 1H pyrazoles have been synthesised by cyclization of aryl chalcones and hydrazine hydrate in the presence of SOCl2. The yields of the pyrazoles are more than 85%. These pyrazoles are characterized by their physical constants and spectral data. The infrared, NMR spectral group frequencies of these pyrazolines have been correlated with Hammett substituent constants, F and R parameters. From the results of statistical analyses the effects of substituent on the spectral frequencies have been studied. The antimicrobial activities of all synthesised pyrazolines have been studied using Bauer-Kirby method. DOI: http://dx.doi.org/10.4314/bcse.v28i2.11
Directory of Open Access Journals (Sweden)
R. Suresh
2015-07-01
Full Text Available Some azomethines including substituted benzylidene-4-chlorobenzenamines (E-imines have been synthesized by fly-ash: PTS catalyzed microwave assisted condensation of 4-chloroaniline and substituted benzaldehydes under solvent-free conditions. The yield of the imines has been found to be more than 85%. The purity of all imines has been checked using their physical constants and UV, IR and NMR spectral data. These spectral data have been correlated with Hammett substituent constants and F and R parameters using single and multi-linear regression analysis. From the results of statistical analysis, the effect of substituents on the above spectral data has been studied. The antimicrobial activities of all imines have been studied using standard methods.
Energy Technology Data Exchange (ETDEWEB)
Zhang, Qing; Li, Yuanyuan; Wang, Xin; Wang, Li, E-mail: chemwangl@henu.edu.cn; Zhang, Jinglai, E-mail: zhangjinglai@henu.edu.cn
2016-07-01
Four iridium(III) complexes, (dfpmpy){sub 2}Ir(pic), (1), (dfpmpy){sub 2}Ir(EO{sub 2}-pic) (2), (dfpmpy){sub 2}Ir(pic-N-O) (3), and (dfpmpy){sub 2}Ir(EO{sub 2}-pic-N-O) (4) (dfpmpy = 2-(2,4-difluorophenyl)-4-methylpyridine, pic = picolinic acid, EO{sub 2}-pic = 4-(2-ethoxyethoxy) picolinic acid, pic-N-O = picolinic acid N-oxide, and EO{sub 2}-pic-N-O = 4-(2-ethoxyethoxy) picolinic acid N-oxide) are investigated by means of the density functional theory/time-dependent density functional theory (DFT/TD-DFT) to explore the influence of the ancillary ligand on the electronic structures, phosphorescent properties, and organic light-emitting diode (OLED) performance. Employing pic-N-O and EO{sub 2}-pic-N-O as the ancillary ligands would decrease the vertical energy and result in the red-shifted wavelength. Then, other four iridium(III) complexes (2a-2d) (See Scheme 1) are designed by introduction of the phenyl and −CHO substituents on the pyridine ring and phenyl ring of complex 2, respectively. As compared with complex 2, theoretical results show that newly designed complexes 2a-2c might be potential candidates for blue-emitting phosphors with better/comparable quantum yield and Δλ. Moreover, the performance of complexes 2a and 2c, i.e., introducing phenyl on the para-position of pyridine ring and phenyl ring in dfpmpy ligand, are better than that of 2b. - Highlights: • The structure-property relationship of Ir(III) complexes are investigated. • The effect of different substituents/positions on properties is explored. • Do the emissions follow the Kasha or non-Kasha scenario? • Newly possible blue-emitting Ir(III) complexes are theoretically designed.
Higashino, Tomohiro; Kawamoto, Kyosuke; Sugiura, Kenichi; Fujimori, Yamato; Tsuji, Yukihiro; Kurotobi, Kei; Ito, Seigo; Imahori, Hiroshi
2016-06-22
To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.
Energy Technology Data Exchange (ETDEWEB)
Huynh, Mioy T.; Anson, Colin W.; Cavell, Andrew C.; Stahl, Shannon S.; Hammes-Schiffer, Sharon
2016-11-10
Quinones participate in diverse electron transfer and proton-coupled electron transfer processes in chemistry and biology. An experimental study of common quinones reveals a non-linear correlation between the 1 e^{–} and 2 e^{–}/2 H^{+} reduction potentials. This unexpected observation prompted a computational study of 128 different quinones, probing their 1 e^{–} reduction potentials, pKa values, and 2 e^{–}/2 H^{+} reduction potentials. The density functional theory calculations reveal an approximately linear correlation between these three properties and an effective Hammett constant associated with the quinone substituent(s). However, deviations from this linear scaling relationship are evident for quinones that feature halogen substituents, charged substituents, intramolecular hydrogen bonding in the hydroquinone, and/or sterically bulky substituents. These results, particularly the different substituent effects on the 1 e^{–} versus 2 e^{–} /2 H^{+} reduction potentials, have important implications for designing quinones with tailored redox properties.
Energy Technology Data Exchange (ETDEWEB)
Goodman, A L [Tulane Univ., New Orleans, LA (United States)
1992-08-01
Statistical orientation fluctuations are calculated with two alternative assumptions: the rotational frequency remains constant as the shape orientation fluctuates; and, the average angular momentum remains constant as the shape orientation fluctuates. (author). 2 refs., 3 figs.
On the constants for some Sobolev imbeddings
Directory of Open Access Journals (Sweden)
Pizzocchero Livio
2001-01-01
Full Text Available We consider the imbedding inequality is the Sobolev space (or Bessel potential space of type and (integer or fractional order . We write down upper bounds for the constants , using an argument previously applied in the literature in particular cases. We prove that the upper bounds computed in this way are in fact the sharp constants if , , and exhibit the maximising functions. Furthermore, using convenient trial functions, we derive lower bounds on for in many cases these are close to the previous upper bounds, as illustrated by a number of examples, thus characterizing the sharp constants with little uncertainty.
On the constant-roll inflation
Yi, Zhu; Gong, Yungui
2018-03-01
The primordial power spectra of scalar and tensor perturbations during slow-roll inflation are usually calculated with the method of Bessel function approximation. For constant-roll or ultra slow-roll inflation, the method of Bessel function approximation may be invalid. We compare the numerical results with the analytical results derived from the Bessel function approximation, and we find that they differ significantly on super-horizon scales if the constant slow-roll parameter ηH is not small. More accurate method is needed for calculating the primordial power spectrum for constant-roll inflation.
Scalar-tensor cosmology with cosmological constant
International Nuclear Information System (INIS)
Maslanka, K.
1983-01-01
The equations of scalar-tensor theory of gravitation with cosmological constant in the case of homogeneous and isotropic cosmological model can be reduced to dynamical system of three differential equations with unknown functions H=R/R, THETA=phi/phi, S=e/phi. When new variables are introduced the system becomes more symmetrical and cosmological solutions R(t), phi(t), e(t) are found. It is shown that when cosmological constant is introduced large class of solutions which depend also on Dicke-Brans parameter can be obtained. Investigations of these solutions give general limits for cosmological constant and mean density of matter in plane model. (author)
Cosmological constant and advanced gravitational wave detectors
International Nuclear Information System (INIS)
Wang, Y.; Turner, E.L.
1997-01-01
Interferometric gravitational wave detectors could measure the frequency sweep of a binary inspiral (characterized by its chirp mass) to high accuracy. The observed chirp mass is the intrinsic chirp mass of the binary source multiplied by (1+z), where z is the redshift of the source. Assuming a nonzero cosmological constant, we compute the expected redshift distribution of observed events for an advanced LIGO detector. We find that the redshift distribution has a robust and sizable dependence on the cosmological constant; the data from advanced LIGO detectors could provide an independent measurement of the cosmological constant. copyright 1997 The American Physical Society
Constant strength fuel-fuel cell
International Nuclear Information System (INIS)
Vaseen, V.A.
1980-01-01
A fuel cell is an electrochemical apparatus composed of both a nonconsumable anode and cathode; and electrolyte, fuel oxidant and controls. This invention guarantees the constant transfer of hydrogen atoms and their respective electrons, thus a constant flow of power by submergence of the negative electrode in a constant strength hydrogen furnishing fuel; when said fuel is an aqueous absorbed hydrocarbon, such as and similar to ethanol or methnol. The objective is accomplished by recirculation of the liquid fuel, as depleted in the cell through specific type membranes which pass water molecules and reject the fuel molecules; thus concentrating them for recycle use
Reactor group constants and benchmark test
Energy Technology Data Exchange (ETDEWEB)
Takano, Hideki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment
2001-08-01
The evaluated nuclear data files such as JENDL, ENDF/B-VI and JEF-2 are validated by analyzing critical mock-up experiments for various type reactors and assessing applicability for nuclear characteristics such as criticality, reaction rates, reactivities, etc. This is called Benchmark Testing. In the nuclear calculations, the diffusion and transport codes use the group constant library which is generated by processing the nuclear data files. In this paper, the calculation methods of the reactor group constants and benchmark test are described. Finally, a new group constants scheme is proposed. (author)
Canonoid transformations and constants of motion
International Nuclear Information System (INIS)
Negri, L.J.; Oliveira, L.C.; Teixeira, J.M.
1986-01-01
The necessary and sufficient conditions for a canonoid transformation with respect to a given Hamiltonian are obtained in terms of the Lagrange brackets of the trasformation. The relation of these conditions with the constants of motion is discussed. (Author) [pt
An improved dosimeter having constant flow pump
International Nuclear Information System (INIS)
Baker, W.B.
1980-01-01
A dosemeter designed for individual use which can be used to monitor toxic radon gas and toxic related products of radon gas in mines and which incorporates a constant air stream flowing through the dosimeter is described. (U.K.)
Interacting universes and the cosmological constant
International Nuclear Information System (INIS)
Alonso-Serrano, A.; Bastos, C.; Bertolami, O.; Robles-Pérez, S.
2013-01-01
In this Letter it is studied the effects that an interaction scheme among universes can have in the values of their cosmological constants. In the case of two interacting universes, the value of the cosmological constant of one of the universes becomes very close to zero at the expense of an increasing value of the cosmological constant of the partner universe. In the more general case of a chain of N interacting universes with periodic boundary conditions, the spectrum of the Hamiltonian splits into a large number of levels, each of them associated with a particular value of the cosmological constant, that can be occupied by single universes revealing a collective behavior that plainly shows that the multiverse is much more than the mere sum of its parts
Interacting universes and the cosmological constant
Energy Technology Data Exchange (ETDEWEB)
Alonso-Serrano, A. [Centro de Física “Miguel Catalán”, Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 121, 28006 Madrid (Spain); Estación Ecológica de Biocosmología, Pedro de Alvarado 14, 06411 Medellín (Spain); Bastos, C. [Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Avenida Rovisco Pais 1, 1049-001 Lisboa (Portugal); Bertolami, O. [Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Avenida Rovisco Pais 1, 1049-001 Lisboa (Portugal); Departamento de Física e Astronomia, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Robles-Pérez, S., E-mail: salvarp@imaff.cfmac.csic.es [Centro de Física “Miguel Catalán”, Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 121, 28006 Madrid (Spain); Estación Ecológica de Biocosmología, Pedro de Alvarado 14, 06411 Medellín (Spain); Física Teórica, Universidad del País Vasco, Apartado 644, 48080 Bilbao (Spain)
2013-02-12
In this Letter it is studied the effects that an interaction scheme among universes can have in the values of their cosmological constants. In the case of two interacting universes, the value of the cosmological constant of one of the universes becomes very close to zero at the expense of an increasing value of the cosmological constant of the partner universe. In the more general case of a chain of N interacting universes with periodic boundary conditions, the spectrum of the Hamiltonian splits into a large number of levels, each of them associated with a particular value of the cosmological constant, that can be occupied by single universes revealing a collective behavior that plainly shows that the multiverse is much more than the mere sum of its parts.
Constant conditional entropy and related hypotheses
International Nuclear Information System (INIS)
Ferrer-i-Cancho, Ramon; Dębowski, Łukasz; Moscoso del Prado Martín, Fermín
2013-01-01
Constant entropy rate (conditional entropies must remain constant as the sequence length increases) and uniform information density (conditional probabilities must remain constant as the sequence length increases) are two information theoretic principles that are argued to underlie a wide range of linguistic phenomena. Here we revise the predictions of these principles in the light of Hilberg’s law on the scaling of conditional entropy in language and related laws. We show that constant entropy rate (CER) and two interpretations for uniform information density (UID), full UID and strong UID, are inconsistent with these laws. Strong UID implies CER but the reverse is not true. Full UID, a particular case of UID, leads to costly uncorrelated sequences that are totally unrealistic. We conclude that CER and its particular cases are incomplete hypotheses about the scaling of conditional entropies. (letter)
New perspectives on constant-roll inflation
Cicciarella, Francesco; Mabillard, Joel; Pieroni, Mauro
2018-01-01
We study constant-roll inflation using the β-function formalism. We show that the constant rate of the inflaton roll is translated into a first order differential equation for the β-function which can be solved easily. The solutions to this equation correspond to the usual constant-roll models. We then construct, by perturbing these exact solutions, more general classes of models that satisfy the constant-roll equation asymptotically. In the case of an asymptotic power law solution, these corrections naturally provide an end to the inflationary phase. Interestingly, while from a theoretical point of view (in particular in terms of the holographic interpretation) these models are intrinsically different from standard slow-roll inflation, they may have phenomenological predictions in good agreement with present cosmological data.
Hydrolysis and formation constants at 250C
International Nuclear Information System (INIS)
Phillips, S.L.
1982-05-01
A database consisting of hydrolysis and formation constants for about 20 metals associated with the disposal of nuclear waste is given. Complexing ligands for the various ionic species of these metals include OH, F, Cl, SO 4 , PO 4 and CO 3 . Table 1 consists of tabulated calculated and experimental values of log K/sub xy/, mainly at 25 0 C and various ionic strengths together with references to the origin of the data. Table 2 consists of a column of recommended stability constants at 25 0 C and zero ionic strength tabulated in the column headed log K/sub xy/(0); other columns contain coefficients for an extended Debye-Huckel equation to permit calculations of stability constants up to 3 ionic strength, and up to 0.7 ionic strength using the Davies equation. Selected stability constants calculated with these coefficients for various ionic strengths agree to an average of +- 2% when compared with published experimental and calculated values
Wormholes and the cosmological constant problem.
Klebanov, I.
The author reviews the cosmological constant problem and the recently proposed wormhole mechanism for its solution. Summation over wormholes in the Euclidean path integral for gravity turns all the coupling parameters into dynamical variables, sampled from a probability distribution. A formal saddle point analysis results in a distribution with a sharp peak at the cosmological constant equal to zero, which appears to solve the cosmological constant problem. He discusses the instabilities of the gravitational Euclidean path integral and the difficulties with its interpretation. He presents an alternate formalism for baby universes, based on the "third quantization" of the Wheeler-De Witt equation. This approach is analyzed in a minisuperspace model for quantum gravity, where it reduces to simple quantum mechanics. Once again, the coupling parameters become dynamical. Unfortunately, the a priori probability distribution for the cosmological constant and other parameters is typically a smooth function, with no sharp peaks.
Feng, Yujie; Wang, Chao; Tian, Xiangge; Huo, Xiaokui; Feng, Lei; Sun, Chengpeng; Ge, Guangbo; Yang, Ling; Ning, Jing; Ma, Xiaochi
2017-09-01
Bufadienolides are a major class of bioactive compounds derived from amphibian skin secretion. Gamabufotalin (GB) and arenobufagin (AB) are among the top of the intensively investigated natural bufadienolides for their outstanding biological activities. This study aimed to characterize the phase I metabolism of GB and AB with respect to the metabolic profiles, enzymes involved, and catalytic efficacy, thereafter tried to reveal substituent effects on metabolism. Two mono-hydroxylated products of GB and AB were detected in the incubation mixtures, and they were accurately identified as 1- and 5-hydroxylated bufadienolides by NMR and HPLC-MS techniques. Reaction phenotyping studies demonstrated that CYP3A mediated the metabolism of the two bufadienolides with a high specific selectivity. Further kinetic evaluation demonstrated that the metabolism stability of GB and AB were better than other reported bufadienolides. Additionally, the CYP3A5 preference for hydroxylation of AB was observed, which was different to the selectivity of CYP3As for bufadienolides suggested by our previous report. This study can provide important data for elucidating the phase I metabolism of GB and AB and can lead to a better understanding of the bufadienolide-CYP3A interaction which is helpful for preclinical development and rational use of bufadienolides. Copyright © 2017 Elsevier B.V. All rights reserved.
Gan, Tao; Zhang, Yanjuan; Chen, Yane; Hu, Huayu; Yang, Mei; Huang, Zuqiang; Chen, Dong; Huang, Aimin
2018-02-01
Three main components of lignocellulose (cellulose, hemicellulose, and lignin isolated from sugarcane bagasse (SCB)) as well as holocellulose and SCB were modified with maleic acid by mechanical activation (MA)-assisted solid phase reaction (MASPR) technology. The order of reactivity was found to be lignin>hemicellulose>cellulose. The amorphous structure of lignin and hemicellulose mainly attributed to their better reactivity, and the modified lignin could reach a maximum degree of esterification (DE) of 93.45%. MA improved the accessibility and reactivity of cellulose, as the DE of modified cellulose gradually increased with milling time and reached the maximum value of 57.30% at 120min, which had significant effect on structure changes and DE of modified holocellulose and SCB. MA enhanced the esterification of all three components in lignocellulose with relatively high substituent distribution in them, and maleated SCB with a maximum DE of 64.17% was successfully prepared by this simple, green, and effective MASPR technology. Copyright © 2017 Elsevier Ltd. All rights reserved.
Oesterling, Sven; Schalk, Oliver; Geng, Ting; Thomas, Richard D; Hansson, Tony; de Vivie-Riedle, Regina
2017-01-18
For the series furan, furfural and β-furfural we investigated the effect of substituents and their positioning on the photoinduced relaxation dynamics in a combined theoretical and experimental approach. Using time resolved photoelectron spectroscopy with a high intensity probe pulse, we can, for the first time, follow the whole deactivation process of furan through a two photon probe signal. Using the extended 2-electron 2-orbital model [Nenov et al., J. Chem. Phys., 2011, 135, 034304] we explain the formation of one central conical intersection and predict the influence of the aldehyde group of the derivatives on its geometry. This, as well as the relaxation mechanisms from photoexcitation to the final outcome was investigated using a variety of theoretical methods. Complete active space self consistent field was used for on-the-fly calculations while complete active space perturbation theory and coupled cluster theory were used to accurately describe critical configurations. Experiment and theory show the relaxation dynamics of furfural and β-furfural to be slowed down, and together they disclose an additional deactivation pathway, which is attributed to the n O lonepair state introduced with the aldehyde group.
Building evolutionary architectures support constant change
Ford, Neal; Kua, Patrick
2017-01-01
The software development ecosystem is constantly changing, providing a constant stream of new tools, frameworks, techniques, and paradigms. Over the past few years, incremental developments in core engineering practices for software development have created the foundations for rethinking how architecture changes over time, along with ways to protect important architectural characteristics as it evolves. This practical guide ties those parts together with a new way to think about architecture and time.
Nuclei quadrupole coupling constants in diatomic molecule
International Nuclear Information System (INIS)
Ivanov, A.I.; Rebane, T.K.
1993-01-01
An approximate relationship between the constants of quadrupole interaction of nuclei in a two-atom molecule is found. It enabled to establish proportionality of oscillatory-rotation corrections to these constants for both nuclei in the molecule. Similar results were obtained for the factors of electrical dipole-quadrupole screening of nuclei. Applicability of these relationships is proven by the example of lithium deuteride molecule. 4 refs., 1 tab
Parametrised Constants and Replication for Spatial Mobility
DEFF Research Database (Denmark)
Hüttel, Hans; Haagensen, Bjørn
2009-01-01
Parametrised replication and replication are common ways of expressing infinite computation in process calculi. While parametrised constants can be encoded using replication in the π-calculus, this changes in the presence of spatial mobility as found in e.g. the distributed π- calculus...... of the distributed π-calculus with parametrised constants and replication are incomparable. On the other hand, we shall see that there exists a simple encoding of recursion in mobile ambients....
A model for solar constant secular changes
Schatten, Kenneth H.
1988-01-01
In this paper, contrast models for solar active region and global photospheric features are used to reproduce the observed Active Cavity Radiometer and Earth Radiation Budget secular trends in reasonably good fashion. A prediction for the next decade of solar constant variations is made using the model. Secular trends in the solar constant obtained from the present model support the view that the Maunder Minimum may be related to the Little Ice Age of the 17th century.
A quadri-constant fraction discriminator
International Nuclear Information System (INIS)
Wang Wei; Gu Zhongdao
1992-01-01
A quad Constant Fraction (Amplitude and Rise Time Compensation) Discriminator Circuit is described, which is based on the ECL high-speed dual comparator AD 9687. The CFD (ARCD) is of the constant fraction timing type (the amplitude and rise time compensation timing type) employing a leading edge discriminator to eliminate error triggers caused by noises. A timing walk measurement indicates a timing walk of less than +- 150 ps from -50 mV to -5 V
Renormalization group equations with multiple coupling constants
International Nuclear Information System (INIS)
Ghika, G.; Visinescu, M.
1975-01-01
The main purpose of this paper is to study the renormalization group equations of a renormalizable field theory with multiple coupling constants. A method for the investigation of the asymptotic stability is presented. This method is applied to a gauge theory with Yukawa and self-quartic couplings of scalar mesons in order to find the domains of asymptotic freedom. An asymptotic expansion for the solutions which tend to the origin of the coupling constants is given
Inflation with a constant rate of roll
International Nuclear Information System (INIS)
Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi
2015-01-01
We consider an inflationary scenario where the rate of inflaton roll defined by ·· φ/H φ-dot remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs for unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime
RNA structure and scalar coupling constants
Energy Technology Data Exchange (ETDEWEB)
Tinoco, I. Jr.; Cai, Z.; Hines, J.V.; Landry, S.M.; SantaLucia, J. Jr.; Shen, L.X.; Varani, G. [Univ. of California, Berkeley, CA (United States)
1994-12-01
Signs and magnitudes of scalar coupling constants-spin-spin splittings-comprise a very large amount of data that can be used to establish the conformations of RNA molecules. Proton-proton and proton-phosphorus splittings have been used the most, but the availability of {sup 13}C-and {sup 15}N-labeled molecules allow many more coupling constants to be used for determining conformation. We will systematically consider the torsion angles that characterize a nucleotide unit and the coupling constants that depend on the values of these torsion angles. Karplus-type equations have been established relating many three-bond coupling constants to torsion angles. However, one- and two-bond coupling constants can also depend on conformation. Serianni and coworkers measured carbon-proton coupling constants in ribonucleosides and have calculated their values as a function of conformation. The signs of two-bond coupling can be very useful because it is easier to measure a sign than an accurate magnitude.
International Nuclear Information System (INIS)
Kim, Eung Ryul; Lim, Jong Wan; Kim, Se Kyong; Ko, Young Shin
2002-01-01
The reactions rates of substituted 6-chloroquinoline, with p-substituted benzoyichlorides (p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15,20,25 .deg. C) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ΔV ≠ , ΔH ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substituents in substrate (p-NO 2 ) with 6-chloroquinoline. When, the activation volume and the activation entropy are all negative. And the Hammett ρ values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in bond formation favored with increasing pressures
International Nuclear Information System (INIS)
Tsvetkov, E.N.; Evreinov, V.I.; Bondarenko, N.A.; Safronova, Z.V.
1996-01-01
The previously revealed unusual effect of alkyl substituents at phosphorus atom in phosphorus-containing monopodands of the general formula o-R 2 P(O)C 6 H 4 (OCH 2 CH 2 ) n OC 6 H 4 P(O)R 2 -o, n=1-5, R = Alk, Ph, OEt on their complexing ability towards alkali metals cations has been interpreted. Alkyl radicals create great spatial obstacles to rotation of R 2 P(O) fragments around the C-P bond as compared with other substituents, which gives rise to the appearance of anomalous alkyl effect. Solvation is an additional factor, which can bring about the anomalous effect appearance or a change in the degree of its pronouncement. 47 refs.; 3 figs.; 7 tabs
International Nuclear Information System (INIS)
Fehlner, T.P.; Czech, P.T.; Fenske, R.F.
1990-01-01
Utilizing Fenske-Hall wave functions and eigenvalues combined with the Ramsey sum over states (SOS) approximation, it is demonstrated that the sign and magnitude of the paramagnetic contribution to the shielding correlates well with the observed 11 B chemical shifts of a substantial variety of boron- and metal-containing compounds. Analysis of the molecular orbital (MO) contributions in the SOS approximation leads to an explanation of the large downfield shifts associated with metal-rich metallaboranes. A similar analysis demonstrates the importance of selected cluster occupied and unoccupied MO's in explaining both exo-cage substituent effects in which the antipodal boron resonance is shifted upfield and endo-cage substituent effects (interchange of isolobal fragments within the cage framework) in which the antipodal boron resonance is shifted downfield. Exo- and endo-cage substitution perturbs these MO's in an understandable fashion, leading to an internally consistent explanation of the observed chemical shift changes. 36 refs., 8 figs., 4 tabs
Martínez-Araya, Jorge I; Yepes, Diana; Jaque, Pablo
2017-12-27
Six organometallic compounds coming from a basic Mo-based complex were analyzed from the perspective of the dual descriptor in order to detect subtle influences that a substituent group could exert on the reactive core at a long range. Since the aforementioned complexes are open-shell systems, the used operational formula for the dual descriptor is that one defined for those aforementioned systems, which was then compared with spin density. In addition, dual descriptor was decomposed into two terms, each of which was also applied on every molecular system. The obtained results indicated that components of dual descriptor could become more useful than the operational formula of dual descriptor because differences exerted by the substituents at the para position were better detected by components of dual descriptor rather than the dual descriptor by itself.
International Nuclear Information System (INIS)
Ciscato, Luiz Francisco M.L.; Bartoloni, Fernando H.; Baader, Wilhelm Josef; Bastos, Erick L.; Guenther, Wolfgang; Weiss, Dieter; Beckert, Rainer
2010-01-01
The synthesis of one fenchyl-substituted alkene and two enol-ethers, containing 3-oxyphenyl substituents by the Barton-Kellogg reaction is described. The tri-substituted aromatic fenchylalkene 1a was prepared in 53% yield from thiofenchone and a diazoanisole; whereas enol-ethers 1b and 1c were obtained (95 and 75% yield, respectively) using an inverse approach based on diazofenchone and aromatic thionoesters. A mixture of Z and E isomers was obtained in all cases; isomer attribution and quantification has been carried out by analysis of NMR spectroscopic data assisted by theoretical calculations (E/Z ratio: 1a = 0.72, 1b = 2.2, 1c = 1.8). Reaction proceeds with low stereoselectivity leading to the preferential formation of diastereoisomeric olefins and enol-ethers where the aromatic substituent resides at the side of the two fenchyl methyl groups. (author)
Energy Technology Data Exchange (ETDEWEB)
Ciscato, Luiz Francisco M.L.; Bartoloni, Fernando H.; Baader, Wilhelm Josef, E-mail: wjbaader@iq.usp.b [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental; Bastos, Erick L. [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas; Guenther, Wolfgang; Weiss, Dieter; Beckert, Rainer [Friedrich-Schiller Universitaet Jena (Germany). Institut fuer Organische Chemie und Makromolekulare Chemie
2010-07-01
The synthesis of one fenchyl-substituted alkene and two enol-ethers, containing 3-oxyphenyl substituents by the Barton-Kellogg reaction is described. The tri-substituted aromatic fenchylalkene 1a was prepared in 53% yield from thiofenchone and a diazoanisole; whereas enol-ethers 1b and 1c were obtained (95 and 75% yield, respectively) using an inverse approach based on diazofenchone and aromatic thionoesters. A mixture of Z and E isomers was obtained in all cases; isomer attribution and quantification has been carried out by analysis of NMR spectroscopic data assisted by theoretical calculations (E/Z ratio: 1a = 0.72, 1b = 2.2, 1c = 1.8). Reaction proceeds with low stereoselectivity leading to the preferential formation of diastereoisomeric olefins and enol-ethers where the aromatic substituent resides at the side of the two fenchyl methyl groups. (author)
Lee, Jong-Seon; Kim, Ju-Hwan; Seo, Young-Seok; Yang, Jung-Bo; Kim, Yong-Il; Kim, Hye-Jin; Lee, Ki-Hwan
2013-09-01
This study was conducted to examine the influences of supplementation of the serum substituents and available period of serum-free Vero cell conditioned media (SF-VCM) manufactured from Dulbecco's modified Eagle medium cultured with Vero cells for in vitro development of mouse preimplantation embryos. A total of 1,099 two-cell embryos collected from imprinting control region mice were cultured in SF-VCM with 10% and 20% human follicular fluid (hFF), serum substitute supplement (SSS), and serum protein substitute (SPS). Development of embryos was observed every 24 hours. Results between different groups were analyzed by chi-square test, and considered statistically significant when P-value was less than 0.05. The rates of embryonic development cultured in SF-VCM supplemented with serum substituents were significantly higher compare with serum-free group (P media up to 4 weeks did not affect on embryonic development.
Credendino, Raffaele
2012-05-16
In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.
Yana I. Pylina; Dmitry M. Shadrin; Oksana G. Shevchenko; Olga M. Startseva; Igor O. Velegzhaninov; Dmitry V. Belykh; Ilya O. Velegzhaninov
2017-01-01
In the present work, we investigated the dark and photoinduced cytotoxic activity of the new chlorophyll-a derivatives which contain the substituents of oligoethylene glycol on the periphery of their macrocycles. These compounds were tested using human cell lines to estimate their potential as photosensitizers for photodynamic therapy of cancer. It was shown that all the tested compounds have expressed photoinduced cytotoxic activity in vitro. Detailed study of the biological activity of one ...
Wcisło, Anna; Niedziałkowski, Paweł; Wnuk, Elżbieta; Zarzeczańska, Dorota; Ossowski, Tadeusz
2013-05-01
A series of novel 1-amino and 1,4-diamino-9,10-anthraquinones, substituted with different alkyl groups, were synthesized as the result of alkylation with amino substituents. All the obtained aminoanthraquinone derivatives were characterized by NMR, IR spectroscopy and mass spectrometry. The spectroscopic properties of these compounds were determined by using UV-Vis spectroscopy in acetonitrile, and in the mixture of acetonitrile and methanol at different pH ranges. The effects of various substituents present in the newly developed anthraquinone derivatives and their ability to form hydrogen bonds between the carbonyl oxygen atom of anthraquinone moiety and nitrogen atom of N-H group in 1-aminoanthraquinone (1-AAQ) and 1,4-diaminoanthraquinone (1,4-DAAQ) were studied. Additionally, the effects of hydrogen bond formation between O-H group in hydroxyethylamino substituent and the carbonyl oxygen atom of anthraquinone were investigated. The spectroscopic behavior of the studied derivatives strongly depended on the solvent-solute interactions and the nature of solvent. The values of pKa for the new anthraquinones were determined by the combined potentiometric and spectrophotometric titration methods. Copyright © 2013 Elsevier B.V. All rights reserved.
Constant-roll (quasi-)linear inflation
Karam, A.; Marzola, L.; Pappas, T.; Racioppi, A.; Tamvakis, K.
2018-05-01
In constant-roll inflation, the scalar field that drives the accelerated expansion of the Universe is rolling down its potential at a constant rate. Within this framework, we highlight the relations between the Hubble slow-roll parameters and the potential ones, studying in detail the case of a single-field Coleman-Weinberg model characterised by a non-minimal coupling of the inflaton to gravity. With respect to the exact constant-roll predictions, we find that assuming an approximate slow-roll behaviour yields a difference of Δ r = 0.001 in the tensor-to-scalar ratio prediction. Such a discrepancy is in principle testable by future satellite missions. As for the scalar spectral index ns, we find that the existing 2-σ bound constrains the value of the non-minimal coupling to ξphi ~ 0.29–0.31 in the model under consideration.
Cosmological constant is a conserved charge
Chernyavsky, Dmitry; Hajian, Kamal
2018-06-01
Cosmological constant can always be considered as the on-shell value of a top form in gravitational theories. The top form is the field strength of a gauge field, and the theory enjoys a gauge symmetry. We show that cosmological constant is the charge of the global part of the gauge symmetry, and is conserved irrespective of the dynamics of the metric and other fields. In addition, we introduce its conjugate chemical potential, and prove the generalized first law of thermodynamics which includes variation of cosmological constant as a conserved charge. We discuss how our new term in the first law is related to the volume–pressure term. In parallel with the seminal Wald entropy, this analysis suggests that pressure can also be considered as a conserved charge.
Fast optimization algorithms and the cosmological constant
Bao, Ning; Bousso, Raphael; Jordan, Stephen; Lackey, Brad
2017-11-01
Denef and Douglas have observed that in certain landscape models the problem of finding small values of the cosmological constant is a large instance of a problem that is hard for the complexity class NP (Nondeterministic Polynomial-time). The number of elementary operations (quantum gates) needed to solve this problem by brute force search exceeds the estimated computational capacity of the observable Universe. Here we describe a way out of this puzzling circumstance: despite being NP-hard, the problem of finding a small cosmological constant can be attacked by more sophisticated algorithms whose performance vastly exceeds brute force search. In fact, in some parameter regimes the average-case complexity is polynomial. We demonstrate this by explicitly finding a cosmological constant of order 10-120 in a randomly generated 1 09-dimensional Arkani-Hamed-Dimopoulos-Kachru landscape.
Conformally invariant braneworld and the cosmological constant
International Nuclear Information System (INIS)
Guendelman, E.I.
2004-01-01
A six-dimensional braneworld scenario based on a model describing the interaction of gravity, gauge fields and 3+1 branes in a conformally invariant way is described. The action of the model is defined using a measure of integration built of degrees of freedom independent of the metric. There is no need to fine tune any bulk cosmological constant or the tension of the two (in the scenario described here) parallel branes to obtain zero cosmological constant, the only solutions are those with zero 4D cosmological constant. The two extra dimensions are compactified in a 'football' fashion and the branes lie on the two opposite poles of the compact 'football-shaped' sphere
Vanishing cosmological constant in elementary particles theory
International Nuclear Information System (INIS)
Pisano, F.; Tonasse, M.D.
1997-01-01
The quest of a vanishing cosmological constant is considered in the simplest anomaly-free chiral gauge extension of the electroweak standard model where the new physics is limited to a well defined additional flavordynamics above the Fermi scale, namely up to a few TeVs by matching the gauge coupling constants at the electroweak scale, and with an extended Higgs structure. In contrast to the electroweak standard model, it is shown how the extended scalar sector of the theory allows a vanishing or a very small cosmological constant. the details of the cancellation mechanism are presented. At accessible energies the theory is indistinguishable from the standard model of elementary particles and it is in agreement with all existing data. (author). 32 refs
Stability constants for silicate adsorbed to ferrihydrite
DEFF Research Database (Denmark)
Hansen, Hans Christian Bruun; Wetche, T.P.; Raulund-Rasmussen, Karsten
1994-01-01
Intrinsic surface acidity constants (K(a1)intr, K(a2)intr) and surface complexation constant for adsorption of orthosilicate onto synthetic ferrihydrite (K(Si) for the complex = FeOSi(OH)3) have been determined from acid/base titrations in 0.001-0.1 m NaClO4 electrolytes and silicate adsorption...... experiments in 0.01 m NaNO3 electrolyte (pH 3-6). The surface equilibrium constants were calculated according to the two-layer model by Dzombak & Morel (1990). Near equilibrium between protons/hydroxyls in solution and the ferrihydrite surface was obtained within minutes while equilibration with silicate...
Derivation of the optical constants of anisotropic
Aronson, J. R.; Emslie, A. G.; Smith, E. M.; Strong, P. F.
1985-07-01
This report concerns the development of methods for obtaining the optical constants of anisotropic crystals of the triclinic and monoclinic systems. The principal method used, classical dispersion theory, is adapted to these crystal systems by extending the Lorentz line parameters to include the angles characterizing the individual resonances, and by replacing the dielectric constant by a dielectric tensor. The sample crystals are gypsium, orthoclase and chalcanthite. The derived optical constants are shown to be suitable for modeling the optical properties of particulate media in the infrared spectral region. For those materials where suitable size single crystals are not available, an extension of a previously used method is applied to alabaster, a polycrystalline material of the monoclinic crystal system.
Effects of quantum entropy on bag constant
International Nuclear Information System (INIS)
Miller, D.E.; Tawfik, A.
2012-01-01
The effects of quantum entropy on the bag constant are studied at low temperatures and for small chemical potentials. The inclusion of the quantum entropy of the quarks in the equation of state provides the hadronic bag with an additional heat which causes a decrease in the effective latent heat inside the bag. We have considered two types of baryonic bags, Δ and Ω - . In both cases we have found that the bag constant without the quantum entropy almost does not change with temperature and quark chemical potential. The contribution from the quantum entropy to the equation of state clearly decreases the value of the bag constant. Furthermore, we construct states densities for quarks using the 'Thomas Fermi model' and take into consideration a thermal potential for the interaction. (author)
First Spectroscopic Studies and Detection in SgrB2 of 13C-DOUBLY Substitued Ethyl Cyanide
Margulès, L.; Motiyenko, R. A.; Guillemin, J.-C.; Müller, Holger S. P.; Belloche, Arnaud
2015-06-01
Ethyl cyanide (CH_3CH_2CN) is one of the most abundant complex organic molecules in the interstellar medium firstly detected in OMC-1 and Sgr B2 in 1977. The vibrationally excited states are enough populated under ISM conditions and could be detected. Apart from the deuterated ones, all mono-substituted isotopologues of ethyl cyanide (13C and 15N have been detected in the ISM. The detection of isotopologues in the ISM is important: it can give information about the formation process of complex organic molecules, and it is essential to clean the ISM spectra from the lines of known molecules in order to detect new ones. The 12C/13C ratio found in SgrB2: 20-30 suggests that the doubly 13C could be present in the spectral line survey recently obtained with ALMA (EMoCA), but no spectroscopic studies exist up to now. We measured and analyzed the spectra of the 13C-doubly-substitued species up to 1 THz with the Lille solid-state based spectrometer. The spectroscopic results and and the detection of the doubly 13C species in SgrB2 will be presented. This work was supported by the CNES and the Action sur Projets de l'INSU, PCMI. This work was also done under ANR-13-BS05-0008-02 IMOLABS. Support by the Deutsche Forschungsgemeinschaft via SFB 956, project B3 is acknowledged D.~R.~Johnson, et al., Astrophys.~J. 1977, 218, L370 A.~Belloche, et al., A&A 2013, 559, A47 A.M.~Daly, et al., Astrophys.~J. 2013, 768, 81 K.~Demyk, et al. A&A 2007 466, 255 Margulès, et al. A&A 2009, 493, 565 Belloche et al. 2014, Science, 345, 1584
James, Andrew M; Laconsay, Croix J; Galbraith, John Morrison
2017-07-13
Bond dissociation energies and resonance energies for H n A-BH m molecules (A, B = H, C, N, O, F, Cl, Li, and Na) have been determined in order to re-evaluate the concept of electronegativity in the context of modern valence bond theory. Following Pauling's original scheme and using the rigorous definition of the covalent-ionic resonance energy provided by the breathing orbital valence bond method, we have derived a charge-shift corrected electronegativity scale for H, C, N, O, F, Cl, Li, and Na. Atomic charge shift character is defined using a similar approach resulting in values of 0.42, 1.06, 1.43, 1.62, 1.64, 1.44, 0.46, and 0.34 for H, C, N, O, F, Cl, Li, and Na, respectively. The charge-shift corrected electronegativity values presented herein follow the same general trends as Pauling's original values with the exception of Li having a smaller value than Na (1.57 and 1.91 for Li and Na respectively). The resonance energy is then broken down into components derived from the atomic charge shift character and polarization effects. It is then shown that most of the resonance energy in the charge-shift bonds H-F, H 3 C-F, and Li-CH 3 and borderline charge-shift H-OH is associated with polarity rather than the intrinsic atomic charge-shift character of the bonding species. This suggests a rebranding of these bonds as "polar charge-shift" rather than simply "charge-shift". Lastly, using a similar breakdown method, it is shown that the small effect the substituents -CH 3 , -NH 2 , -OH, and -F have on the resonance energy (<10%) is mostly due to changes in the charge-shift character of the bonding atom.
International Nuclear Information System (INIS)
Basken, Nathan E.; Green, Mark A.
2009-01-01
Introduction: The pyruvaldehyde bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.
Energy Technology Data Exchange (ETDEWEB)
Basken, Nathan E. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States); Green, Mark A. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States)], E-mail: magreen@purdue.edu
2009-07-15
Introduction: The pyruvaldehyde bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.
Ferrer-Ugalde, Albert; Juárez-Pérez, Emilio José; Teixidor, Francesc; Viñas, Clara; Sillanpää, Reijo; Pérez-Inestrosa, Ezequiel; Núñez, Rosario
2012-01-09
A set of neutral and anionic carborane derivatives in which the styrenyl fragment is introduced as a fluorophore group has been successfully synthesized and characterized. The reaction of the monolithium salts of 1-Ph-1,2-C(2)B(10)H(11), 1-Me-1,2-C(2)B(10)H(11) and 1,2-C(2)B(10)H(12) with one equivalent of 4-vinylbenzyl chloride leads to the formation of compounds 1-3, whereas the reaction of the dilithium salt of 1,2-C(2)B(10)H(12) with two equivalents of 4-vinylbenzyl chloride gives disubstituted compound 4. The closo clusters were degraded using the classical method, KOH in EtOH, to afford the corresponding nido species, which were isolated as tetramethylammonium salts. The crystal structure of the four closo compounds 1-4 were analyzed by X-ray diffraction. All compounds, except 1, display emission properties, with quantum yields dependent on the nature of the cluster (closo or nido) and the substituent on the second C(cluster) atom. In general, closo compounds 2-4 exhibit high fluorescence emission, whereas the presence of a nido cluster produces a decrease of the emission intensity. The presence of a phenyl group bonded to the C(cluster) results in an excellent electron-acceptor unit that produces a quenching of the fluorescence. DFT calculations have confirmed the charge-separation state in 1 to explain the quenching of the fluorescence and the key role of the carboranyl fragment in this luminescent process. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
The Cosmological Constant Problem (1/2)
CERN. Geneva
2015-01-01
I will review the cosmological constant problem as a serious challenge to our notion of naturalness in Physics. Weinberg’s no go theorem is worked through in detail. I review a number of proposals possibly including Linde's universe multiplication, Coleman's wormholes, the fat graviton, and SLED, to name a few. Large distance modifications of gravity are also discussed, with causality considerations pointing towards a global modification as being the most sensible option. The global nature of the cosmological constant problem is also emphasized, and as a result, the sequestering scenario is reviewed in some detail, demonstrating the cancellation of the Standard Model vacuum energy through a global modification of General Relativity.
The Cosmological Constant Problem (2/2)
CERN. Geneva
2015-01-01
I will review the cosmological constant problem as a serious challenge to our notion of naturalness in Physics. Weinberg’s no go theorem is worked through in detail. I review a number of proposals possibly including Linde's universe multiplication, Coleman's wormholes, the fat graviton, and SLED, to name a few. Large distance modifications of gravity are also discussed, with causality considerations pointing towards a global modification as being the most sensible option. The global nature of the cosmological constant problem is also emphasized, and as a result, the sequestering scenario is reviewed in some detail, demonstrating the cancellation of the Standard Model vacuum energy through a global modification of General Relativity.
Atomic weights: no longer constants of nature
Coplen, Tyler B.; Holden, Norman E.
2011-01-01
Many of us were taught that the standard atomic weights we found in the back of our chemistry textbooks or on the Periodic Table of the Chemical Elements hanging on the wall of our chemistry classroom are constants of nature. This was common knowledge for more than a century and a half, but not anymore. The following text explains how advances in chemical instrumentation and isotopic analysis have changed the way we view atomic weights and why they are no longer constants of nature
International Nuclear Information System (INIS)
Bertolami, Orfeu; Paramos, Jorge
2011-01-01
The purpose of this study is to describe a perfect fluid matter distribution that leads to a constant curvature region, thanks to the effect of a nonminimal coupling. This distribution exhibits a density profile within the range found in the interstellar medium and an adequate matching of the metric components at its boundary. By identifying this constant curvature with the value of the cosmological constant and superimposing the spherical distributions arising from different matter sources throughout the universe, one is able to mimic a large-scale homogeneous cosmological constant solution.
Shiely, Amy E; Slattery, Catherine N; Ford, Alan; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R
2017-03-22
Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.
Time constant of logarithmic creep and relaxation
CSIR Research Space (South Africa)
Nabarro, FRN
2001-07-15
Full Text Available length and hardness which vary logarithmically with time. For dimensional reasons, a logarithmic variation must involve a time constant tau characteristic of the process, so that the deformation is proportional to ln(t/tau). Two distinct mechanisms...
The Nature of the Cosmological Constant Problem
Maia, M. D.; Capistrano, A. J. S.; Monte, E. M.
General relativity postulates the Minkowski space-time as the standard (flat) geometry against which we compare all curved space-times and also as the gravitational ground state where particles, quantum fields and their vacua are defined. On the other hand, experimental evidences tell that there exists a non-zero cosmological constant, which implies in a deSitter ground state, which not compatible with the assumed Minkowski structure. Such inconsistency is an evidence of the missing standard of curvature in Riemann's geometry, which in general relativity manifests itself in the form of the cosmological constant problem. We show how the lack of a curvature standard in Riemann's geometry can be fixed by Nash's theorem on metric perturbations. The resulting higher dimensional gravitational theory is more general than general relativity, similar to brane-world gravity, but where the propagation of the gravitational field along the extra dimensions is a mathematical necessity, rather than a postulate. After a brief introduction to Nash's theorem, we show that the vacuum energy density must remain confined to four-dimensional space-times, but the cosmological constant resulting from the contracted Bianchi identity represents a gravitational term which is not confined. In this case, the comparison between the vacuum energy and the cosmological constant in general relativity does not make sense. Instead, the geometrical fix provided by Nash's theorem suggests that the vacuum energy density contributes to the perturbations of the gravitational field.
A Memorandum Report: Physical Constants of MCE
2016-08-01
the density and surface tension. In effect, this constant is a corrected molar volume = P = MS / = S / where P = Parachor M = molar volume ...3 3. Vapor Pressure of MCE Calculated from the Experimental Data by Method of Least Squares...values were obtained by averaging the determinations for each sample separately, and then averaging those values. **No average was calculated due to
Study on electromagnetic constants of rotational bands
International Nuclear Information System (INIS)
Abdurazakov, A.A.; Adib, Yu.Sh.; Karakhodzhaev, A.K.
1991-01-01
Values of electromagnetic constant S and rotation bands of odd nuclei with Z=64-70 within the mass number change interval A=153-173 are determined. Values of γ-transition mixing parameter with M1+E2 multipolarity are presented. ρ parameter dependence on mass number A is discussed
On the determination of the Hubble constant
International Nuclear Information System (INIS)
Gurzadyan, V.G.; Harutyunyan, V.V.; Kocharyan, A.A.
1990-10-01
The possibility of an alternative determination of the distance scale of the Universe and the Hubble constant based on the numerical analysis of the hierarchical nature of the large scale Universe (galaxies, clusters and superclusters) is proposed. The results of computer experiments performed by means of special numerical algorithms are represented. (author). 9 refs, 7 figs
Dissociative electron attachment to ozone: rate constant
International Nuclear Information System (INIS)
Skalny, J.D.; Cicman, P.; Maerk, T.D.
2002-01-01
The rate constant for dissociative electron attachment to ozone has been derived over the energy range of 0-10 eV by using previously measured cross section data revisited here in regards to discrimination effect occurring during the extraction of ions. The obtained data for both possible channels exhibit the maximum at mean electron energies close to 1 eV. (author)
Running coupling constants of the Luttinger liquid
International Nuclear Information System (INIS)
Boose, D.; Jacquot, J.L.; Polonyi, J.
2005-01-01
We compute the one-loop expressions of two running coupling constants of the Luttinger model. The obtained expressions have a nontrivial momentum dependence with Landau poles. The reason for the discrepancy between our results and those of other studies, which find that the scaling laws are trivial, is explained
Constant force linear permanent magnet actuators
Paulides, J.J.H.; Encica, L.; Meessen, K.J.; Lomonova, E.A.
2009-01-01
In applications, such as vibration isolation, gravity compensation, pick-and-place machines, etc., there is a need for (long-stroke) passive constant force actuators combined with tubular permanent magnet actuators to minimize the power consumption, hence, passively counteract the gravitational
Lifetime of titanium filament at constant current
International Nuclear Information System (INIS)
Chou, T.S.; Lanni, C.
1981-01-01
Titanium Sublimation Pump (TSP) represents the most efficient and the least expensive method to produce Ultra High Vacuum (UHV) in storage rings. In ISABELLE, a proton storage accelerator under construction at Brookhaven National Laboratory, for example, TSP provides a pumping speed for hydrogen of > 2 x 10 6 l/s. Due to the finite life of titanium filaments, new filaments have to be switched in before the end of filament burn out, to ensure smooth operation of the accelerator. Therefore, several operational modes that can be used to activate the TSP were studied. The constant current mode is a convenient way of maintaining constant evaporating rate by increasing the power input while the filament diameter decreases as titanium evaporates. The filaments used in this experiment were standard Varian 916-0024 filaments made of Ti 85%, Mo 15% alloy. During their lifetime at a constant current of 48 amperes, the evaporation rate rose to a maximum at about 10% of their life and then flattened out to a constant value, 0.25 g/hr. The maximum evaporation rate occurs coincidently with the recrystallization of 74% Ti 26% Mo 2 from microstructure crystalline at higher titanium concentration to macrostructure crystalline at lower titanium concentration. As the macrocrystal grows, the slip plane develops at the grain boundary resulting in high resistance at the slip plane which will eventually cause the filament burn out due to local heating
Derivation of the fine-structure constant
International Nuclear Information System (INIS)
Samec, A.
1980-01-01
The fine-structure constant is derived as a dynamical property of quantum electrodynamics. Single-particle solutions of the coupled Maxwell and Dirac equations have a physical charge spectrum. The solutions are used to construct lepton-and quark-like particles. The strong, weak, electromagnetic, and gravitational forces are described as the interactions of complex charges in multiple combinations
Directory of Open Access Journals (Sweden)
Tadafumi Uchimaru
2002-04-01
Full Text Available Abstract: The accurate O-H bond dissociation enthalpies for a series of meta and para substituted phenols (X-C6H4-OH, X=H, F, Cl, CH3, OCH3, OH, NH2, CF3, CN, and NO2 have been calculated by using the (ROB3LYP procedure with 6-311G(d,p and 6-311++G(2df,2p basis sets. The proton affinities of the corresponding phenoxide ions (XC6H4-O- have also been computed at the same level of theory. The effect of change of substituent position on the energetics of substituted phenols has been analyzed. The correlations of HammettÃ¢Â€Â™s substituent constants with the bond dissociation enthalpies of the O-H bonds of phenols and proton affinities of phenoxide ions have been explored.
Construction of Lines of Constant Density and Constant Refractive Index for Ternary Liquid Mixtures.
Tasic, Aleksandar Z.; Djordjevic, Bojan D.
1983-01-01
Demonstrates construction of density constant and refractive index constant lines in triangular coordinate system on basis of systematic experimental determinations of density and refractive index for both homogeneous (single-phase) ternary liquid mixtures (of known composition) and the corresponding binary compositions. Background information,…
DEFF Research Database (Denmark)
Pawlowski, F; Jorgensen, P; Olsen, Jeppe
2002-01-01
A detailed study is carried out of the accuracy of molecular equilibrium geometries obtained from least-squares fits involving experimental rotational constants B(0) and sums of ab initio vibration-rotation interaction constants alpha(r)(B). The vibration-rotation interaction constants have been...... calculated for 18 single-configuration dominated molecules containing hydrogen and first-row atoms at various standard levels of ab initio theory. Comparisons with the experimental data and tests for the internal consistency of the calculations show that the equilibrium structures generated using Hartree......-Fock vibration-rotation interaction constants have an accuracy similar to that obtained by a direct minimization of the CCSD(T) energy. The most accurate vibration-rotation interaction constants are those calculated at the CCSD(T)/cc-pVQZ level. The equilibrium bond distances determined from these interaction...
Obali, Aslihan Yilmaz; Ucan, Halil Ismet
2016-09-01
Novel different substitued polypyridine ligands 4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzaldehyde (BA-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzylidene)-pyrene-4-amine (PR-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10] phenanthroline-2-yl)phenoxy)methyl)benzylidene)-1,10-phenanthroline-5amine (FN-PPY), 2-(4-(bromomethyl)phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (BR-PPY), 2-(4-(azidomethyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (N3-PPY) and triazole containing polypyridine ligand 3,4-bis[(4-(metoxy)-1,2,3-triazole)1-methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)] benzaldehyde (BA-DIPPY) and Ruthenium(II) complexes were synthesized and characterized. Their photopysical properties were investigated. The complexes RuP(PR-PPY), RuB(PR-PPY, RuP(FN-PPY) and RuB(FN-PPY) exhibited a broad absorption bands at 485, 475, 476, and 453 nm, respectively, assignable to the spin-allowed MLCT (dπ-π*) transition. The emission maxima of the pyrene-appended polypyridine ligand PR-PPY was observed at λems = 616 nm and the phenanthroline-appended polypyridine ligand FN-PPY was observed at λems = 668 nm. And the emission maxima of the complexes RuP(PR-PPY), RuB(PR-PPY), RuP(FN-PPY) and RuB(FN-PPY) were observed at λems = 646, 646, 685 and 685 nm, respectively. As seen in fluorescence spectra, the fluorescence intensities of the ligands are higher than their metal complexes. This is because of quenching effect of Ruthenium(II) metal on chromophore groups.
Constant force extensional rheometry of polymer solutions
DEFF Research Database (Denmark)
Szabo, Peter; McKinley, Gareth H.; Clasen, Christian
2012-01-01
We revisit the rapid stretching of a liquid filament under the action of a constant imposed tensile force, a problem which was first considered by Matta and Tytus [J. Non-Newton. Fluid Mech. 35 (1990) 215–229]. A liquid bridge formed from a viscous Newtonian fluid or from a dilute polymer solution...... is first established between two cylindrical disks. The upper disk is held fixed and may be connected to a force transducer while the lower cylinder falls due to gravity. By varying the mass of the falling cylinder and measuring its resulting acceleration, the viscoelastic nature of the elongating fluid...... filament can be probed. In particular, we show that with this constant force pull (CFP) technique it is possible to readily impose very large material strains and strain rates so that the maximum extensibility of the polymer molecules may be quantified. This unique characteristic of the experiment...
Energy Technology Data Exchange (ETDEWEB)
Motohashi, Hayato [Universidad de Valencia-CSIC, Instituto de Fisica Corpuscular (IFIC), Valencia (Spain); Starobinsky, Alexei A. [L.D. Landau Institute for Theoretical Physics, RAS, Moscow (Russian Federation); National Research University Higher School of Economics, Moscow (Russian Federation)
2017-08-15
The previously introduced class of two-parametric phenomenological inflationary models in general relativity in which the slow-roll assumption is replaced by the more general, constant-roll condition is generalized to the case of f(R) gravity. A simple constant-roll condition is defined in the original Jordan frame, and exact expressions for a scalaron potential in the Einstein frame, for a function f(R) (in the parametric form) and for inflationary dynamics are obtained. The region of the model parameters permitted by the latest observational constraints on the scalar spectral index and the tensor-to-scalar ratio of primordial metric perturbations generated during inflation is determined. (orig.)
Benjamin Constant. Libertad, democracia y pluralismo
Directory of Open Access Journals (Sweden)
Claudia Patricia Fonnegra Osorio
2015-12-01
Full Text Available A partir de un enfoque interpretativo, en este artículo se aborda por qué para Benjamin Constant la democracia solo puede darse en donde se presenta una relación necesaria entre la libertad entendida como defensa de los derechos individuales -libertad como independencia o negativa- y la libertad concebida como principio de la participación pública -libertad como autonomía o positiva-. Asimismo, se presenta la importancia que atribuye el autor a las tradiciones que dan vida a la configuración del universo cultural de un pueblo. Se concluye que en la obra de Constant se encuentra una clara defensa del Estado de derecho y del pluralismo, la cual puede iluminar la comprensión de los problemas políticos de la contemporaneidad.
Varying constants, black holes, and quantum gravity
International Nuclear Information System (INIS)
Carlip, S.
2003-01-01
Tentative observations and theoretical considerations have recently led to renewed interest in models of fundamental physics in which certain 'constants' vary in time. Assuming fixed black hole mass and the standard form of the Bekenstein-Hawking entropy, Davies, Davis and Lineweaver have argued that the laws of black hole thermodynamics disfavor models in which the fundamental electric charge e changes. I show that with these assumptions, similar considerations severely constrain 'varying speed of light' models, unless we are prepared to abandon cherished assumptions about quantum gravity. Relaxation of these assumptions permits sensible theories of quantum gravity with ''varying constants,'' but also eliminates the thermodynamic constraints, though the black hole mass spectrum may still provide some restrictions on the range of allowable models
Cosmological constant in the quantum multiverse
International Nuclear Information System (INIS)
Larsen, Grant; Nomura, Yasunori; Roberts, Hannes L. L.
2011-01-01
Recently, a new framework for describing the multiverse has been proposed which is based on the principles of quantum mechanics. The framework allows for well-defined predictions, both regarding global properties of the universe and outcomes of particular experiments, according to a single probability formula. This provides complete unification of the eternally inflating multiverse and many worlds in quantum mechanics. In this paper, we elucidate how cosmological parameters can be calculated in this framework, and study the probability distribution for the value of the cosmological constant. We consider both positive and negative values, and find that the observed value is consistent with the calculated distribution at an order of magnitude level. In particular, in contrast to the case of earlier measure proposals, our framework prefers a positive cosmological constant over a negative one. These results depend only moderately on how we model galaxy formation and life evolution therein.
On determining dose rate constants spectroscopically
International Nuclear Information System (INIS)
Rodriguez, M.; Rogers, D. W. O.
2013-01-01
Purpose: To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of 125 I and 103 Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089–6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated 125 I and 103 Pd sources. Methods: Spectra generated by 14 125 I and 6 103 Pd seeds were calculated in vacuo at 10 cm from the source in a 2.7 × 2.7 × 0.05 cm 3 voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the 125 I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for 103 Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were ⩽0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. Results: The ratio of the intensity of the 31 keV line relative to that of the main peak in 125 I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The 103 Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak when calculated with the TG-43U1 rather than the NNDC(2000) initial spectrum. The measured values from three different
Some Dynamical Effects of the Cosmological Constant
Axenides, M.; Floratos, E. G.; Perivolaropoulos, L.
Newton's law gets modified in the presence of a cosmological constant by a small repulsive term (antigravity) that is proportional to the distance. Assuming a value of the cosmological constant consistent with the recent SnIa data (Λ~=10-52 m-2), we investigate the significance of this term on various astrophysical scales. We find that on galactic scales or smaller (less than a few tens of kpc), the dynamical effects of the vacuum energy are negligible by several orders of magnitude. On scales of 1 Mpc or larger however we find that the vacuum energy can significantly affect the dynamics. For example we show that the velocity data in the local group of galaxies correspond to galactic masses increased by 35% in the presence of vacuum energy. The effect is even more important on larger low density systems like clusters of galaxies or superclusters.
Daylight calculations using constant luminance curves
Energy Technology Data Exchange (ETDEWEB)
Betman, E. [CRICYT, Mendoza (Argentina). Laboratorio de Ambiente Humano y Vivienda
2005-02-01
This paper presents a simple method to manually estimate daylight availability and to make daylight calculations using constant luminance curves calculated with local illuminance and irradiance data and the all-weather model for sky luminance distribution developed in the Atmospheric Science Research Center of the University of New York (ARSC) by Richard Perez et al. Work with constant luminance curves has the advantage that daylight calculations include the problem's directionality and preserve the information of the luminous climate of the place. This permits accurate knowledge of the resource and a strong basis to establish conclusions concerning topics related to the energy efficiency and comfort in buildings. The characteristics of the proposed method are compared with the method that uses the daylight factor. (author)
Understanding fine structure constants and three generations
International Nuclear Information System (INIS)
Bennett, D.L.; Nielsen, H.B.
1988-02-01
We put forward a model inspired by random dynamics that relates the smallness of the gauge coupling constants to the number of generations being 'large'. The new element in the present version of our model is the appearance of a free parameter χ that is a measure of the (presumably relatively minor) importance of a term in the plaquette action proportional to the trace in the (1/6, 2, 3) representation of the Standard Model. Calling N gen the number of generations, the sets of allowed (N gen , χN gen )-pairs obtained by imposing the three measured coupling constant values of the Standard Model form three lines. In addition to finding that these lines cross at a single point (as needed for a consistent fit), the intersection occurs with surprising accuracy at the integer N gen = 3 (thereby predicting exactly three generations). It is also encouraging that the parameter χ turns out to be small and positive as expected. (orig.)
Bardeen-Cooper-Schrieffer universal constants generalized
International Nuclear Information System (INIS)
Hazaimeh, A.H.
1992-01-01
Weak- and moderate-coupling BCS superconductivity theory is shown to admit a more general T c formula, wherein T c approaches zero somewhat faster than with the familiar BCS T c -formula. This theory leads to a departure from the universal behavior of the gap-to-T c ratio and is consistent with some recent empirical values for exotic superconductors. This ratio is smaller than the universal BCS value of 3.53 in a way which is consistent with weak electron-boson coupling. Similarly, other universal constants related to specific heat and critical magnetic field are modified. In this dissertation, The author investigates the latter constants for weak-coupling and moderate-coupling and carry out detailed comparisons with experimental data for the cuprates and with the corresponding predictions of strong-coupling theory. This effort is to elucidate the nature of these superconductors with regards to coupling strength within an electron-boson mechanism
Multiphoton amplitude in a constant background field
Ahmad, Aftab; Ahmadiniaz, Naser; Corradini, Olindo; Kim, Sang Pyo; Schubert, Christian
2018-01-01
In this contribution, we present our recent compact master formulas for the multiphoton amplitudes of a scalar propagator in a constant background field using the worldline fomulation of quantum field theory. The constant field has been included nonperturbatively, which is crucial for strong external fields. A possible application is the scattering of photons by electrons in a strong magnetic field, a process that has been a subject of great interest since the discovery of astrophysical objects like radio pulsars, which provide evidence that magnetic fields of the order of 1012G are present in nature. The presence of a strong external field leads to a strong deviation from the classical scattering amplitudes. We explicitly work out the Compton scattering amplitude in a magnetic field, which is a process of potential relevance for astrophysics. Our final result is compact and suitable for numerical integration.
Piezooptical constants of Rochelle salt crystals
V.Yo. Stadnyk; M.O. Romanyuk; V.Yu. Kurlyak; V.F.Vachulovych
2000-01-01
The influence of uniaxial mechanical pressure applied along the principal axes and the corresponding bisectors on the birefringent properties of Rochelle salt (RS) crystals are studied. The temperature (77-300 K) and spectral (300-700 nm) dependencies of the effective and absolute piezooptical constants of the RS crystals are calculated. The intercept of dispersion curves of is revealed in the region of the birefringence sign inversion. This testifies that the anizotropy of the piezooptical ...
Simulated annealing with constant thermodynamic speed
International Nuclear Information System (INIS)
Salamon, P.; Ruppeiner, G.; Liao, L.; Pedersen, J.
1987-01-01
Arguments are presented to the effect that the optimal annealing schedule for simulated annealing proceeds with constant thermodynamic speed, i.e., with dT/dt = -(v T)/(ε-√C), where T is the temperature, ε- is the relaxation time, C ist the heat capacity, t is the time, and v is the thermodynamic speed. Experimental results consistent with this conjecture are presented from simulated annealing on graph partitioning problems. (orig.)
A noteworthy dimensionless constant in gravitation theory
International Nuclear Information System (INIS)
Fayos, F.; Lobo, J.A.; Llanta, E.
1986-01-01
A simple problem of gravitation is studied classically and in the Schwarzchild framework. A relationship is found between the parameters that define the trajectories of two particles (the first in radial motion and the second in a circular orbit) which are initially together and meet again after one revolution of particle 2. Dimensional analysis is the clue to explain the appearance of a dimensionless constant in the Newtonian case. (author)
Electromagnetic corrections to pseudoscalar decay constants
Energy Technology Data Exchange (ETDEWEB)
Glaessle, Benjamin Simon
2017-03-06
First principles Lattice quantum chromodynamics (LQCD) calculations enable the determination of low energy hadronic amplitudes. Precision LQCD calculations with relative errors smaller than approximately 1% require the inclusion of electromagnetic effects. We demonstrate that including (quenched) quantum electrodynamics effects in the LQCD calculation effects the values obtained for pseudoscalar decay constants in the per mille range. The importance of systematic effects, including finite volume effects and the charge dependence of renormalization and improvement coefficients, is highlighted.
Cosmological Constant and the Final Anthropic Hypothesis
Cirkovic, Milan M.; Bostrom, Nick
1999-01-01
The influence of recent detections of a finite vacuum energy ("cosmological constant") on our formulation of anthropic conjectures, particularly the so-called Final Anthropic Principle is investigated. It is shown that non-zero vacuum energy implies the onset of a quasi-exponential expansion of our causally connected domain ("the universe") at some point in the future, a stage similar to the inflationary expansion at the very beginning of time. The transition to this future inflationary phase...
Singlet axial constant from QCD sum rules
International Nuclear Information System (INIS)
Belitskij, A.V.; Teryaev, O.V.
1995-01-01
We analyze the singlet axial form factor of the proton for small momentum transferred in the framework of QCD sum rules using the interpolating nucleon current which explicitly accounts for the gluonic degrees of freedom. As the result we come to the quantitative prediction of the singlet axial constant. It is shown that the bilocal power corrections play the most important role in the analysis. 21 refs., 3 figs
Lattice Paths and the Constant Term
International Nuclear Information System (INIS)
Brak, R; Essam, J; Osborn, J; Owczarek, A L; Rechnitzer, A
2006-01-01
We firstly review the constant term method (CTM), illustrating its combinatorial connections and show how it can be used to solve a certain class of lattice path problems. We show the connection between the CTM, the transfer matrix method (eigenvectors and eigenvalues), partial difference equations, the Bethe Ansatz and orthogonal polynomials. Secondly, we solve a lattice path problem first posed in 1971. The model stated in 1971 was only solved for a special case - we solve the full model
Elastic constants from microscopic strain fluctuations
Sengupta; Nielaba; Rao; Binder
2000-02-01
Fluctuations of the instantaneous local Lagrangian strain epsilon(ij)(r,t), measured with respect to a static "reference" lattice, are used to obtain accurate estimates of the elastic constants of model solids from atomistic computer simulations. The measured strains are systematically coarse-grained by averaging them within subsystems (of size L(b)) of a system (of total size L) in the canonical ensemble. Using a simple finite size scaling theory we predict the behavior of the fluctuations as a function of L(b)/L and extract elastic constants of the system in the thermodynamic limit at nonzero temperature. Our method is simple to implement, efficient, and general enough to be able to handle a wide class of model systems, including those with singular potentials without any essential modification. We illustrate the technique by computing isothermal elastic constants of "hard" and "soft" disk triangular solids in two dimensions from Monte Carlo and molecular dynamics simulations. We compare our results with those from earlier simulations and theory.
Emergent gravity in spaces of constant curvature
Energy Technology Data Exchange (ETDEWEB)
Alvarez, Orlando; Haddad, Matthew [Department of Physics, University of Miami,1320 Campo Sano Ave, Coral Gables, FL 33146 (United States)
2017-03-07
In physical theories where the energy (action) is localized near a submanifold of a constant curvature space, there is a universal expression for the energy (or the action). We derive a multipole expansion for the energy that has a finite number of terms, and depends on intrinsic geometric invariants of the submanifold and extrinsic invariants of the embedding of the submanifold. This is the second of a pair of articles in which we try to develop a theory of emergent gravity arising from the embedding of a submanifold into an ambient space equipped with a quantum field theory. Our theoretical method requires a generalization of a formula due to by Hermann Weyl. While the first paper discussed the framework in Euclidean (Minkowski) space, here we discuss how this framework generalizes to spaces of constant sectional curvature. We focus primarily on anti de Sitter space. We then discuss how such a theory can give rise to a cosmological constant and Planck mass that are within reasonable bounds of the experimental values.
Planck Constant Determination from Power Equivalence
Newell, David B.
2000-04-01
Equating mechanical to electrical power links the kilogram, the meter, and the second to the practical realizations of the ohm and the volt derived from the quantum Hall and the Josephson effects, yielding an SI determination of the Planck constant. The NIST watt balance uses this power equivalence principle, and in 1998 measured the Planck constant with a combined relative standard uncertainty of 8.7 x 10-8, the most accurate determination to date. The next generation of the NIST watt balance is now being assembled. Modification to the experimental facilities have been made to reduce the uncertainty components from vibrations and electromagnetic interference. A vacuum chamber has been installed to reduce the uncertainty components associated with performing the experiment in air. Most of the apparatus is in place and diagnostic testing of the balance should begin this year. Once a combined relative standard uncertainty of one part in 10-8 has been reached, the power equivalence principle can be used to monitor the possible drift in the artifact mass standard, the kilogram, and provide an accurate alternative definition of mass in terms of fundamental constants. *Electricity Division, Electronics and Electrical Engineering Laboratory, Technology Administration, U.S. Department of Commerce. Contribution of the National Institute of Standards and Technology, not subject to copyright in the U.S.
Constant leverage and constant cost of capital : A common knowledge half-truth
Vélez Pareja, Ignacio; Ibragimov, Rauf; Tham , Joseph
2008-01-01
Un enfoque típico para valorar flujos de caja finitos es suponer que el endeudamiento es constante (generalmente como un endeudamiento objetivo o deseado) y que por tanto, el costo del patrimonio, Ke y el costo promedio ponderado de capital CPPC, también son constantes. Para los flujos de caja perpetuos, y con el costo de la deuda, Kd como la tasa de descuento para el ahorro en impuestos o escudo fiscal, Ke y el CPPC aplicado al flujo de caja libre FCL son constantes si el endeudamiento es co...
Poirier, Stéphanie; Czympiel, Lisa; Bélanger-Desmarais, Nicolas; Mathur, Sanjay; Reber, Christian
2016-04-21
Luminescence spectra of two d(8)-configured bis(pyridylalkenolato)palladium(ii) complexes, [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12,100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}2] show a shift of -0.9 ± 0.1 cm(-1) K(-1) due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}2] shift in the opposite direction by +7.2 ± 0.7 cm(-1) K(-1). Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of +13 ± 2 cm(-1) kbar(-1) and -15 ± 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(ii) center and a vinylic proton of a neighboring complex.
Directory of Open Access Journals (Sweden)
José Cláudio Caraschi
1999-06-01
Full Text Available Amostras de carboximetilcelulose foram preparadas por reação heterogênea de polpa soda/antraquinona obtida de fibras pré-hidrolisadas de bagaço de cana-de-açúcar. As amostras com os menores graus de substituição ( > 1,0 apresentaram comportamentos diferentes quanto a: i variação de constante aparente de acidez (pk ap com o grau de dissociação; ii concordância entre os valores de determinados por titulações e por espectroscopia ¹H rmn e iii concordância entre os valores experimentais de coeficientes de transporte e os previstos pelo modelo de Manning. Todas as amostras apresentaram um padrão de substituição em blocos que, nas amostras menos substituídas são curtos e espaçados, favorecendo interações associativas que levam à agregação. Efeitos de volume excluído eletrostático, mais importantes nas amostras mais substituídas, inibem a agregação e explicam o comportamento observado nesses casos.Samples of carboxymethylcellulose were prepared by the heterogeneous reaction of the soda/anthraquinone pulp obtained from sugar cane bagasse. The less substituted samples (DS 1,0 showed different behaviors concerning to: i the dependence of pk ap on the degree of neutralization; ii the agreement between DS values determined by titrations and by ¹H nmr spectroscopy and iii the agreement between the experimental values of transport coefficients (f and the ones calculated by applying the Manning theoretical approach. All samples showed a block distribution of substituents which, in the case of the less substituted samples, are short and well separated, favoring the occurrence of associative interactions and of aggregation. Electrostatic excluded volume effects, which are more important for the more substituted samples, inhibit the aggregation and may explain the behavior of these samples.
Directory of Open Access Journals (Sweden)
Hooshang Hamidian
2013-01-01
Full Text Available Six azo disperse dyes were prepared by diazotizing 4-amino hippuric acid and coupled with barbituric acid and 2-thiobarbituric acid. Then, the products were reacted with aromatic aldehyde, sodium acetate, and acetic anhydride, and oxazolone derivatives were formed. Characterization of the dyes was carried out by using UV-Vis, FT-IR, 1H NMR and 13C NMR, and mass spectroscopic techniques. The solvatochromic behavior of azo disperse dyes was evaluated in various solvents. The effects of substituents of aromatic aldehyde, barbiturate, and thiobarbiturate ring on the color of dyes were investigated.
DFT studies for the substituent effect on the diels-alder reaction of 1,4-diaza-1,3-butadienes
International Nuclear Information System (INIS)
Lee, Gab Yong
2001-01-01
DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular orbital) energies for the optimized 1,4-disubstituted-1,4DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively
International Nuclear Information System (INIS)
Volkov, O.V.; Il'inchik, E.A.; Volkov, V.V.; Voronina, G.S.; Yur'eva, O.P.
1997-01-01
The synthesis of bromo- and iodo substituents 7,8-C 2 B 9 H 11 xRu is accomplished and their comparative study is carried out through the methods of NMR 11 B-, PMR-, IR- and UV-spectroscopy. It is established that by introduction of halogen into carborane polyhedron there takes place increase in the acceptor capability of the latter and in the result the adduct stabilization. At the same time the introduction of halogen atom leads to sharp decrease in the intensity of the adduct fluorescence in the crystal state
Pratt, Derek A.; Pesavento, Russell P.; van der Donk, Wilfred A.
2010-01-01
Experimental and theoretical studies were carried out to interrogate the effect of an imidazole substituent in each of the ortho, meta, and para positions on the pKa, E°, and O–H BDE of phenol. The results reveal that imidazole substitution lowers the pKa of phenol and increases the E° of phenoxide due to its σ-electron withdrawing ability (σp− = +0.21, σm− = +0.45) but decreases the O–H BDE and E° of phenol due to its σ-electron-donating ability (σp+ = −0.45). PMID:15957934
International Nuclear Information System (INIS)
Sawant, R.M.; Ramakumar, K.L.; Sharma, R.S.
2003-01-01
Protonation constants of hydroquinone and stability constants of thorium hydroquinone complexes were determined in 1 M NaClO 4 medium at 25 ± 0.5 degC, by varying concentration of thorium, using pH titration technique. Protonation constants of hydroquinone (β 1H = [HQ]/[H][Q] and β 2H = [H 2 Q]/[H] 2 [Q]) were found to be β 1H = 11.404 ± 0.014 and β 2H = 21.402 ± 0.012. The analysis of titration data of thorium-hydroquinone system appears to indicate the formation of species Th(H 2 Q) 3 (OH) and Th(H 2 O) 4 (OH). Equilibrium constants obtained for these species are -log β 13-I = 48.51 ± 0.67 and -log β 14-1 64.86 ± 1.25 respectively which are not reported in the literature. (author)
Constant load and constant displacement stress corrosion in simulated water reactor environments
International Nuclear Information System (INIS)
Lloyd, G.J.
1987-02-01
The stress corrosion behaviour of selected water reactor constructional materials, as determined by constant load or constant displacement test techniques, is reviewed. Experimental results obtained using a very wide range of conditions have been collected in a form for easy reference. A discussion is given of some apparent trends in these data. The possible reasons for these trends are considered together with a discussion of how the observed discrepancies may be resolved. (author)
CONSTANT LEVERAGE AND CONSTANT COST OF CAPITAL: A COMMON KNOWLEDGE HALF-TRUTH
Directory of Open Access Journals (Sweden)
IGNACIO VÉLEZ-PAREJA
2008-01-01
Full Text Available Un enfoque típico para valorar flujos de caja finitos es suponer que el endeudamiento es constante (generalmente como un endeudamiento objetivo o deseado y que por tanto, el costo del patrimonio, Ke y el costo promedio ponderado de capital CPPC, también son constantes. Para los flujos de caja perpetuos, y con el costo de la deuda, Kd como la tasa de descuento para el ahorro en impuestos o escudo fiscal, Ke y el CPPC aplicado al flujo de caja libre FCL son constantes si el endeudamiento es constante. Sin embargo esto no es verdad para los flujos de caja finitos. En este documento mostramos que para flujos de caja finitos, Ke y por lo tanto el CPPC dependen de la tasa de descuento que se utiliza para valorar el ahorro en impuestos, AI y según lo esperado, Ke y el CPPC no son constantes con Kd como la tasa de descuento para el ahorro en impuestos, aunque el endeudamiento sea constante. Ilustramos esta situación con un ejemplo simple. Analizamos cinco métodos: el flujo de caja descontado, FCD, usando APV, el FCD y la formulación tradicional y general del CPPC, el valor presente del flujo de caja del accionista, FCA más deuda y el flujo de caja de capital, FCC.
Inflation with a smooth constant-roll to constant-roll era transition
Odintsov, S. D.; Oikonomou, V. K.
2017-07-01
In this paper, we study canonical scalar field models, with a varying second slow-roll parameter, that allow transitions between constant-roll eras. In the models with two constant-roll eras, it is possible to avoid fine-tunings in the initial conditions of the scalar field. We mainly focus on the stability of the resulting solutions, and we also investigate if these solutions are attractors of the cosmological system. We shall calculate the resulting scalar potential and, by using a numerical approach, we examine the stability and attractor properties of the solutions. As we show, the first constant-roll era is dynamically unstable towards linear perturbations, and the cosmological system is driven by the attractor solution to the final constant-roll era. As we demonstrate, it is possible to have a nearly scale-invariant power spectrum of primordial curvature perturbations in some cases; however, this is strongly model dependent and depends on the rate of the final constant-roll era. Finally, we present, in brief, the essential features of a model that allows oscillations between constant-roll eras.
TASI Lectures on the cosmological constant
Energy Technology Data Exchange (ETDEWEB)
Bousso, Raphael; Bousso, Raphael
2007-08-30
The energy density of the vacuum, Lambda, is at least 60 orders of magnitude smaller than several known contributions to it. Approaches to this problem are tightly constrained by data ranging from elementary observations to precision experiments. Absent overwhelming evidence to the contrary, dark energy can only be interpreted as vacuum energy, so the venerable assumption that Lambda=0 conflicts with observation. The possibility remains that Lambda is fundamentally variable, though constant over large spacetime regions. This can explain the observed value, but only in a theory satisfying a number of restrictive kinematic and dynamical conditions. String theory offers a concrete realization through its landscape of metastable vacua.
Theoretical isochrones with decreasing gravitational constant
International Nuclear Information System (INIS)
Vandenberg, D.A.
1976-01-01
Van Flandern has postulated a variation of the gravitational constant at the rate approximately -8 x 10 -11 /yr. This variation, consistent with Hoyle-Narlikar and Dirac cosmologies, has been assumed in the computation of a 5 x 10 9 yr theoretical isochrone. Present results show that, even for this age, theory predicts a cluster turn-off luminosity approximately 0.5 to 1.0 mag fainter than the observed turn-offs of globular clusters. Unsatisfactory agreement between theoretical and observed luminosity functions is also indicated. (author)
Quantum black holes and Planck's constant
International Nuclear Information System (INIS)
Ross, D.K.
1987-01-01
It is shown that the Planck-scale black holes of quantum gravity must obey a consistency condition relating Planck's constant to the integral of the mass of the black holes over time, if the usual path integral formulation of quantum mechanics is to make sense on physical spacetime. It is also shown, using time-dependent perturbation theory in ordinary quantum mechanics, that a massless particle will not propagate on physical spacetime with the black holes present unless the same condition is met. (author)
Constant displacement rate testing at elevated temperatures
International Nuclear Information System (INIS)
Pepe, J.J.; Gonyea, D.C.
1989-01-01
A short time test has been developed which is capable of determining the long time notch sensitivity tendencies of CrMoV rotor forging materials. This test is based on Constant Displacement Rate (CDR) testing of a specific notch bar specimen at 1200 0 F at 2 mils/in/hour displacement rate. These data were correlated to conventional smooth and notch bar rupture behavior for a series of CrMoV materials with varying long time ductility tendencies. The purpose of this paper is to describe the details of this new test procedure and some of the relevant mechanics of material information generated during its development
Radiation balances and the solar constant
Crommelynck, D.
1981-01-01
The radiometric concepts are defined in order to consider various types of radiation balances and relate them to the diabetic form of the energy balance. Variability in space and time of the components of the radiation field are presented. A specific concept for sweeping which is tailored to the requirements is proposed. Finally, after establishing the truncated character of the present knowledge of the radiation balance. The results of the last observations of the solar constant are given. Ground and satellite measurement techniques are discussed.
O(4) texture with a cosmological constant
International Nuclear Information System (INIS)
Cho, Inyong
2002-01-01
We investigate O(4) textures in a background with a positive cosmological constant. We find static solutions which comove with the expanding background. There exists a solution in which the scalar field is regular at the horizon. This solution has a noninteger winding number smaller than 1. There also exist solutions in which scalar-field derivatives are singular at the horizon. Such solutions can complete one winding within the horizon. If the winding number is larger than some critical value, static solutions including the regular one are unstable under perturbations
Can the cosmological constant undergo abrupt changes?
Cabo-Montes de Oca, Alejandro; Rosabal, A; Cabo, Alejandro; Garcia-Chung, Alejandro; Rosabal, Alejandro
2005-01-01
The existence of a simple spherically symmetric and static solution of the Einstein equations in the presence of a cosmological constant vanishing outside a definite value of the radial distance is investigated. A particular succession of field configurations, which are solutions of the Einstein equations in the presence of the considered cosmological term and auxiliary external sources, is constructed. Then, it is shown that the associated succession of external sources tend to zero in the sense of the generalized functions. The type of weak solution that is found becomes the deSitter homogeneous space-time for the interior region, and the Schwartzschild space in the outside zone.
The Boltzmann constant from a snifter
International Nuclear Information System (INIS)
Tyukodi, B; Sárközi, Zs; Néda, Z; Tunyagi, A; Györke, E
2012-01-01
Evaporation of a small glass of ethylic alcohol is studied both experimentally and through an elementary thermal physics approach. For a cylindrical beaker and no air flow in the room, a simple quadratic relation is found between the evaporation time and the mass of evaporated liquid. This problem and the obtained results offer excellent possibilities for simple student experiments and for testing basic principles of thermal physics. As an example, we use the obtained results for estimating the value of the Boltzmann constant from evaporation experiments. (paper)
Asymptotics with a positive cosmological constant II
Kesavan, Aruna; Ashtekar, Abhay; Bonga, Beatrice
2015-04-01
The study of isolated systems has been vastly successful in the context of vanishing cosmological constant, Λ = 0 . However, there is no physically useful notion of asymptotics for the universe we inhabit with Λ > 0 . This means that presently there is no fundamental understanding of gravitational waves in our own universe. The full non-linear framework is still under development, but some interesting results at the linearized level have been obtained. In particular, I will discuss the quadrupole formula for gravitational radiation and its implications.
Positive Cosmological Constant and Quantum Theory
Directory of Open Access Journals (Sweden)
Felix M. Lev
2010-11-01
Full Text Available We argue that quantum theory should proceed not from a spacetime background but from a Lie algebra, which is treated as a symmetry algebra. Then the fact that the cosmological constant is positive means not that the spacetime background is curved but that the de Sitter (dS algebra as the symmetry algebra is more relevant than the Poincare or anti de Sitter ones. The physical interpretation of irreducible representations (IRs of the dS algebra is considerably different from that for the other two algebras. One IR of the dS algebra splits into independent IRs for a particle and its antiparticle only when Poincare approximation works with a high accuracy. Only in this case additive quantum numbers such as electric, baryon and lepton charges are conserved, while at early stages of the Universe they could not be conserved. Another property of IRs of the dS algebra is that only fermions can be elementary and there can be no neutral elementary particles. The cosmological repulsion is a simple kinematical consequence of dS symmetry on quantum level when quasiclassical approximation is valid. Therefore the cosmological constant problem does not exist and there is no need to involve dark energy or other fields for explaining this phenomenon (in agreement with a similar conclusion by Bianchi and Rovelli.
Advances in constant-velocity Moessbauer instrumentation
International Nuclear Information System (INIS)
Veiga, A.; Martinez, N.; Zelis, P. Mendoza; Pasquevich, G. A.; Sanchez, F. H.
2006-01-01
A prototype of a programmable constant-velocity scaler is presented. This instrument allows the acquisition of partial Moessbauer spectra in selected energy regions using standard drivers and transducers. It can be fully operated by a remote application, thus data acquisition can be automated. The instrument consists of a programmable counter and a constant-velocity reference. The reference waveform generator is amplitude modulated with 13-bit resolution, and is programmable in a wide range of frequencies and waveforms in order to optimize the performance of the transducer. The counter is compatible with most standard SCA, and is configured as a rate-meter that provides counts per selectable time slice at the programmed velocity. As a demonstration of the instrument applications, a partial Moessbauer spectrum of a natural iron foil was taken. Only positive energies were studied in 512 channels, accumulating 20 s per channel. A line width of 0.20 mm/s was achieved, performing with an efficiency of 80%.
Local Pain Dynamics during Constant Exhaustive Exercise.
Directory of Open Access Journals (Sweden)
Agne Slapsinskaite
Full Text Available The purpose of this study was to delineate the topological dynamics of pain and discomfort during constant exercise performed until volitional exhaustion. Eleven physical education students were tested while cycling and running at a "hard" intensity level (e.g., corresponding to Borg's RPE (6-20 = 15. During the tests, participants reported their discomfort and pain on a body map every 15s. "Time on task" for each participant was divided into five equal non-overlapping temporal windows within which their ratings were considered for analysis. The analyses revealed that the number of body locations with perceived pain and discomfort increased throughout the five temporal windows until reaching the mean (± SE values of 4.2 ± 0.7 and 4.1 ± 0.6 in cycling and running, respectively. The dominant locations included the quadriceps and hamstrings during cycling and quadriceps and chest during running. In conclusion, pain seemed to spread throughout the body during constant cycling and running performed up to volitional exhaustion with differences between cycling and running in the upper body but not in the lower body dynamics.
Ventricular fibrillation time constant for swine
International Nuclear Information System (INIS)
Wu, Jiun-Yan; Sun, Hongyu; Nimunkar, Amit J; Webster, John G; O'Rourke, Ann; Huebner, Shane; Will, James A
2008-01-01
The strength–duration curve for cardiac excitation can be modeled by a parallel resistor–capacitor circuit that has a time constant. Experiments on six pigs were performed by delivering current from the X26 Taser dart at a distance from the heart to cause ventricular fibrillation (VF). The X26 Taser is an electromuscular incapacitation device (EMD), which generates about 50 kV and delivers a pulse train of about 15–19 pulses s −1 with a pulse duration of about 150 µs and peak current about 2 A. Similarly a continuous 60 Hz alternating current of the amplitude required to cause VF was delivered from the same distance. The average current and duration of the current pulse were estimated in both sets of experiments. The strength–duration equation was solved to yield an average time constant of 2.87 ms ± 1.90 (SD). Results obtained may help in the development of safety standards for future electromuscular incapacitation devices (EMDs) without requiring additional animal tests
Simple liquid models with corrected dielectric constants
Fennell, Christopher J.; Li, Libo; Dill, Ken A.
2012-01-01
Molecular simulations often use explicit-solvent models. Sometimes explicit-solvent models can give inaccurate values for basic liquid properties, such as the density, heat capacity, and permittivity, as well as inaccurate values for molecular transfer free energies. Such errors have motivated the development of more complex solvents, such as polarizable models. We describe an alternative here. We give new fixed-charge models of solvents for molecular simulations – water, carbon tetrachloride, chloroform and dichloromethane. Normally, such solvent models are parameterized to agree with experimental values of the neat liquid density and enthalpy of vaporization. Here, in addition to those properties, our parameters are chosen to give the correct dielectric constant. We find that these new parameterizations also happen to give better values for other properties, such as the self-diffusion coefficient. We believe that parameterizing fixed-charge solvent models to fit experimental dielectric constants may provide better and more efficient ways to treat solvents in computer simulations. PMID:22397577
Holographic dark energy with cosmological constant
Hu, Yazhou; Li, Miao; Li, Nan; Zhang, Zhenhui
2015-08-01
Inspired by the multiverse scenario, we study a heterotic dark energy model in which there are two parts, the first being the cosmological constant and the second being the holographic dark energy, thus this model is named the ΛHDE model. By studying the ΛHDE model theoretically, we find that the parameters d and Ωhde are divided into a few domains in which the fate of the universe is quite different. We investigate dynamical behaviors of this model, and especially the future evolution of the universe. We perform fitting analysis on the cosmological parameters in the ΛHDE model by using the recent observational data. We find the model yields χ2min=426.27 when constrained by Planck+SNLS3+BAO+HST, comparable to the results of the HDE model (428.20) and the concordant ΛCDM model (431.35). At 68.3% CL, we obtain -0.07<ΩΛ0<0.68 and correspondingly 0.04<Ωhde0<0.79, implying at present there is considerable degeneracy between the holographic dark energy and cosmological constant components in the ΛHDE model.
Holographic dark energy with cosmological constant
Energy Technology Data Exchange (ETDEWEB)
Hu, Yazhou; Li, Nan; Zhang, Zhenhui [State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, Beijing, 100190 (China); Li, Miao, E-mail: asiahu@itp.ac.cn, E-mail: mli@itp.ac.cn, E-mail: linan@itp.ac.cn, E-mail: zhangzhh@mail.ustc.edu.cn [School of Astronomy and Space Science, Sun Yat-Sen University, Guangzhou 510275 (China)
2015-08-01
Inspired by the multiverse scenario, we study a heterotic dark energy model in which there are two parts, the first being the cosmological constant and the second being the holographic dark energy, thus this model is named the ΛHDE model. By studying the ΛHDE model theoretically, we find that the parameters d and Ω{sub hde} are divided into a few domains in which the fate of the universe is quite different. We investigate dynamical behaviors of this model, and especially the future evolution of the universe. We perform fitting analysis on the cosmological parameters in the ΛHDE model by using the recent observational data. We find the model yields χ{sup 2}{sub min}=426.27 when constrained by Planck+SNLS3+BAO+HST, comparable to the results of the HDE model (428.20) and the concordant ΛCDM model (431.35). At 68.3% CL, we obtain −0.07<Ω{sub Λ0}<0.68 and correspondingly 0.04<Ω{sub hde0}<0.79, implying at present there is considerable degeneracy between the holographic dark energy and cosmological constant components in the ΛHDE model.
Holographic dark energy with cosmological constant
International Nuclear Information System (INIS)
Hu, Yazhou; Li, Nan; Zhang, Zhenhui; Li, Miao
2015-01-01
Inspired by the multiverse scenario, we study a heterotic dark energy model in which there are two parts, the first being the cosmological constant and the second being the holographic dark energy, thus this model is named the ΛHDE model. By studying the ΛHDE model theoretically, we find that the parameters d and Ω hde are divided into a few domains in which the fate of the universe is quite different. We investigate dynamical behaviors of this model, and especially the future evolution of the universe. We perform fitting analysis on the cosmological parameters in the ΛHDE model by using the recent observational data. We find the model yields χ 2 min =426.27 when constrained by Planck+SNLS3+BAO+HST, comparable to the results of the HDE model (428.20) and the concordant ΛCDM model (431.35). At 68.3% CL, we obtain −0.07<Ω Λ0 <0.68 and correspondingly 0.04<Ω hde0 <0.79, implying at present there is considerable degeneracy between the holographic dark energy and cosmological constant components in the ΛHDE model
Modified large number theory with constant G
International Nuclear Information System (INIS)
Recami, E.
1983-01-01
The inspiring ''numerology'' uncovered by Dirac, Eddington, Weyl, et al. can be explained and derived when it is slightly modified so to connect the ''gravitational world'' (cosmos) with the ''strong world'' (hadron), rather than with the electromagnetic one. The aim of this note is to show the following. In the present approach to the ''Large Number Theory,'' cosmos and hadrons are considered to be (finite) similar systems, so that the ratio R-bar/r-bar of the cosmos typical length R-bar to the hadron typical length r-bar is constant in time (for instance, if both cosmos and hadrons undergo an expansion/contraction cycle: according to the ''cyclical big-bang'' hypothesis: then R-bar and r-bar can be chosen to be the maximum radii, or the average radii). As a consequence, then gravitational constant G results to be independent of time. The present note is based on work done in collaboration with P.Caldirola, G. D. Maccarrone, and M. Pavsic
Lepton Collider Operation with Constant Currents
Wienands, Ulrich
2005-01-01
Traditionally, electron-positron colliders have been operating in a top-off-and-coast fashion with a cycle time depending on the beam life time, typically on the order of an hour. Each top-off involves ramping detector systems in addition to the actual filling time. The loss in accumulated luminosity is typically 20-50%. During the last year, both B-Factories have commissioned a continuous-injection mode of operation in which beam is injected without ramping the detector, thus raising luminosity integration by constant operation at peak luminosity. Constant beam currents reduce thermal drift and trips caused by change in beam loading. To achieve this level of operation, special efforts were made to reduce the injection losses and also to implement special gating procedures in the detectors, minimizing dead time. Bunch-injection control decides which bunch to inject into next while maintaining small charge variation between bunches. Beam collimation can reduce injection noise but also cause an increase in back...
PREFACE: Fundamental Constants in Physics and Metrology
Klose, Volkmar; Kramer, Bernhard
1986-01-01
This volume contains the papers presented at the 70th PTB Seminar which, the second on the subject "Fundamental Constants in Physics and Metrology", was held at the Physikalisch-Technische Bundesanstalt in Braunschweig from October 21 to 22, 1985. About 100 participants from the universities and various research institutes of the Federal Republic of Germany participated in the meeting. Besides a number of review lectures on various broader subjects there was a poster session which contained a variety of topical contributed papers ranging from the theory of the quantum Hall effect to reports on the status of the metrological experiments at the PTB. In addition, the participants were also offered the possibility to visit the PTB laboratories during the course of the seminar. During the preparation of the meeting we noticed that even most of the general subjects which were going to be discussed in the lectures are of great importance in connection with metrological experiments and should be made accessible to the scientific community. This eventually resulted in the idea of the publication of the papers in a regular journal. We are grateful to the editor of Metrologia for providing this opportunity. We have included quite a number of papers from basic physical research. For example, certain aspects of high-energy physics and quantum optics, as well as the many-faceted role of Sommerfeld's fine-structure constant, are covered. We think that questions such as "What are the intrinsic fundamental parameters of nature?" or "What are we doing when we perform an experiment?" can shed new light on the art of metrology, and do, potentially, lead to new ideas. This appears to be especially necessary when we notice the increasing importance of the role of the fundamental constants and macroscopic quantum effects for the definition and the realization of the physical units. In some cases we have reached a point where the limitations of our knowledge of a fundamental constant and
Han, Won-Sik; Han, Jung-Kyu; Kim, Hyun-Young; Choi, Mi Jin; Kang, Yong-Soo; Pac, Chyongjin; Kang, Sang Ook
2011-04-18
We prepared a series of new heteroleptic ruthenium(II) complexes, Ru(NCS)(2)LL' (3a-3e), where L is 4,4'-di(hydroxycarbonyl)-2,2'-bipyridine and L' is 4,4'-di(p-X-phenyl)-2,2'-pyridine (X = CN (a), F (b), H (c), OMe (d), and NMe(2) (e)), in an attempt to explore the structure-activity relationships in their photophysical and electrochemical behavior and in their performance in dye-sensitized solar cells (DSSCs). When substituent X is changed from electron-donating NMe(2) to electron-withdrawing CN, the absorption and emission maxima reveal systematic bathochromic shifts. The redox potentials of these dyes are also significantly influenced by X. The electronic properties of the dyes were theoretically analyzed using density functional theory calculations; the results show good correlations with the experimental results. The solar-cell performance of DSSCs based on dye-grafted nanocrystalline TiO(2) using 3a-3e and standard N3 (bis[(4,4'-carboxy-2,2'-bipyridine)(thiocyanato)]ruthenium(II)) were compared, revealing substantial dependences on the dye structures, particularly on the remote substituent X. The 3d-based device showed the best performance: η = 8.30%, J(SC) = 16.0 mA·cm(-2), V(OC) = 717 mV, and ff = 0.72. These values are better than N3-based device.
Search for a Variation of Fundamental Constants
Ubachs, W.
2013-06-01
Since the days of Dirac scientists have speculated about the possibility that the laws of nature, and the fundamental constants appearing in those laws, are not rock-solid and eternal but may be subject to change in time or space. Such a scenario of evolving constants might provide an answer to the deepest puzzle of contemporary science, namely why the conditions in our local Universe allow for extreme complexity: the fine-tuning problem. In the past decade it has been established that spectral lines of atoms and molecules, which can currently be measured at ever-higher accuracies, form an ideal test ground for probing drifting constants. This has brought this subject from the realm of metaphysics to that of experimental science. In particular the spectra of molecules are sensitive for probing a variation of the proton-electron mass ratio μ, either on a cosmological time scale, or on a laboratory time scale. A comparison can be made between spectra of molecular hydrogen observed in the laboratory and at a high redshift (z=2-3), using the Very Large Telescope (Paranal, Chile) and the Keck telescope (Hawaii). This puts a constraint on a varying mass ratio Δμ/μ at the 10^{-5} level. The optical work can also be extended to include CO molecules. Further a novel direction will be discussed: it was discovered that molecules exhibiting hindered internal rotation have spectral lines in the radio-spectrum that are extremely sensitive to a varying proton-electron mass ratio. Such lines in the spectrum of methanol were recently observed with the radio-telescope in Effelsberg (Germany). F. van Weerdenburg, M.T. Murphy, A.L. Malec, L. Kaper, W. Ubachs, Phys. Rev. Lett. 106, 180802 (2011). A. Malec, R. Buning, M.T. Murphy, N. Milutinovic, S.L. Ellison, J.X. Prochaska, L. Kaper, J. Tumlinson, R.F. Carswell, W. Ubachs, Mon. Not. Roy. Astron. Soc. 403, 1541 (2010). E.J. Salumbides, M.L. Niu, J. Bagdonaite, N. de Oliveira, D. Joyeux, L. Nahon, W. Ubachs, Phys. Rev. A 86, 022510
Statistical Modelling of the Soil Dielectric Constant
Usowicz, Boguslaw; Marczewski, Wojciech; Bogdan Usowicz, Jerzy; Lipiec, Jerzy
2010-05-01
The dielectric constant of soil is the physical property being very sensitive on water content. It funds several electrical measurement techniques for determining the water content by means of direct (TDR, FDR, and others related to effects of electrical conductance and/or capacitance) and indirect RS (Remote Sensing) methods. The work is devoted to a particular statistical manner of modelling the dielectric constant as the property accounting a wide range of specific soil composition, porosity, and mass density, within the unsaturated water content. Usually, similar models are determined for few particular soil types, and changing the soil type one needs switching the model on another type or to adjust it by parametrization of soil compounds. Therefore, it is difficult comparing and referring results between models. The presented model was developed for a generic representation of soil being a hypothetical mixture of spheres, each representing a soil fraction, in its proper phase state. The model generates a serial-parallel mesh of conductive and capacitive paths, which is analysed for a total conductive or capacitive property. The model was firstly developed to determine the thermal conductivity property, and now it is extended on the dielectric constant by analysing the capacitive mesh. The analysis is provided by statistical means obeying physical laws related to the serial-parallel branching of the representative electrical mesh. Physical relevance of the analysis is established electrically, but the definition of the electrical mesh is controlled statistically by parametrization of compound fractions, by determining the number of representative spheres per unitary volume per fraction, and by determining the number of fractions. That way the model is capable covering properties of nearly all possible soil types, all phase states within recognition of the Lorenz and Knudsen conditions. In effect the model allows on generating a hypothetical representative of
Development code for group constant processing
International Nuclear Information System (INIS)
Su'ud, Z.
1997-01-01
In this paper methods, formalism and algorithm related to group constant processing problem from basic library such as ENDF/B VI will be described. Basically the problems can be grouped as follows; the treatment of resolved resonance using NR approximation, the treatment of unresolved resonance using statistical method, the treatment of low lying resonance using intermediate resonance approximation, the treatment of thermal energy regions, and the treatment group transfer matrices cross sections. it is necessary to treat interference between resonance properly especially in the unresolved region. in this paper the resonance problems are treated based on Breit-wigner method, and doppler function is treated using Pade approximation for calculation efficiency. finally, some samples of calculational result for some nuclei, mainly for comparison between many methods are discussed in this paper
Hawking temperature of constant curvature black holes
International Nuclear Information System (INIS)
Cai Ronggen; Myung, Yun Soo
2011-01-01
The constant curvature (CC) black holes are higher dimensional generalizations of Banados-Teitelboim-Zanelli black holes. It is known that these black holes have the unusual topology of M D-1 xS 1 , where D is the spacetime dimension and M D-1 stands for a conformal Minkowski spacetime in D-1 dimensions. The unusual topology and time-dependence for the exterior of these black holes cause some difficulties to derive their thermodynamic quantities. In this work, by using a globally embedding approach, we obtain the Hawking temperature of the CC black holes. We find that the Hawking temperature takes the same form when using both the static and global coordinates. Also, it is identical to the Gibbons-Hawking temperature of the boundary de Sitter spaces of these CC black holes.
Dielectric Constant Measurements of Solid 4He
Yin, L.; Xia, J. S.; Huan, C.; Sullivan, N. S.; Chan, M. H. W.
2011-03-01
Careful measurements of the dielectric properties of solid 4He have been carried out down to 35 mK, considerably lower than the temperature range of previous studies. The sample was prepared from high purity gas with 3He concentrations of the order of 200 ppb and were formed by the blocked capillary method. The molar volume of the sample was 20.30 cm3. The dielectric constant of the samples was found to be independent of temperature down to 120 mK before showing a continuous increase with decreasing temperature and saturating below 50 mK. The total increase in ɛ is 2 parts in 10-5. The temperature dependence of ɛ mimics the increase in the resonant frequency found in the torsional oscillator studies and also the increase found in the shear modulus measurements.
Parallel computational in nuclear group constant calculation
International Nuclear Information System (INIS)
Su'ud, Zaki; Rustandi, Yaddi K.; Kurniadi, Rizal
2002-01-01
In this paper parallel computational method in nuclear group constant calculation using collision probability method will be discuss. The main focus is on the calculation of collision matrix which need large amount of computational time. The geometry treated here is concentric cylinder. The calculation of collision probability matrix is carried out using semi analytic method using Beckley Naylor Function. To accelerate computation speed some computer parallel used to solve the problem. We used LINUX based parallelization using PVM software with C or fortran language. While in windows based we used socket programming using DELPHI or C builder. The calculation results shows the important of optimal weight for each processor in case there area many type of processor speed
Cosmological constant and general isocurvature initial conditions
International Nuclear Information System (INIS)
Trotta, R.; Riazuelo, A.; Durrer, R.
2003-01-01
We investigate in detail the question of whether a nonvanishing cosmological constant is required by the present-day cosmic microwave background and large scale structure data when general isocurvature initial conditions are taken into account. We also discuss the differences between the usual Bayesian and the frequentist approaches in data analysis. We show that the Cosmic Background Explorer (COBE)-normalized matter power spectrum is dominated by the adiabatic mode and therefore breaks the degeneracy between initial conditions which is present in the cosmic microwave background anisotropies. We find that in a flat universe the Bayesian analysis requires Ω Λ =e0 to more than 3σ, while in the frequentist approach Ω Λ =0 is still within 3σ for a value of h≤0.48. Both conclusions hold regardless of the initial conditions
Constant-parameter capture-recapture models
Brownie, C.; Hines, J.E.; Nichols, J.D.
1986-01-01
Jolly (1982, Biometrics 38, 301-321) presented modifications of the Jolly-Seber model for capture-recapture data, which assume constant survival and/or capture rates. Where appropriate, because of the reduced number of parameters, these models lead to more efficient estimators than the Jolly-Seber model. The tests to compare models given by Jolly do not make complete use of the data, and we present here the appropriate modifications, and also indicate how to carry out goodness-of-fit tests which utilize individual capture history information. We also describe analogous models for the case where young and adult animals are tagged. The availability of computer programs to perform the analysis is noted, and examples are given using output from these programs.
Lepton Collider Operation With Constant Currents
International Nuclear Information System (INIS)
Wienands, U.
2006-01-01
Electron-positron colliders have been operating in a top-up-and-coast fashion with a cycle time depending on the beam life time, typically one or more hours. Each top-up involves ramping detector systems in addition to the actual filling time. The loss in accumulated luminosity may be 20-50%. During the last year, both B-Factories have commissioned a continuous-injection mode of operation in which beam is injected without ramping the detector, thus raising luminosity integration by always operating at peak luminosity. Constant beam currents also reduce thermal drift and trips caused by change in beam loading. To achieve this level of operation, special efforts were made to reduce the injection losses and also to implement gating procedures in the detectors, minimizing dead time. Beam collimation can reduce injection noise but also cause an increase in background rates. A challenge can be determining beam lifetime, important to maintain tuning of the beams
Higgs inflation and the cosmological constant
Energy Technology Data Exchange (ETDEWEB)
Jegerlehner, Fred [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Physik; Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany)
2014-02-15
The Higgs not only induces the masses of all SM particles, the Higgs, given its special mass value, is the natural candidate for the inflaton and in fact is ruling the evolution of the early universe, by providing the necessary dark energy which remains the dominant energy density. SM running couplings not only allow us to extrapolate SM physics up to the Planck scale, but equally important they are triggering the Higgs mechanism. This is possible by the fact that the bare mass term in the Higgs potential changes sign at about μ{sub 0}≅1.40 x 10{sup 16} GeV and in the symmetric phase is enhanced by quadratic terms in the Planck mass. Such a huge Higgs mass term is able to play a key role in triggering inflation in the early universe. In this article we extend our previous investigation by working out the details of a Higgs inflation scenario. We show how different terms contributing to the Higgs Lagrangian are affecting inflation. Given the SM and its extrapolation to scales μ>μ{sub 0} we find a calculable cosmological constant V(0) which is weakly scale dependent and actually remains large during inflation. This is different to the Higgs fluctuation field dependent ΔV(φ), which decays exponentially during inflation, and actually would not provide a sufficient amount of inflation. The fluctuation field has a different effective mass which shifts the bare Higgs transition point to a lower value μ'{sub 0} ≅7.7 x 10{sup 14} GeV. The vacuum energy V(0) being proportional to M{sub Pl}{sup 4} has a coefficient which vanishes near the Higgs transition point, such that the bare and the renormalized cosmological constant match at this point. The role of the Higgs in reheating and baryogenesis is emphasized.
Universal equations and constants of turbulent motion
International Nuclear Information System (INIS)
Baumert, H Z
2013-01-01
This paper presents a parameter-free theory of shear-generated turbulence at asymptotically high Reynolds numbers in incompressible fluids. It is based on a two-fluids concept. Both components are materially identical and inviscid. The first component is an ensemble of quasi-rigid dipole-vortex tubes (vortex filaments, excitations) as quasi-particles in chaotic motion. The second is a superfluid performing evasive motions between the tubes. The local dipole motions follow Helmholtz' law. The vortex radii scale with the energy-containing length scale. Collisions between quasi-particles lead either to annihilation (likewise rotation, turbulent dissipation) or to scattering (counterrotation, turbulent diffusion). There are analogies with birth and death processes of population dynamics and their master equations and with Landau's two-fluid theory of liquid helium. For free homogeneous decay the theory predicts the turbulent kinetic energy to follow t −1 . With an adiabatic wall condition it predicts the logarithmic law with von Kármán's constant as 1/√(2 π)= 0.399. Likewise rotating couples form localized dissipative patches almost at rest (→ intermittency) wherein under local quasi-steady conditions the spectrum evolves into an ‘Apollonian gear’ as discussed first by Herrmann (1990 Correlation and Connectivity (Dordrecht: Kluwer) pp 108–20). Dissipation happens exclusively at scale zero and at finite scales this system is frictionless and reminds of Prigogine's (1947 Etude Thermodynamique des Phenomenes Irreversibles (Liege: Desoer) p 143) law of minimum (here: zero) entropy production. The theory predicts further the prefactor of the 3D-wavenumber spectrum (a Kolmogorov constant) as 1/3 (4 π) 2/3 =1.802, well within the scatter range of observational, experimental and direct numerical simulation results. (paper)
Universal equations and constants of turbulent motion
Baumert, H. Z.
2013-07-01
This paper presents a parameter-free theory of shear-generated turbulence at asymptotically high Reynolds numbers in incompressible fluids. It is based on a two-fluids concept. Both components are materially identical and inviscid. The first component is an ensemble of quasi-rigid dipole-vortex tubes (vortex filaments, excitations) as quasi-particles in chaotic motion. The second is a superfluid performing evasive motions between the tubes. The local dipole motions follow Helmholtz' law. The vortex radii scale with the energy-containing length scale. Collisions between quasi-particles lead either to annihilation (likewise rotation, turbulent dissipation) or to scattering (counterrotation, turbulent diffusion). There are analogies with birth and death processes of population dynamics and their master equations and with Landau's two-fluid theory of liquid helium. For free homogeneous decay the theory predicts the turbulent kinetic energy to follow t-1. With an adiabatic wall condition it predicts the logarithmic law with von Kármán's constant as 1/\\sqrt {2\\,\\pi }= 0.399 . Likewise rotating couples form localized dissipative patches almost at rest (→ intermittency) wherein under local quasi-steady conditions the spectrum evolves into an ‘Apollonian gear’ as discussed first by Herrmann (1990 Correlation and Connectivity (Dordrecht: Kluwer) pp 108-20). Dissipation happens exclusively at scale zero and at finite scales this system is frictionless and reminds of Prigogine's (1947 Etude Thermodynamique des Phenomenes Irreversibles (Liege: Desoer) p 143) law of minimum (here: zero) entropy production. The theory predicts further the prefactor of the 3D-wavenumber spectrum (a Kolmogorov constant) as \\frac {1}{3}(4\\,\\pi )^{2/3}=1.802 , well within the scatter range of observational, experimental and direct numerical simulation results.
Constant Leverage And Constant Cost Of Capital: A Common Knowledge Half-Truth
Directory of Open Access Journals (Sweden)
Ignacio Vélez–Pareja
2008-04-01
In this document we show that for finite cash flows, Ke and hence WACC depend on the discount rate that is used to value the tax shield, TS and as expected, Ke and WACC are not constant with Kd as the discount rate for the tax shield, even if the leverage is constant. We illustrate this situation with a simple example. We analyze five methods: DCF using APV, FCF and traditional and general formulation for WACC, present value of CFE plus debt and Capital Cash Flow, CCF.
Dihydroazulene Photochromism:Synthesis, Molecular Electronics and Hammett Correlations
DEFF Research Database (Denmark)
Broman, Søren Lindbæk
This thesis describes the development of a versatile synthetic protocol for preparation of a large selection of dihydroazulenes (DHAs) with both electron withdrawing and donating groups. By UV-Vis and NMR spectroscopies and even in a single-molecule junction, their ability to undergo a light...... will be discussed in detail. The second chapter describes the design and synthesis of DHA/VHFs intended for use in molecular electronics and their solution and single-molecule junction switching properties. By the expansion of the recently reported procedure for functionalization of this system by Suzuki cross...
Some aspects of preparation and testing of group constants group constant system ABBN-90
International Nuclear Information System (INIS)
Nikolaev, M.N.; Tsiboulia, A.M.; Manturov, G.N.
1996-01-01
This paper presents an overview of activities performed to prepare and test the group constants ABBN-90. The ABBN-90 set is designed for application calculations of fast, intermediate and thermal nuclear reactors. The calculations of subgroup parameters are discussed. The processing code system GRUCON is mentioned in comparison to the NJOY code system. Proposals are made for future activities. (author). Figs, tabs
International Nuclear Information System (INIS)
Nesterov, S.V.; Panov, O.Yu.
1998-01-01
Intermediates stabilized in γ-irradiated mono- and dibenzosubstituted crown ethers are studied by ESR spectroscopy at 77 K. PhO · radicals and radicals with H-atom abstraction from polyether ring are the main products at low temperature γ-radiolysis. The nature of radicals produced in radiolysis and the yield of radicals, G R , depend on macroring size and on the number of aromatic substituents. Negative deviation from additive rule in function of G R versus ε of substituents is an evidence of efficient transfer of adsorbed energy to the π-system of aromatic group. (author)
Gao, Yingning; Ma, Pan; Chen, Yanli; Zhang, Ying; Bian, Yongzhong; Li, Xiyou; Jiang, Jianzhuang; Ma, Changqin
2009-01-05
Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10
Price of shifting the Hubble constant
Evslin, Jarah; Sen, Anjan A.; Ruchika
2018-05-01
An anisotropic measurement of the baryon acoustic oscillation (BAO) feature fixes the product of the Hubble constant and the acoustic scale H0rd. Therefore, regardless of the dark energy dynamics, to accommodate a higher value of H0 one needs a lower rd and so necessarily a modification of early time cosmology. One must either reduce the age of the Universe at the drag epoch or else the speed of sound in the primordial plasma. The first can be achieved, for example, with dark radiation or very early dark energy, automatically preserving the angular size of the acoustic scale in the cosmic microwave background (CMB) with no modifications to post-recombination dark energy. However, it is known that the simplest such modifications fall afoul of CMB constraints at higher multipoles. As an example, we combine anisotropic BAO with geometric measurements from strong lensing time delays from H0LiCOW and megamasers from the Megamaser Cosmology Project to measure rd, with and without the local distance ladder measurement of H0. We find that the best fit value of rd is indeed quite insensitive to the dark energy model and is also hardly affected by the inclusion of the local distance ladder data.
Trinucleon asymptotic normalization constants including Coulomb effects
International Nuclear Information System (INIS)
Friar, J.L.; Gibson, B.F.; Lehman, D.R.; Payne, G.L.
1982-01-01
Exact theoretical expressions for calculating the trinucleon S- and D-wave asymptotic normalization constants, with and without Coulomb effects, are presented. Coordinate-space Faddeev-type equations are used to generate the trinucleon wave functions, and integral relations for the asymptotic norms are derived within this framework. The definition of the asymptotic norms in the presence of the Coulomb interaction is emphasized. Numerical calculations are carried out for the s-wave NN interaction models of Malfliet and Tjon and the tensor force model of Reid. Comparison with previously published results is made. The first estimate of Coulomb effects for the D-wave asymptotic norm is given. All theoretical values are carefully compared with experiment and suggestions are made for improving the experimental situation. We find that Coulomb effects increase the 3 He S-wave asymptotic norm by less than 1% relative to that of 3 H, that Coulomb effects decrease the 3 He D-wave asymptotic norm by approximately 8% relative to that of 3 H, and that the distorted-wave Born approximation D-state parameter, D 2 , is only 1% smaller in magnitude for 3 He than for 3 H due to compensating Coulomb effects
Magnetically modified biocells in constant magnetic field
Energy Technology Data Exchange (ETDEWEB)
Abramov, E.G.; Panina, L.K. [Saint Petersburg State University, St. Petersburg (Russian Federation); Kolikov, V.A., E-mail: kolikov1@yandex.ru [Institute for Electrophysics and Electric Power of the RAS, St. Petersburg (Russian Federation); Bogomolova, E.V. [Botanical Institute of the RAS after V.L.Komarov, St. Petersburg (Russian Federation); Snetov, V.N. [Institute for Electrophysics and Electric Power of the RAS, St. Petersburg (Russian Federation); Cherepkova, I.A. [Saint Petersburg State Institute of Technology, St. Petersburg (Russian Federation); Kiselev, A.A. [Institute for Electrophysics and Electric Power of the RAS, St. Petersburg (Russian Federation)
2017-02-01
Paper addresses the inverse problem in determining the area, where the external constant magnetic field captures the biological cells modified by the magnetic nanoparticles. Zero velocity isolines, in area where the modified cells are captured by the magnetic field were determined by numerical method for two locations of the magnet. The problem was solved taking into account the gravitational field, magnetic induction, density of medium, concentration and size of cells, and size and magnetization of nanoparticles attached to the cell. Increase in the number of the nanoparticles attached to the cell and decrease in the cell’ size, enlarges the area, where the modified cells are captured and concentrated by the magnet. Solution is confirmed by the visible pattern formation of the modified cells Saccharomyces cerevisiae. - Highlights: • The inverse problem was solved for finding zero velocity isolines of magnetically modified biological cells. • Solution of the inverse problem depends on the size of cells and the number of nanoparticles attached to the single cell. • The experimental data are in agreement with theoretical solution.
Analysis of the chemical equilibrium of combustion at constant volume
Directory of Open Access Journals (Sweden)
Marius BREBENEL
2014-04-01
Full Text Available Determining the composition of a mixture of combustion gases at a given temperature is based on chemical equilibrium, when the equilibrium constants are calculated on the assumption of constant pressure and temperature. In this paper, an analysis of changes occurring when combustion takes place at constant volume is presented, deriving a specific formula of the equilibrium constant. The simple reaction of carbon combustion in pure oxygen in both cases (constant pressure and constant volume is next considered as example of application, observing the changes occurring in the composition of the combustion gases depending on temperature.
Berber, Hatice; Lameiras, Pedro; Denhez, Clément; Antheaume, Cyril; Clayden, Jonathan
2014-07-03
Terpenylation reactions of substituted phenols were used to prepare cannabidiol and linderatin derivatives, and their structure and conformational behavior in solution were investigated by NMR and, for some representative examples, by DFT. VT-NMR spectra and DFT calculations were used to determine the activation energies of the conformational change arising from restricted rotation about the aryl-Csp(3) bond that lead to two unequally populated rotameric epimers. The NBO calculation was applied to explain the electronic stabilization of one conformer over another by donor-acceptor charge transfer interactions. Conformational control arises from a combination of stereoelectronic and steric effects between substituents in close contact with each other on the two rings of the endocyclic epoxide atropisomers. This study represents the first exploration of the stereoelectronic origins of atropisomerism around C(sp(2))-C(sp(3)) single bonds through theoretical calculations.
Pouzar, Vladimír; Cerný, Ivan; Hill, Martin; Bicíková, Marie; Hampl, Richard
2005-10-01
Derivatives of 16alpha-hydroxy-dehydroepiandrosterone, which have an additional oxygen substituent at position 7 (oxo or hydroxy group), were synthesized. Firstly, 17,17-dimethoxyandrost-5-ene-3beta,16alpha-diyl diacetate was prepared and then oxidized with a complex of chromium(VI) oxide and 2,5-dimethylpyrazole to the respective 7-oxo derivative. This key intermediate was both deprotected or reduced by l-Selectride or sodium borohydride in the presence of cerium(III) chloride and then deprotected to give 7-oxo, 7alpha-hydroxy and 7beta-hydroxy derivatives of 16alpha-hydroxy-dehydroepiandrosterone. The target compounds were characterized by (1)H and (13)C NMR spectra and in the form of O-methyloxime-trimethylsilyl derivatives, by gas chromatography/mass spectrometry methods.
Fröhlich, Richard F G; Furneaux, Richard H; Mahuran, Don J; Saf, Robert; Stütz, Arnold E; Tropak, Michael B; Wicki, Jacqueline; Withers, Stephen G; Wrodnigg, Tanja M
2011-09-06
Two simple and reliably accessible intermediates, N-carboxypentyl- and N-aminohexyl-1-deoxy-D-galactonojirimycin were employed for the synthesis of a set of terminally N-dansyl substituted derivatives. Reaction of the terminal carboxylic acid of N-carboxypentyl-1-deoxy-D-galactonojirimycin with N-dansyl-1,6-diaminohexane provided the chain-extended fluorescent derivative. Employing bis(6-dansylaminohexyl)amine, the corresponding branched di-N-dansyl compound was obtained. Partially protected N-aminohexyl-1-deoxy-D-galactonojirimycin served as intermediate for two additional chain-extended fluorescent 1-deoxy-D-galactonojirimycin (1-DGJ) derivatives featuring terminal dansyl groups in the N-alkyl substituent. These new compounds are strong inhibitors of d-galactosidases and may serve as leads en route to pharmacological chaperones for GM1-gangliosidosis. Copyright © 2011. Published by Elsevier Ltd.
DEFF Research Database (Denmark)
Dahl, Bjarne H.; Nielsen, John; Dahl, Otto
1987-01-01
, and that dialkylammonium tetrazolide salts are inhibitors. These and other facts are evidence that the reactions are subjected to nucleophilic catalysis by tetrazole, in addition to acid catalysis. The rate variations with phosphorus substituents of 1a-h are NEt 2 > NRr12 > N(CH 2CH 2)O > NMePh, and OMe > OCH 2CH 2CN......Tetrazole catalyzed reactions of a series of phosphoramidites, 5′ -O- DMTdT-3′-O-P(OR 1)NRNR22 (1a-h), with 3′ O-SiBu tPh 2-6-N-benzoyl-dA (2a) in acetonitrite solution have been studied. It is found that the coupling rate depends very much on whether tetrazole is added before or after 2a...
Weiss, Stefan; Keller, Max; Bernhardt, Günther; Buschauer, Armin; König, Burkhard
2010-09-01
N(G)-Acylated argininamides, covering a broad range of lipophilicity (calculated logD values: -1.8-12.5), were synthesized and investigated for NPY Y(1) receptor (Y(1)R) antagonism, Y(1)R affinity and stability in buffer (N(G)-deacylation, yielding BIBP 3226). Broad structural variation of substituents was tolerated. The K(i) (binding) and K(b) values (Y(1)R antagonism) varied from low nM to one-digit muM. Most of the compounds proved to be sufficiently stable at pH 7.4 over 90min to determine reliable pharmacological data in vitro. Exceptionally high instability was detected when a succinyl moiety was attached to the guanidine, probably, due to an intramolecular cleavage mechanism. Copyright 2010 Elsevier Ltd. All rights reserved.
Energy Technology Data Exchange (ETDEWEB)
Shi, Ming W.; Stewart, Scott G.; Sobolev, Alexandre N.; Dittrich, Birger; Schirmeister, Tanja; Luger, Peter; Hesse, Malte; Chen, Yu-Sheng; Spackman, Peter R.; Spackman, Mark A.; Grabowsky, Simon (Heinrich-Heine); (Freie); (UC); (Bremen); (JG-UM); (UWA)
2017-01-24
The trans-epoxysuccinyl amide group as a biologically active moiety in cysteine protease inhibitors such as loxistatin acid E64c has been used as a benchmark system for theoretical studies of environmental effects on the electron density of small active ingredients in relation to their biological activity. Here, the synthesis and the electronic properties of the smallest possible active site model compound are reported to close the gap between the unknown experimental electron density of trans-epoxysuccinyl amides and the well-known function of related drugs. Intramolecular substituent effects are separated from intermolecular crystal packing effects on the electron density, which allows us to predict the conditions under which an experimental electron density investigation on trans-epoxysuccinyl amides will be possible. In this context, the special importance of the carboxylic acid function in the model compound for both crystal packing and biological activity is revealed through the novel tool of model energy analysis.
Ziółkowska, Natasza E.; Michejda, Christopher J.; Bujacz, Grzegorz D.
2010-03-01
Over the past 10 years, several anti-viral drugs have become available to fight the HIV infection. Antiretroviral treatment reduces the mortality of AIDS. Nonnucleoside inhibitors of HIV-1 reverse transcriptase are specific and potentially nontoxic drugs against AIDS. The crystal structures of five nonnucleoside inhibitors of HIV-1 reverse transcriptase are presented here. The structural parameters, especially those describing the angular orientation of the π-electron systems and influencing biological activity, were determined for all of the investigated inhibitors. The chemical character and orientation of the substituent at C4 position of the benzimidazole moiety substantially influences the anti-viral activity. The structural data of the investigated inhibitors is a good basis for modeling enzyme-inhibitor interactions for structure-assisted drug design.
International Nuclear Information System (INIS)
Shi Minmin; Lin Jiajun; Shi Yuewen; Ouyang Mi; Wang Mang; Chen Hongzheng
2009-01-01
A novel blue-emissive Alq 3 derivative, tris-(4-methyl-6-fluoro-8-hydroxyquinoline) aluminum (6), has been designed and prepared. Because the strong electronegative F atom at 6-position lowers the HOMO significantly and the weak electron-donating methyl group at 4-position retains the drop of the LUMO, the band gap of 6 is broadened, and a blue-shift by 53 nm of the emission peak (λ em ) with substantially enhanced intensity is demonstrated when compared to that of Alq 3 . It is also found that 6 possesses good thermal stability and solubility in common solvents. Through theoretical simulations of the frontier orbitals, it is disclosed that 6's λ em can be blue-shifted further if methyl is replaced with a stronger electron-donating substituent, such as methoxy or N,N'-dimethylamino group.
Energy Technology Data Exchange (ETDEWEB)
Savvin, S B; Dedkova, V P; Azarashvili, M A; Likhonina, E A
1988-08-01
Effect of acceptor and donor substituents in a reagent on degree of contrast and selectivity of spectrophotometric beryllium determination as well as other elements was considered taking derivatives of orthanilic-azo-chromotropic acid as an example. The optimal pH region of aminoorthanilic-azo-chromotropic acid interaction with Be 5-6.5; the optimal wavelength is 640 nm. The solution colour changes from violet-red to blue during complex formation. Selectivity increases after addition of masking substances. Be determination on the background of 4-fold Cu and VO/sup 2+/ amounts 8-fold Al amounts, 2-fold Zn amounts is possible in the presence of 5-fold EDTA amounts unsubstituted reagent is characterized by the lowest degree of contrast and selectivity of reactions with metals.
International Nuclear Information System (INIS)
Kochetkova, N.E.; Kojro, O.Eh.; Nesterova, N.P.; Medved', T.Ya.; Chmutova, M.K.; Myasoedov, B.F.; Kabachnik, M.I.
1986-01-01
The influence of substituents in methylene bridge on solubility, extractivity and selectivity of bidentate neutral phosphorus- and phosphorus-nitrogen-containing reagents in the process of U(6), TUE, Eu extraction has been studied. It is ascertained that hydrogen substitution in the bridge of tetraphenylmethylenediphosphine dioxide (1) causes a decrease in the extractivity of reagent as to TPE, uranium (6) and europium. There is no visible regular relation between basicity and extractivity of substituted reagents. Hydrogen substitution in the bridge of diphenyl[diethylcarbamoylmethyl]phosphine oxide (2) causes a decrease in extractivity of the reagent as to TPE, uranium (6) and europium. In contrast to monodentate neutral reagents, when bidentate neutral reagents are used, sometimes no increase in the reagent extractivity with an increase in its basicity is observed. When fragments restricting the conformation mobility of bidentate reagent molecule are introduced in it (here substituents in methylene bridge), it may result in the violation of the regularity, since of all the factors affecting the reagent extractivity the spatial factor may become the prevailing one. On hydrogen substitution in the bridge of 1 separation factors of practically all (with few exceptions) studied pairs of elements increase. Hydrogen substitution in the bridge of 2 causes an increase in separation factor of U (6) /Am pair and it does not affect the separation factor of Am/Eu pair. Hydrogen substitution in the bridge of 1 and 2 does not result in the preparation of more efficient and considerably more selective reagents for extractive isolation and separation of the elements, but some of the substituted reagents (Cl-substituted 1, for instance) may turn out useful for the element separation
Tao, Ran; Umeyama, Tomokazu; Kurotobi, Kei; Imahori, Hiroshi
2014-10-08
A series of alkoxycarbonyl-substituted dihydronaphthyl-based [60]fullerene bis-adduct derivatives (denoted as C2BA, C4BA, and C6BA with the alkyl chain of ethyl, n-butyl, and n-hexyl, respectively) have been synthesized to investigate the effects of alkyl chain length and substituent pattern of fullerene bis-adducts on the film structures and photovoltaic properties of bulk heterojunction polymer solar cells. The shorter alkyl chain length caused lower solubility of the fullerene bis-adducts (C6BA > C4BA > C2BA), thereby resulting in the increased separation difficulty of respective bis-adduct isomers. The device performance based on poly(3-hexylthiophene) (P3HT) and the fullerene bis-adduct regioisomer mixtures was enhanced by shortening the alkyl chain length. When using the regioisomerically separated fullerene bis-adducts, the devices based on trans-2 and a mixture of trans-4 and e of C4BA exhibited the highest power conversion efficiencies of ca. 2.4%, which are considerably higher than those of the C6BA counterparts (ca. 1.4%) and the C4BA regioisomer mixture (1.10%). The film morphologies as well as electron mobilities of the P3HT:bis-adduct blend films were found to affect the photovoltaic properties considerably. These results reveal that the alkyl chain length and substituent pattern of fullerene bis-adducts significantly influence the photovoltaic properties as well as the film structures of bulk heterojunction solar cells.
Directory of Open Access Journals (Sweden)
Li-Na Zhu
Full Text Available The discovery of uncommon DNA structures and speculation about their potential functions in genes has brought attention to specific DNA structure recognition. G-quadruplexes are four-stranded nucleic acid structures formed by G-rich DNA (or RNA sequences. G-rich sequences with a high potential to form G-quadruplexes have been found in many important genomic regions. Porphyrin derivatives with cationic side arm substituents are important G-quadruplex-binding ligands. For example, 5,10,15,20-Tetrakis(N-methylpyridinium-4-yl-21H,23H-porphyrin (TMPyP4, interacts strongly with G-quadruplexes, but has poor selectivity for G-quadruplex versus duplex DNA. To increase the G-quadruplex recognition specificity, a new cationic porphyrin derivative, 5,10,15,20-tetra-{4-[2-(1-methyl-1-piperidinylethoxy]phenyl} porphyrin (TMPipEOPP, with large side arm substituents was synthesized, and the interactions between TMPipEOPP and different DNA structures were compared. The results show that G-quadruplexes cause large changes in the UV-Vis absorption and fluorescence spectra of TMPipEOPP, but duplex and single-stranded DNAs do not, indicating that TMPipEOPP can be developed as a highly specific optical probe for discriminating G-quadruplex from duplex and single-stranded DNA. Visual discrimination is also possible. Job plot and Scatchard analysis suggest that a complicated binding interaction occurs between TMPipEOPP and G-quadruplexes. At a low [G-quadruplex]/[TMPipEOPP] ratio, one G-quadruplex binds two TMPipEOPP molecules by end-stacking and outside binding modes. At a high [G-quadruplex]/[TMPipEOPP] ratio, two G-quadruplexes bind to one TMPipEOPP molecule in a sandwich-like end-stacking mode.
Zhu, Li-Na; Zhao, Shu-Juan; Wu, Bin; Li, Xiao-Zeng; Kong, De-Ming
2012-01-01
The discovery of uncommon DNA structures and speculation about their potential functions in genes has brought attention to specific DNA structure recognition. G-quadruplexes are four-stranded nucleic acid structures formed by G-rich DNA (or RNA) sequences. G-rich sequences with a high potential to form G-quadruplexes have been found in many important genomic regions. Porphyrin derivatives with cationic side arm substituents are important G-quadruplex-binding ligands. For example, 5,10,15,20-Tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphyrin (TMPyP4), interacts strongly with G-quadruplexes, but has poor selectivity for G-quadruplex versus duplex DNA. To increase the G-quadruplex recognition specificity, a new cationic porphyrin derivative, 5,10,15,20-tetra-{4-[2-(1-methyl-1-piperidinyl)ethoxy]phenyl} porphyrin (TMPipEOPP), with large side arm substituents was synthesized, and the interactions between TMPipEOPP and different DNA structures were compared. The results show that G-quadruplexes cause large changes in the UV-Vis absorption and fluorescence spectra of TMPipEOPP, but duplex and single-stranded DNAs do not, indicating that TMPipEOPP can be developed as a highly specific optical probe for discriminating G-quadruplex from duplex and single-stranded DNA. Visual discrimination is also possible. Job plot and Scatchard analysis suggest that a complicated binding interaction occurs between TMPipEOPP and G-quadruplexes. At a low [G-quadruplex]/[TMPipEOPP] ratio, one G-quadruplex binds two TMPipEOPP molecules by end-stacking and outside binding modes. At a high [G-quadruplex]/[TMPipEOPP] ratio, two G-quadruplexes bind to one TMPipEOPP molecule in a sandwich-like end-stacking mode.
Griffith, Olga Lobanova; Anthony, John E; Jones, Adolphus G; Shu, Ying; Lichtenberger, Dennis L
2012-08-29
The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]-pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.
Bondi mass with a cosmological constant
Saw, Vee-Liem
2018-04-01
The mass loss of an isolated gravitating system due to energy carried away by gravitational waves with a cosmological constant Λ ∈R was recently worked out, using the Newman-Penrose-Unti approach. In that same article, an expression for the Bondi mass of the isolated system, MΛ, for the Λ >0 case was proposed. The stipulated mass MΛ would ensure that in the absence of any incoming gravitational radiation from elsewhere the emitted gravitational waves must carry away a positive-definite energy. That suggested quantity, however, introduced a Λ -correction term to the Bondi mass MB (where MB is the usual Bondi mass for asymptotically flat spacetimes), which would involve information not just on the state of the system at that moment but ostensibly also its past history. In this paper, we derive the identical mass-loss equation using an integral formula on a hypersurface formulated by Frauendiener based on the Nester-Witten identity and argue that one may adopt a generalization of the Bondi mass with Λ ∈R without any correction, viz., MΛ=MB for any Λ ∈R . Furthermore, with MΛ=MB, we show that for purely quadrupole gravitational waves given off by the isolated system (i.e., when the "Bondi news" σo comprises only the l =2 components of the spherical harmonics with spin-weight 2) the energy carried away is manifestly positive definite for the Λ >0 case. For a general σo having higher multipole moments, this perspicuous property in the Λ >0 case still holds if those l >2 contributions are weak—more precisely, if they satisfy any of the inequalities given in this paper.
Pinkas, Jiří; Gyepes, Róbert; Císařová, Ivana; Kubišta, Jiří; Horáček, Michal; Mach, Karel
2015-04-28
The titanocene-ethene complex [Ti(II)(η(2)-C2H4)(η(5)-C5Me5)2] (1) with simple internal alkynes R(1)C≡CR(2) gives complexes [Ti(II)(η(2)-R(1)C≡CR(2))(η(5)-C5Me5)2] {R(1), R(2): Ph, Ph (3), Ph, Me (4), Me, SiMe3 (5), Ph, SiMe3 (6), t-Bu, SiMe3 (7), and SiMe3, SiMe3 (8). In contrast, alkynes with R(1) = Me and R(2) = t-Bu or i-Pr afford allene complexes [Ti(II)(η(2)-CH2=C=CHR(2))(η(5)-C5Me5)2] (11) and (12), whereas for R(2) = Et a mixture of alkyne complex (13A) and minor allene (13) is obtained. Crystal structures of 4, 6, 7 and 11 have been determined; the latter structure proved the back-bonding interaction of the allene terminal double bond. Only the synthesis of 8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiC≡CSiMe3] ⇌ [8] + [C2H4] approached 1. Compound 9 (R(1), R(2): Me), not obtainable from 1, together with compounds 3–6 and 10 (R(1), R(2): Et) were also prepared by alkyne exchange with 8, however this reaction did not take place in attempts to obtain 7. Compounds 1 and 3–9 display the longest-wavelength electronic absorption band in the range 670-940 nm due to the HOMO → LUMO transition. The assignment of the first excitation to be of predominantly a b2 → a1 transition was confirmed by DFT calculations. The calculated first excitation energies for 3–9 followed the order of hypsochromic shifts of the absorption band relative to 8 that were induced by acetylene substituents: Me > Ph ≫ SiMe3. Computational results have also affirmed the back-bonding nature in the alkyne-to-metal coordination.
Computing the Gromov hyperbolicity constant of a discrete metric space
Ismail, Anas
2012-01-01
, and many other areas of research. The Gromov hyperbolicity constant of several families of graphs and geometric spaces has been determined. However, so far, the only known algorithm for calculating the Gromov hyperbolicity constant δ of a discrete metric
Tampubolon, Marojahan; Pamungkas, Laskar; Hsieh, Yao Ching; Chiu, Huang Jen
2018-04-01
This paper presents the implementation of Constant Voltage (CV) and Constant Current (CC) control for a wireless charger system. A battery charging system needs these control modes to ensure the safety of the battery and the effectiveness of the charging system. Here, the wireless charger system does not employ any post-regulator stage to control the output voltage and output current of the charger. But, it uses a variable frequency control incorporated with a conventional PI control. As a result, the size and the weight of the system are reduced. This paper discusses the brief review of the SS-WPT, control strategy and implementation of the CV and CC control. Experimental hardware with 2kW output power has been performed and tested. The results show that the proposed CV and CC control method works well with the system.
International Nuclear Information System (INIS)
2001-02-01
This report contains translations of eleven papers published in the Nuclear Constants journal (Voprosy Atomnoj Nauki I Teknniki, seriya: Yadernye Konstanty (YK), vypusk 2, 1999). They are marked as ''Translated from Russian''. Four original papers published in YK in English are included with correction of found misprints and small format changes. As a result the report contains all papers presented in YK, 2 (1999). (author)
International Nuclear Information System (INIS)
2002-12-01
This report contains translations of eight papers published in the Nuclear Constants journal (Voprosy Atomnoj Nauki I Teknniki, seriya: Yadernye Konstanty (YK), vypusk 1, 2001). They are marked as 'Translated from Russian'. Six original papers published in YK in English are included with correction of found misprints and small format changes. As a result the report contains all papers presented in YK, 1 (2001). (author)
Energy Technology Data Exchange (ETDEWEB)
NONE
2001-10-01
This report contains translations of five papers published in the Nuclear Constants journal (Voprosy Atomnoj Nauki I Teknniki, seriya: Yadernye Konstanty (YK), vypusk 2, 2000). They are marked as 'Translated from Russian'. Two original papers published in YK in English are included with correction of found misprints and small format changes. As a result, the report contains all papers presented in YK, 2 (2000). (author)
International Nuclear Information System (INIS)
2001-12-01
This report contains translations of seven papers published in the Nuclear Constants journal (Voprosy Atomnoj Nauki I Teknniki, seriya: Yadernye Konstanty (YK), vypusk 1, 2000). They are marked as 'Translated from Russian'. Two original papers published in YK in English are included with correction of found misprints and small format changes. As a result the report contains all papers presented in YK, 1 (2000). (author)
Determination of constants of factorized pairing force from conservation laws
International Nuclear Information System (INIS)
Voronkov, Yu.P.; Mikhajlov, V.M.
1975-01-01
The constants of a factorized interaction in the particle-particle channel are evaluated on the basis of average field parameters and Cooper pairing. The relations between the constants of multipole particle-particle forces are derived for the spherical nuclei. The constants of the quadrupole pairing are obtained for deformed nuclei from the angular momentum conservation law. The calculated constants are compared with empiricalones
The fine-structure constant before quantum mechanics
International Nuclear Information System (INIS)
Kragh, Helge
2003-01-01
This paper focuses on the early history of the fine-structure constant, largely the period until 1925. Contrary to what is generally assumed, speculations concerning the interdependence of the elementary electric charge and Planck's constant predated Arnold Sommerfeld's 1916 discussion of the dimensionless constant. This paper pays particular attention to a little known work from 1914 in which G N Lewis and E Q Adams derived what is effectively a numerical expression for the fine-structure constant
Association constants of telluronium salts; Konstanty assotsiatsii telluronievykh solej
Energy Technology Data Exchange (ETDEWEB)
Kovach, N A; Rivkin, B B; Sadekov, T D; Shvajka, O P
1997-12-31
Association constants in acetonitrile of triphenyl telluronium salts, which are dilute electrolytes, are determined through the conductometry method. Satisfactory correlation dependence of constants of interion association and threshold molar electroconductivity on the Litvinenko-Popov constants for depositing groups is identified. 6 refs.
Nuclear magnetic resonance J coupling constant polarizabilities of hydrogen peroxide
DEFF Research Database (Denmark)
Kjær, Hanna; Nielsen, Monia R.; Pagola, Gabriel I.
2012-01-01
In this paper we present the so far most extended investigation of the calculation of the coupling constant polarizability of a molecule. The components of the coupling constant polarizability are derivatives of the NMR indirect nuclear spin-spin coupling constant with respect to an external elec...
Towards Grothendieck constants and LHV models in quantum mechanics
International Nuclear Information System (INIS)
Hua, Bobo; Li, Ming; Zhang, Tinggui; Zhou, Chunqin; Li-Jost, Xianqing; Fei, Shao-Ming
2015-01-01
We adopt a continuous model to estimate the Grothendieck constants. An analytical formula to compute the lower bounds of Grothendieck constants has been explicitly derived for arbitrary orders, which improves previous bounds. Moreover, our lower bound of the Grothendieck constant of order three gives a refined bound of the threshold value for the nonlocality of the two-qubit Werner states. (paper)
Reliability concerns with logical constants in Xilinx FPGA designs
Energy Technology Data Exchange (ETDEWEB)
Quinn, Heather M [Los Alamos National Laboratory; Graham, Paul [Los Alamos National Laboratory; Morgan, Keith [Los Alamos National Laboratory; Ostler, Patrick [Los Alamos National Laboratory; Allen, Greg [JPL; Swift, Gary [XILINX; Tseng, Chen W [XILINX
2009-01-01
In Xilinx Field Programmable Gate Arrays logical constants, which ground unused inputs and provide constants for designs, are implemented in SEU-susceptible logic. In the past, these logical constants have been shown to cause the user circuit to output bad data and were not resetable through off-line rcconfiguration. In the more recent devices, logical constants are less problematic, though mitigation should still be considered for high reliability applications. In conclusion, we have presented a number of reliability concerns with logical constants in the Xilinx Virtex family. There are two main categories of logical constants: implicit and explicit logical constants. In all of the Virtex devices, the implicit logical constants are implemented using half latches, which in the most recent devices are several orders of magnitudes smaller than configuration bit cells. Explicit logical constants are implemented exclusively using constant LUTs in the Virtex-I and Virtex-II, and use a combination of constant LUTs and architectural posts to the ground plane in the Virtex-4. We have also presented mitigation methods and options for these devices. While SEUs in implicit and some types of explicit logical constants can cause data corrupt, the chance of failure from these components is now much smaller than it was in the Virtex-I device. Therefore, for many cases, mitigation might not be necessary, except under extremely high reliability situations.
Stability constant of the trisglycinto metal complexes | Na'aliya ...
African Journals Online (AJOL)
The stability constants of iron, manganese, cobalt, and nickel complexes of glycine have been determined in aqueous solution by potentiometric titration with standard sodium hydroxide solution. The values of the stepwise stability constants were obtained by ORIGIN '50' program. The overall stability constants of the ...
DFT computations of the lattice constant, stable atomic structure and ...
African Journals Online (AJOL)
This paper presents the most stable atomic structure and lattice constant of Fullerenes (C60). FHI-aims DFT code was used to predict the stable structure and the computational lattice constant of C60. These were compared with known experimental structures and lattice constants of C60. The results obtained showed that ...
Some comments on the universal constant in DSR
Energy Technology Data Exchange (ETDEWEB)
Girelli, Florian [SISSA, Via Beirut 2-4, 34014 Trieste (Italy); INFN, Sezione di Trieste (Italy); Livine, Etera R [Laborat. de Physique, ENS Lyon, CNRS UMR 5672, 46 Allee d' Italie, 69364 Lyon Cedex 07 (France)
2007-05-15
Deformed Special Relativity is usually presented as a deformation of Special Relativity accommodating a new universal constant, the Planck mass, while respecting the relativity principle. In order to avoid some fundamental problems (e.g. soccer ball problem), we argue that we should switch point of view and consider instead the Newton constant G as the universal constant.
Some comments on the universal constant in DSR
International Nuclear Information System (INIS)
Girelli, Florian; Livine, Etera R
2007-01-01
Deformed Special Relativity is usually presented as a deformation of Special Relativity accommodating a new universal constant, the Planck mass, while respecting the relativity principle. In order to avoid some fundamental problems (e.g. soccer ball problem), we argue that we should switch point of view and consider instead the Newton constant G as the universal constant
Stability constants of the Europium complexes with the chloride ions
International Nuclear Information System (INIS)
Jimenez R, M.; Solache R, M.; Rojas H, A.
2000-01-01
The stability constants of lanthanides complexes with chloride ions which were determined at the same ionic force but in different media, are significantly different. It does not exist a systematic study over these stability constants. The purpose of this work is to determine the stability constants of the europium complexes with chloride ions at 303 K, by the solvents extraction method. (Author)
Garbage-free reversible constant multipliers for arbitrary integers
DEFF Research Database (Denmark)
Mogensen, Torben Ægidius
2013-01-01
We present a method for constructing reversible circuitry for multiplying integers by arbitrary integer constants. The method is based on Mealy machines and gives circuits whose size are (in the worst case) linear in the size of the constant. This makes the method unsuitable for large constants...
Beauty vector meson decay constants from QCD sum rules
Energy Technology Data Exchange (ETDEWEB)
Lucha, Wolfgang [Institute for High Energy Physics, Austrian Academy of Sciences, Nikolsdorfergasse 18, A-1050 Vienna (Austria); Melikhov, Dmitri [Institute for High Energy Physics, Austrian Academy of Sciences, Nikolsdorfergasse 18, A-1050 Vienna (Austria); D. V. Skobeltsyn Institute of Nuclear Physics, M. V. Lomonosov Moscow State University, 119991, Moscow (Russian Federation); Simula, Silvano [Istituto Nazionale di Fisica Nucleare, Sezione di Roma Tre, Via della Vasca Navale 84, I-00146, Roma (Italy)
2016-01-22
We present the outcomes of a very recent investigation of the decay constants of nonstrange and strange heavy-light beauty vector mesons, with special emphasis on the ratio of any such decay constant to the decay constant of the corresponding pseudoscalar meson, by means of Borel-transformed QCD sum rules. Our results suggest that both these ratios are below unity.
Wang, Fang; Sun, Wei; Xia, Chungu; Wang, Yong
2017-10-01
Through the introduction of dimethylamino (Me 2 N) substituent at the pyridine ring of 2-((R)-2-[(R)-1-(pyridine-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-ylmethyl)pyridine (PDP) ligand, the non-heme Fe II ( Me2N PDP)/H 2 O 2 /AcOH catalyst system was found to exhibit significant higher catalytic activity and enantioselectivity than the non-substituent one in the asymmetric epoxidation experiments. The mechanistic origin of the remarkable substituent effects in these oxidation reactions has not been well established. To ascertain the potent oxidant and the related reaction mechanism, a detailed DFT calculation was performed. Interestingly, a novel Fe(IV)-oxo Me2N PDP cation radical species, [( Me2N PDP) + · Fe IV (O)(OAc)] 2+ ( Me2N 5), with about one spin spreading over the non-heme Me2N PDP ligand was formed via a carboxylic-acid-assisted O-O bond heterolysis, which is reminiscent of Compound I (an Fe(IV)(O)(porphyrin cation radical) species) in cytochrome P450 chemistry. Me2N 5 is energetically comparable with the cyclic ferric peracetate species Me2N 6, while in the pristine Fe(PDP) catalyst system, H 6 is more stable than H 5. Comparison of the activation energy for the ethylene epoxidation promoted by Me2N 5 and Me2N 6, Me2N 5 is supposed as the true oxidant triggering the epoxidation of olefins. In addition, a systematic research on the substituent effects varied from the electron-donating substituent (dMM, the substituents at sites 3, 4, and 5 of the pyridine ring: methyl, methoxyl, and methyl) to the electron-withdrawing one (CF 3 , 2,6-bis(trifluoromethyl)phenyl) on the electronic structure of the reaction intermediates has also been investigated. An alternative cyclic ferric peracetate complex is obtained, indicating that the substituents at the pyridine ring of PDP ligands have significant impacts on the electronic structure of the oxidants.
The cosmological constant in theories with finite spacetime
International Nuclear Information System (INIS)
Kummer, Janis
2014-08-01
We study the role of the cosmological constant in different theories with finite spacetime. The cosmological constant appears both as an initial condition and as a constant of integration. In the context of the cosmological constant problem a new model will be presented. This modification of general relativity generates a small, non-vanishing cosmological constant, which is radiatively stable. The dynamics of the expansion of the universe in this model will be analyzed. Eventually, we try to solve the emergent problems concerning the generation of accelerated expansion using a quintessence model of dark energy.
Constant-roll tachyon inflation and observational constraints
Gao, Qing; Gong, Yungui; Fei, Qin
2018-05-01
For the constant-roll tachyon inflation, we derive the analytical expressions for the scalar and tensor power spectra, the scalar and tensor spectral tilts and the tensor to scalar ratio to the first order of epsilon1 by using the method of Bessel function approximation. The derived ns-r results are compared with the observations, we find that only the constant-roll inflation with ηH being a constant is consistent with the observations and observations constrain the constant-roll inflation to be slow-roll inflation. The tachyon potential is also reconstructed for the constant-roll inflation which is consistent with the observations.
Multiple constant multiplication optimizations for field programmable gate arrays
Kumm, Martin
2016-01-01
This work covers field programmable gate array (FPGA)-specific optimizations of circuits computing the multiplication of a variable by several constants, commonly denoted as multiple constant multiplication (MCM). These optimizations focus on low resource usage but high performance. They comprise the use of fast carry-chains in adder-based constant multiplications including ternary (3-input) adders as well as the integration of look-up table-based constant multipliers and embedded multipliers to get the optimal mapping to modern FPGAs. The proposed methods can be used for the efficient implementation of digital filters, discrete transforms and many other circuits in the domain of digital signal processing, communication and image processing. Contents Heuristic and ILP-Based Optimal Solutions for the Pipelined Multiple Constant Multiplication Problem Methods to Integrate Embedded Multipliers, LUT-Based Constant Multipliers and Ternary (3-Input) Adders An Optimized Multiple Constant Multiplication Architecture ...
Massa, Enrico; Nicolaus, Arnold
2011-04-01
This issue of Metrologia collects papers about the results of an international research project aimed at the determination of the Avogadro constant, NA, by counting the atoms in a silicon crystal highly enriched with the isotope 28Si. Fifty years ago, Egidi [1] thought about realizing an atomic mass standard. In 1965, Bonse and Hart [2] operated the first x-ray interferometer, thus paving the way to the achievement of Egidi's dream, and soon Deslattes et al [3] completed the first counting of the atoms in a natural silicon crystal. The present project, outlined by Zosi [4] in 1983, began in 2004 by combining the experiences and capabilities of the BIPM, INRIM, IRMM, NIST, NPL, NMIA, NMIJ and PTB. The start signal, ratified by a memorandum of understanding, was a contract for the production of a silicon crystal highly enriched with 28Si. The enrichment process was undertaken by the Central Design Bureau of Machine Building in St Petersburg. Subsequently, a polycrystal was grown in the Institute of Chemistry of High-Purity Substances of the Russian Academy of Sciences in Nizhny Novgorod and a 28Si boule was grown and purified by the Leibniz-Institut für Kristallzüchtung in Berlin. Isotope enrichment made it possible to apply isotope dilution mass spectroscopy, to determine the Avogadro constant with unprecedented accuracy, and to fulfil Egidi's dream. To convey Egidi's 'fantasy' into practice, two 28Si kilogram prototypes shaped as quasi-perfect spheres were manufactured by the Australian Centre for Precision Optics; their isotopic composition, molar mass, mass, volume, density and lattice parameter were accurately determined and their surfaces were chemically and physically characterized at the atomic scale. The paper by Andreas et al reviews the work carried out; it collates all the findings and illustrates how Avogadro's constant was obtained. Impurity concentration and gradients in the enriched crystal were measured by infrared spectroscopy and taken into
Directory of Open Access Journals (Sweden)
Jussara Bertho Fantinatti
2007-01-01
Full Text Available This work aimed to analyse Eucalyptus grandis W.Hill ex Maiden seed behaviour, under controlled deterioration, and to estimate viability equation constants for the species. Seeds were harvested in the growing season of 1999, and the moisture contents were adjusted from 11.3% to a range between 1.2 and 18.1% at 25ºC. The subsamples were sealed into laminate aluminium-foil packets, for storage in incubators at 40, 50 and 65±0.5ºC. The seeds presented orthodox performance, in which the constants for predicting seed longevity of E. grandis were K E = 9.661, C W = 6.467, C H = 0.03498 and C Q = 0.0002330. The usual and inverse relationship between water content and seed longevity was also observed. The lowest moisture content limit for application of the viability equation at 65ºC was 4.9%, estimated under hygroscopic equilibrium with 23% of relative humidity in the storage environment.Este trabalho teve como objetivos verificar o desempenho de sementes de Eucalyptus grandis W.Hill ex Maiden, após a deterioração em condições controladas, e obter as constantes da equação de viabilidade. As sementes foram colhidas na safra de 1999, e a umidade foi ajustada de 11,3% para valores entre 1,2 e 18,1% a 25ºC As subamostras foram acondicionadas em embalagens de alumínio termossoldadas, armazenadas a 40, 50 e 65±0,5ºC. As sementes apresentaram um desempenho ortodoxo em relação ao armazenamento. As constantes para a predição da longevidade foram K E = 9,661, C W = 6,467, C H = 0,03498 e C Q = 0,0002330. Foi observada a relação inversa entre teor de água e longevidade. O limite inferior de grau de umidade, calculado para aplicação da equação a 65ºC, foi de 4,9%, estimativa obtida sob equilíbrio higroscópico com umidade relativa de 23% no ambiente de armazenamento.
Directory of Open Access Journals (Sweden)
S. D. Deosarkar
2012-01-01
Full Text Available The proton-ligand stability constants of some biologically important new pyrazoles and formation constants of their complexes with Ni(II were determined at 0.1 mol dm-3 ionic strength and at 303.15 K in different dielectric constant of dioxane-water mixture by potentiometric method. The Calvin-Bjerrum's pH-titration technique as used by Irving and Rossotti was used for determination of stability constants. The results enabled to study the electrostatic forces of attraction between metal ion and ligand with changes in dielectric constant of the medium.
Amami, P; Mascia, M M; Franzini, A; Saba, F; Albanese, A
2017-08-01
The study aimed to evaluate safety and efficacy of shifting stimulation settings from constant-voltage (CV) to constant-current (CC) programming in patients with Parkinson's disease (PD) and chronic subthalamic nucleus deep brain stimulation (STN DBS). Twenty PD patients with chronic STN DBS set in CV programming were shifted to CC and followed for 3 months; the other stimulation settings and the medication regimen remained unchanged. Side effects, motor, non-motor, executive functions, and impedance were assessed at baseline and during follow-up. No adverse events were observed at time of shifting or during CC stimulation. Motor and non-motor measures remained unchanged at follow-up despite impedance decreased. Compared to baseline, inhibition processes improved at follow-up. The shifting strategy was well tolerated and the clinical outcome was maintained with no need to adjust stimulation settings or medications notwithstanding a decrease of impedance. Improvement of inhibition processes is a finding which needed further investigation.
Temperature dependence of grain boundary free energy and elastic constants
International Nuclear Information System (INIS)
Foiles, Stephen M.
2010-01-01
This work explores the suggestion that the temperature dependence of the grain boundary free energy can be estimated from the temperature dependence of the elastic constants. The temperature-dependent elastic constants and free energy of a symmetric Σ79 tilt boundary are computed for an embedded atom method model of Ni. The grain boundary free energy scales with the product of the shear modulus times the lattice constant for temperatures up to about 0.75 the melting temperature.
On Riemannian manifolds (Mn, g) of quasi-constant curvature
International Nuclear Information System (INIS)
Rahman, M.S.
1995-07-01
A Riemannian manifold (M n , g) of quasi-constant curvature is defined. It is shown that an (M n , g) in association with other class of manifolds gives rise, under certain conditions, to a manifold of quasi-constant curvature. Some observations on how a manifold of quasi-constant curvature accounts for a pseudo Ricci-symmetric manifold and quasi-umbilical hypersurface are made. (author). 10 refs
Effects of constant voltage and constant current stress in PCBM:P3HT solar cells
DEFF Research Database (Denmark)
Cester, Andrea; Rizzo, Aldo; Bazzega, A.
2015-01-01
The aimof this work is the investigation of forward and reverse bias stress effects, cell self-heating and annealing in roll coated organic solar cells with PCBM:P3HT active layer. In reverse bias stress cells show a constant degradation over time. In forward current stress cells alternate...... mechanisms: the decrease of the net generation rate (due to formation of exciton quenching centres or the reduction of exciton separation rate); the formation of small leaky paths between anode and cathode, which reduces the total current extracted from the cell. The stress-induced damage can be recovered...... degradation and annealing phases, which are explained through the high power dissipation during the current stress, and the consequent self-heating. The high temperature is able to recover the cell performances at least until a critical temperature is reached. The degradation can be explained by the following...
An Einstein-Cartan Fine Structure Constant Definition
Directory of Open Access Journals (Sweden)
Stone R. A. Jr.
2010-01-01
Full Text Available The fine structure constant definition given in Stone R.A. Jr. Progress in Physics, 2010, v.1, 11-13 is compared to an Einstein-Cartan fine structure constant definition. It is shown that the Einstein-Cartan definition produces the correct pure theory value, just not the measure value. To produce the measured value, the pure theory Einstein-Cartan fine structure constant requires only the new variables and spin coupling of the fine structure constant definition in [1].
GRUCAL, a computer program for calculating macroscopic group constants
International Nuclear Information System (INIS)
Woll, D.
1975-06-01
Nuclear reactor calculations require material- and composition-dependent, energy averaged nuclear data to describe the interaction of neutrons with individual isotopes in material compositions of reactor zones. The code GRUCAL calculates these macroscopic group constants for given compositions from the material-dependent data of the group constant library GRUBA. The instructions for calculating group constants are not fixed in the program, but will be read at the actual execution time from a separate instruction file. This allows to accomodate GRUCAL to various problems or different group constant concepts. (orig.) [de
Directory of Open Access Journals (Sweden)
BRATISLAV Ž. JOVANOVIĆ
2009-12-01
Full Text Available The rate constants for the reactions of diazodiphenylmethane (DDM with 6-substituted nicotinic acids in aprotic solvents at 30 °C were determined. The obtained second order rate constants in aprotic solvents, together with literature data for benzoic and nicotinic acids in protic solvents, were used for the calculation of solvent effects, employing the Kamlet-Taft solvatochromic equation (linear solvation energy relationship – LSER in the form: log k = log k0 + s* + a + b. The correlations of the kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The sign of the equation coefficients (s, a and b were in agreement with the postulated reaction mechanism, and the mode of the solvent influences on the reaction rate is discussed based on the correlation results. A similar contribution of the non-specific solvent effect and electrophilic solvation was observed for all acids, while the highest contribution of nucleophilic solvation was influenced by their high acidity. Correlation analysis of the rate data with substituent p parameters in an appropriate solvent using the Hammett equation was also performed. The substituent effect on the acid reactivity was higher in aprotic solvents of higher dipolarity/polarizability. The mode of the transmission of the substituent effect is discussed in light of the contribution of solute–solvent interaction on the acid reactivity.
Goszczycki, Piotr; Stadnicka, Katarzyna; Brela, Mateusz Z.; Grolik, Jarosław; Ostrowska, Katarzyna
2017-10-01
Three (E/Z)-diastereoisomers, based on pyrrolo[2,3-b]quinoxaline system as fluorophore and containing: 2-thienylmethyl (1), bis(2-thienylmethyl)-2-aminoethyl (3a), bis(2-thienylmethyl)-3-aminopropyl (3b) groups as substituents, were synthesized and characterized by X-ray structural analysis, PXRD, NMR, UV-Vis as well as fluorescence. These compounds are non-fluorescent in acetonitrile solution, however, they exhibit aggregation induced emission enhancement (AIEE) upon water addition and in solid state. X-ray structural analysis revealed that molecules with 2-thienylmethyl and bis(2-thienylmethyl)-2-aminoethyl groups form dimers and π-stacks through π-π interactions between anitiparallel oriented pyrroloquinoxaline cores with interplanar distances 3.45 Å and 3.20 Å, respectively. Conformation of bis(2-thienylmethyl)-3-aminopropyl group is imposed by incorporated DMSO-d6 solvent molecule and weak intermolecular S-π and CH-π interactions, that prevents π-π interaction between fluorophore cores. The correlation between crystal structure and fluorescent properties of synthesized molecules was discussed. The DFT calculations were performed to rationalize the differences between considered systems.
Directory of Open Access Journals (Sweden)
I. Blanco
2012-12-01
Full Text Available Some new Polystyrene (PS nanocomposites were prepared by using two Polyhedral Oligomeric Silsesquioxanes (POSSs, namely RR’7(SiO1.58 (where R = 4-methoxyphenyl or 2,4-difluorophenyl and R’ = cyclopentyl, as fillers, and their degradation was studied to investigate the effect of the electron-donor or electron-withdrawing character of the phenyl group substituents on thermal stability. Nanocomposites were synthesized by in situ polymerization of styrene in the presence of various concentrations of POSS. Proton nuclear magnetic resonance (1H NMR spectra indicated that the POSS content in the obtained nanocomposites was higher than that in reactant mixtures. Inherent viscosity (ηinh and glass transition temperature (Tg determinations indicated that the average molar mass of polymer in 4-methoxynanocomposites was the same than neat PS, while it was much lower in 2,4-difluoro derivatives. Degradations were carried out in both flowing nitrogen and static air atmospheres, in the scanning mode, at various heating rates, and temperature at 5% mass loss (T5% and the activation energy (Ea of degradation of various nanocomposites were determined. The values obtained for 4-methoxyderivatives were higher than unfilled PS thus indicating higher thermal stability. Conversely, the values found for 2,4-difluoro derivatives were lower, in some cases even than those of neat PS. The results were discussed and interpreted.
International Nuclear Information System (INIS)
Lakshmi Praveen, P.; Ojha, Durga P.
2012-01-01
The photoresponsive behaviour of fluorinated liquid crystals p-phenylene-4-methoxy benzoate-4-trifluoromethylbenzoate (FLUORO1), and 4-propyloxyphenyl-4-(4-trifluoromethylbenzoyloxy) benzoate (FLUORO2) has been systematically investigated using the CNDO/S + CI and INDO/S + CI methods. These methods have been employed to calculate/analyze the spectral shifts, and absorbance measurements in UV–visible region of the systems. The electronic transitions, absorption wavelength, HOMO (highest occupied molecular orbital), and LUMO (lowest unoccupied molecular orbital) energies have been calculated. Further, ultraviolet (UV) stability of the molecules has been discussed in the light of absorption wavelength and electronic transition oscillator strength (f). The effect of different solvent media and substituents on transition energies, oscillator strength, and other absorption parameters have also been reported. The present article provides valuable information regarding enhancing the UV stability of molecules by marinating their conductivity. Highlights: ► The strongest bands of FLUORO molecules can be assigned as π → π ∗ transitions. ► A small red-shift indicates a weak exciton coupling of chromophores. ► No n → π ∗ transition occurs due to the rigidity of the ring system of the molecules. ► The HOMO, LUMO, and E g values have been found to be independent of solvent effect.
Energy Technology Data Exchange (ETDEWEB)
Lakshmi Praveen, P. [Liquid Crystal Research Laboratory, Post-Graduate Department of Physics, Andhra Loyola College, Vijayawada 520 008, A.P. (India); Ojha, Durga P., E-mail: durga_ojha@hotmail.com [Liquid Crystal Research Laboratory, Post-Graduate Department of Physics, Andhra Loyola College, Vijayawada 520 008, A.P. (India)
2012-08-15
The photoresponsive behaviour of fluorinated liquid crystals p-phenylene-4-methoxy benzoate-4-trifluoromethylbenzoate (FLUORO1), and 4-propyloxyphenyl-4-(4-trifluoromethylbenzoyloxy) benzoate (FLUORO2) has been systematically investigated using the CNDO/S + CI and INDO/S + CI methods. These methods have been employed to calculate/analyze the spectral shifts, and absorbance measurements in UV-visible region of the systems. The electronic transitions, absorption wavelength, HOMO (highest occupied molecular orbital), and LUMO (lowest unoccupied molecular orbital) energies have been calculated. Further, ultraviolet (UV) stability of the molecules has been discussed in the light of absorption wavelength and electronic transition oscillator strength (f). The effect of different solvent media and substituents on transition energies, oscillator strength, and other absorption parameters have also been reported. The present article provides valuable information regarding enhancing the UV stability of molecules by marinating their conductivity. Highlights: Black-Right-Pointing-Pointer The strongest bands of FLUORO molecules can be assigned as {pi} {yields} {pi}{sup Asterisk-Operator} transitions. Black-Right-Pointing-Pointer A small red-shift indicates a weak exciton coupling of chromophores. Black-Right-Pointing-Pointer No n {yields} {pi}{sup Asterisk-Operator} transition occurs due to the rigidity of the ring system of the molecules. Black-Right-Pointing-Pointer The HOMO, LUMO, and E{sub g} values have been found to be independent of solvent effect.
DEFF Research Database (Denmark)
Álvarez-Asencio, R.; Thormann, Esben; Rutland, M.W.
2013-01-01
A technique has been developed for the calculation of torsional spring constants for AFM cantilevers based on the combination of the normal spring constant and plate/beam theory. It is easy to apply and allow the determination of torsional constants for stiff cantilevers where the thermal power s...... spectrum is difficult to obtain due to the high resonance frequency and low signal/noise ratio. The applicability is shown to be general and this simple approach can thus be used to obtain torsional constants for any beam shaped cantilever. © 2013 AIP Publishing LLC....
Using Constant Time Delay to Teach Braille Word Recognition
Hooper, Jonathan; Ivy, Sarah; Hatton, Deborah
2014-01-01
Introduction: Constant time delay has been identified as an evidence-based practice to teach print sight words and picture recognition (Browder, Ahlbrim-Delzell, Spooner, Mims, & Baker, 2009). For the study presented here, we tested the effectiveness of constant time delay to teach new braille words. Methods: A single-subject multiple baseline…
Constant Cremer, voetballer in Tilburg met Afrikaanse wortels
Drs. Thijs Kemmeren
2012-01-01
Constant Cremer is de eerste zwarte voetballer in Nederland. Hij is geboren in Belgisch Congo. Hij speelde bij Willem II in het seizoen 1904 -1905 en werd met Willem II Brabvants kampioen. Constant werd, als een donkere mulat een held in Tilburg. Hij kwam uiteindelijk terecht in Nederland Indie en
Pricing constant maturity credit default swaps under jumo dynamics
Jönsson, H.; Schoutens, W.
2009-01-01
In this paper we discuss the pricing of Constant Maturity Credit Default Swaps (CMCDS) under single sided jump models. The CMCDS offers default protection in exchange for a floating premium which is periodically reset and indexed to the market spread on a CDS with constant maturity tenor written on
Lattice constant measurement from electron backscatter diffraction patterns
DEFF Research Database (Denmark)
Saowadee, Nath; Agersted, Karsten; Bowen, Jacob R.
2017-01-01
Kikuchi bands in election backscattered diffraction patterns (EBSP) contain information about lattice constants of crystallographic samples that can be extracted via the Bragg equation. An advantage of lattice constant measurement from EBSPs over diffraction (XRD) is the ability to perform local ...
Cosmological constant--the weight of the vacuum
International Nuclear Information System (INIS)
Padmanabhan, T.
2003-01-01
Recent cosmological observations suggest the existence of a positive cosmological constant Λ with the magnitude Λ(Gℎ/c 3 )∼10 -123 . This review discusses several aspects of the cosmological constant both from the cosmological (Sections 1-6) and field theoretical (Sections 7-11) perspectives. After a brief introduction to the key issues related to cosmological constant and a historical overview, a summary of the kinematics and dynamics of the standard Friedmann model of the universe is provided. The observational evidence for cosmological constant, especially from the supernova results, and the constraints from the age of the universe, structure formation, Cosmic Microwave Background Radiation (CMBR) anisotropies and a few others are described in detail, followed by a discussion of the theoretical models (quintessence, tachyonic scalar field, ...) from different perspectives. The latter part of the review (Sections 7-11) concentrates on more conceptual and fundamental aspects of the cosmological constant like some alternative interpretations of the cosmological constant, relaxation mechanisms to reduce the cosmological constant to the currently observed value, the geometrical structure of the de Sitter spacetime, thermodynamics of the de Sitter universe and the role of string theory in the cosmological constant problem
Coupler tuning for constant gradient travelling wave accelerating structures
International Nuclear Information System (INIS)
Guo Xingkun; Ma Yanyun; Wang Xiulong
2013-01-01
The method of the coupler tuning for the constant gradient traveling wave accelerating structure was described and the formula of coupling coefficient p was deduced on the basis of analyzing the existing methods for the constant impedance traveling wave accelerating structures and coupling-cavity chain equivalent circuits. The method and formula were validated by the simulation result by CST and experiment data. (authors)
Coupling constants (Tdn) and (Td*n) for local potentials
International Nuclear Information System (INIS)
Belyaev, V.B.; Irgaziev, B.F.; Orlov, Yu.V.
1976-01-01
The coupling constants (Tdn) and (Td*n) are found solving the Faddeev equations with local potentials. It is shown that the polinomial extrapolation of the wave function to the nonphysical region of the variable Q 2 turns not to be sure for determination of the coupling constants
Vector and axial constants of the baryon decuplet
International Nuclear Information System (INIS)
Belyaev, V.M.; Blok, B.Y.; Kogan, Y.I.
1985-01-01
On the basis of the QCD sum rules for the polarization operator in external axial and vector fields we determine the vector and axial transition constants in the 3/2 + baryon decuplet. We show that the renormalization of the axial constant is due to the interaction of the external axial field with the quark condensate
Measuring Boltzmann's Constant with Carbon Dioxide
Ivanov, Dragia; Nikolov, Stefan
2013-01-01
In this paper we present two experiments to measure Boltzmann's constant--one of the fundamental constants of modern-day physics, which lies at the base of statistical mechanics and thermodynamics. The experiments use very basic theory, simple equipment and cheap and safe materials yet provide very precise results. They are very easy and…
Elastic constants of diamond from molecular dynamics simulations
International Nuclear Information System (INIS)
Gao Guangtu; Van Workum, Kevin; Schall, J David; Harrison, Judith A
2006-01-01
The elastic constants of diamond between 100 and 1100 K have been calculated for the first time using molecular dynamics and the second-generation, reactive empirical bond-order potential (REBO). This version of the REBO potential was used because it was redesigned to be able to model the elastic properties of diamond and graphite at 0 K while maintaining its original capabilities. The independent elastic constants of diamond, C 11 , C 12 , and C 44 , and the bulk modulus were all calculated as a function of temperature, and the results from the three different methods are in excellent agreement. By extrapolating the elastic constant data to 0 K, it is clear that the values obtained here agree with the previously calculated 0 K elastic constants. Because the second-generation REBO potential was fit to obtain better solid-state force constants for diamond and graphite, the agreement with the 0 K elastic constants is not surprising. In addition, the functional form of the second-generation REBO potential is able to qualitatively model the functional dependence of the elastic constants and bulk modulus of diamond at non-zero temperatures. In contrast, reactive potentials based on other functional forms do not reproduce the correct temperature dependence of the elastic constants. The second-generation REBO potential also correctly predicts that diamond has a negative Cauchy pressure in the temperature range examined
Theory of the change of elastic constants by interstitials
International Nuclear Information System (INIS)
Breuer, N.; Dederichs, P.H.; Lehmann, C.; Leibfried, G.; Scholz, A.
1975-01-01
The theory of the change of elastic constants by point-defects, in particular by interstitials, is briefly summarized. The typical effects of spring changes in a defect lattice on the elastic data are discussed qualitatively. Numerical results for the change of elastic constants by self-interstitials and vacancies are given and compared with experimental data for Cu and Al
Constant Width Planar Computation Characterizes ACC^{0}
DEFF Research Database (Denmark)
Hansen, K.A.
2004-01-01
We obtain a characterization of ACC 0 in terms of a natural class of constant width circuits, namely in terms of constant width polynomial size planar circuits. This is shown via a characterization of the class of acyclic digraphs which can be embedded on a cylinder surface in such a way that all...
International Nuclear Information System (INIS)
Mohamadou, Youssoufa; Oh, Tong In; Wi, Hun; Sohal, Harsh; Farooq, Adnan; Woo, Eung Je; McEwan, Alistair Lee
2012-01-01
Current sources are widely used in bio-impedance spectroscopy (BIS) measurement systems to maximize current injection for increased signal to noise while keeping within medical safety specifications. High-performance current sources based on the Howland current pump with optimized impedance converters are able to minimize stray capacitance of the cables and setup. This approach is limited at high frequencies primarily due to the deteriorated output impedance of the constant current source when situated in a real measurement system. For this reason, voltage sources have been suggested, but they require a current sensing resistor, and the SNR reduces at low impedance loads due to the lower current required to maintain constant voltage. In this paper, we compare the performance of a current source-based BIS and a voltage source-based BIS, which use common components. The current source BIS is based on a Howland current pump and generalized impedance converters to maintain a high output impedance of more than 1 MΩ at 2 MHz. The voltage source BIS is based on voltage division between an internal current sensing resistor (R s ) and an external sample. To maintain high SNR, R s is varied so that the source voltage is divided more or less equally. In order to calibrate the systems, we measured the transfer function of the BIS systems with several known resistor and capacitor loads. From this we may estimate the resistance and capacitance of biological tissues using the least-squares method to minimize error between the measured transimpedance excluding the system transfer function and that from an impedance model. When tested on realistic loads including discrete resistors and capacitors, and saline and agar phantoms, the voltage source-based BIS system had a wider bandwidth of 10 Hz to 2.2 MHz with less than 1% deviation from the expected spectra compared to more than 10% with the current source. The voltage source also showed an SNR of at least 60 dB up to 2.2 MHz
Time variable cosmological constants from the age of universe
International Nuclear Information System (INIS)
Xu Lixin; Lu Jianbo; Li Wenbo
2010-01-01
In this Letter, time variable cosmological constant, dubbed age cosmological constant, is investigated motivated by the fact: any cosmological length scale and time scale can introduce a cosmological constant or vacuum energy density into Einstein's theory. The age cosmological constant takes the form ρ Λ =3c 2 M P 2 /t Λ 2 , where t Λ is the age or conformal age of our universe. The effective equation of state (EoS) of age cosmological constant are w Λ eff =-1+2/3 (√(Ω Λ ))/c and w Λ eff =-1+2/3 (√(Ω Λ ))/c (1+z) when the age and conformal age of universe are taken as the role of cosmological time scales respectively. The EoS are the same as the so-called agegraphic dark energy models. However, the evolution histories are different from the agegraphic ones for their different evolution equations.
Fundamental Constants in Physics and their Time Dependence
CERN. Geneva
2008-01-01
In the Standard Model of Particle Physics we are dealing with 28 fundamental constants. In the experiments these constants can be measured, but theoretically they are not understood. I will discuss these constants, which are mostly mass parameters. Astrophysical measurements indicate that the finestructure constant is not a real constant, but depends on time. Grand unification then implies also a time variation of the QCD scale. Thus the masses of the atomic nuclei and the magnetic moments of the nuclei will depend on time. I proposed an experiment, which is currently done by Prof. Haensch in Munich and his group. The first results indicate a time dependence of the QCD scale. I will discuss the theoretical implications.
Transport equivalent diffusion constants for reflector region in PWRs
International Nuclear Information System (INIS)
Tahara, Yoshihisa; Sekimoto, Hiroshi
2002-01-01
The diffusion-theory-based nodal method is widely used in PWR core designs for reason of its high computing speed in three-dimensional calculations. The baffle/reflector (B/R) constants used in nodal calculations are usually calculated based on a one-dimensional transport calculation. However, to achieve high accuracy of assembly power prediction, two-dimensional model is needed. For this reason, the method for calculating transport equivalent diffusion constants of reflector material was developed so that the neutron currents on the material boundaries could be calculated exactly in diffusion calculations. Two-dimensional B/R constants were calculated using the transport equivalent diffusion constants in the two-dimensional diffusion calculation whose geometry reflected the actual material configuration in the reflector region. The two-dimensional B/R constants enabled us to predict assembly power within an error of 1.5% at hot full power conditions. (author)
Beauhaire, Josiane; Es-Safi, Nour-Eddine; Boyer, François-Didier; Kerhoas, Lucien; Guernevé, Christine le; Ducrot, Paul-Henri
2005-02-01
The regioselective introduction of substituents at C-8 of (+)-catechin is described, leading to the synthesis of several catechin derivatives with various substitution patterns to be used for the further synthesis of modified proanthocyanidins. Thereafter, a new 3-O-4 ether-linked procyanidin-like derivative was synthesized. Its formation was selectively achieved through TiCl(4)-catalyzed condensation of 4-(2-hydroxyethoxy)tetra-O-benzyl catechin with the 8-trifluoroacetyl adduct of tetra-O-benzyl catechin.
International Nuclear Information System (INIS)
1989-01-01
The dissociation constants of the weak acids derived from quinizarin (1,4-dihydroxy anthraquinone); QMF (2-(2-fury l methyl)), QMPH (2-(2-phenyl methyl)) and QMN (2-(2-naphthyl methyl)) quinizarin were determined. The stability constants of uranyl complexes with the above mentioned ligands were investigated by: 1. The molar-ratio method. 2. Computer program
Ramirez de Noriega, Fernando; Eitan, Renana; Marmor, Odeya; Lavi, Adi; Linetzky, Eduard; Bergman, Hagai; Israel, Zvi
2015-02-18
Background: Subthalamic nucleus (STN) deep brain stimulation (DBS) is an established therapy for advanced Parkinson's disease (PD). Motor efficacy and safety have been established for constant voltage (CV) devices and more recently for constant current (CC) devices. CC devices adjust output voltage to provide CC stimulation irrespective of impedance fluctuation, while the current applied by CV stimulation depends on the impedance that may change over time. No study has directly compared the clinical effects of these two stimulation modalities. Objective: To compare the safety and clinical impact of CC STN DBS to CV STN DBS in patients with advanced PD 2 years after surgery. Methods: Patients were eligible for inclusion if they had undergone STN DBS surgery for idiopathic PD, had been implanted with a Medtronic Activa PC and if their stimulation program and medication had been stable for at least 1 year. This single-center trial was designed as a double-blind, randomized, prospective study with crossover after 2 weeks. Motor equivalence of the 2 modalities was confirmed utilizing part III of the Unified Parkinson's Disease Rating Scale (UPDRS). PD diaries and multiple subjective and objective evaluations of quality of life, depression, cognition and emotional processing were evaluated on both CV and on CC stimulation. Analysis using the paired t test with Bonferroni correction for multiple comparisons was performed to identify any significant difference between the stimulation modalities. Results: 8 patients were recruited (6 men, 2 women); 1 patient did not complete the study. The average age at surgery was 56.7 years (range 47-63). Disease duration at the time of surgery was 7.5 years (range 3-12). Patients were recruited 23.8 months (range 22.5-24) after surgery. At the postoperative study baseline, this patient group showed an average motor improvement of 69% (range 51-97) as measured by the change in UPDRS part III with stimulation alone. Levodopa equivalent
Charge dependence of the pion-nucleon coupling constant
Directory of Open Access Journals (Sweden)
V. A. Babenko
2015-07-01
Full Text Available On the basis of the Yukawa potential we study the pion-nucleon coupling constants for the neutral and charged pions assuming that nuclear forces at low energies are mainly determined by the exchange of virtual pions. We obtain the charged pseudovector pion-nucleon coupling constant f2π± = 0.0804(7 by making the use of experimental low-energy scattering parameters for the singlet pp- and np-scattering, and also by use of the neutral pseudovector pion-nucleon coupling constant f2π0 = 0.0749(7. Corresponding value of the charged pseudoscalar pion-nucleon coupling constant g2π0 / 4π = 14.55(13 is also determined. This calculated value of the charged pseudoscalar pion-nucleon coupling constant is in fully agreement with the experimental constant g2π0 / 4π = 14.52(26 obtained by the Uppsala Neutron Research Group. Our results show considerable charge splitting of the pion-nucleon coupling constant.
Larson-Miller Constant of Heat-Resistant Steel
Tamura, Manabu; Abe, Fujio; Shiba, Kiyoyuki; Sakasegawa, Hideo; Tanigawa, Hiroyasu
2013-06-01
Long-term rupture data for 79 types of heat-resistant steels including carbon steel, low-alloy steel, high-alloy steel, austenitic stainless steel, and superalloy were analyzed, and a constant for the Larson-Miller (LM) parameter was obtained in the current study for each material. The calculated LM constant, C, is approximately 20 for heat-resistant steels and alloys except for high-alloy martensitic steels with high creep resistance, for which C ≈ 30 . The apparent activation energy was also calculated, and the LM constant was found to be proportional to the apparent activation energy with a high correlation coefficient, which suggests that the LM constant is a material constant possessing intrinsic physical meaning. The contribution of the entropy change to the LM constant is not small, especially for several martensitic steels with large values of C. Deformation of such martensitic steels should accompany a large entropy change of 10 times the gas constant at least, besides the entropy change due to self-diffusion.
Computing the Gromov hyperbolicity constant of a discrete metric space
Ismail, Anas
2012-07-01
Although it was invented by Mikhail Gromov, in 1987, to describe some family of groups[1], the notion of Gromov hyperbolicity has many applications and interpretations in different fields. It has applications in Biology, Networking, Graph Theory, and many other areas of research. The Gromov hyperbolicity constant of several families of graphs and geometric spaces has been determined. However, so far, the only known algorithm for calculating the Gromov hyperbolicity constant δ of a discrete metric space is the brute force algorithm with running time O (n4) using the four-point condition. In this thesis, we first introduce an approximation algorithm which calculates a O (log n)-approximation of the hyperbolicity constant δ, based on a layering approach, in time O(n2), where n is the number of points in the metric space. We also calculate the fixed base point hyperbolicity constant δr for a fixed point r using a (max, min)−matrix multiplication algorithm by Duan in time O(n2.688)[2]. We use this result to present a 2-approximation algorithm for calculating the hyper-bolicity constant in time O(n2.688). We also provide an exact algorithm to compute the hyperbolicity constant δ in time O(n3.688) for a discrete metric space. We then present some partial results we obtained for designing some approximation algorithms to compute the hyperbolicity constant δ.
Large numbers hypothesis. IV - The cosmological constant and quantum physics
Adams, P. J.
1983-01-01
In standard physics quantum field theory is based on a flat vacuum space-time. This quantum field theory predicts a nonzero cosmological constant. Hence the gravitational field equations do not admit a flat vacuum space-time. This dilemma is resolved using the units covariant gravitational field equations. This paper shows that the field equations admit a flat vacuum space-time with nonzero cosmological constant if and only if the canonical LNH is valid. This allows an interpretation of the LNH phenomena in terms of a time-dependent vacuum state. If this is correct then the cosmological constant must be positive.
Behaviour of coupling constants at high temperature in supersymmetric theories
International Nuclear Information System (INIS)
Swee Ping Chia.
1986-04-01
An analysis is presented of the temperature dependence of the coupling constants using the improved one-loop approximation in the Wess-Zumino model and the supersymmetric O(N) model. It is found that all the coupling constants, both bosonic (Φ 4 type) and Yukawa, approach constant nonzero values as T→∞. The asymptotic values of the bosonic couplings are slightly smaller than the corresponding zero-temperature values, and those of the Yukawa couplings are the same as the zero-temperature values. (author)
On time variation of fundamental constants in superstring theories
International Nuclear Information System (INIS)
Maeda, K.I.
1988-01-01
Assuming the action from the string theory and taking into account the dynamical freedom of a dilaton and its coupling to matter fluid, the authors show that fundamental 'constants' in string theories are independent of the 'radius' of the internal space. Since the scalar related to the 'constants' is coupled to the 4-dimensional gravity and matter fluid in the same way as in the Jordan-Brans Dicke theory with ω = -1, it must be massive and can get a mass easily through some symmetry breaking mechanism (e.g. the SUSY breaking due to a gluino condensation). Consequently, time variation of fundamental constants is too small to be observed
Procedures for determining MATMOD-4V material constants
Energy Technology Data Exchange (ETDEWEB)
Lowe, T.C.
1993-11-01
The MATMOD-4V constitutive relations were developed from the original MATMOD model to extend the range of nonelastic deformation behaviors represented to include transient phenomena such as strain softening. Improvements in MATMOD-4V increased the number of independent material constants and the difficulty in determining their values. Though the constitutive relations are conceptually simple, their form and procedures for obtaining their constants can be complex. This paper reviews in detail the experiments, numerical procedures, and assumptions that have been used to determine a complete set of MATMOD-4V constants for high purity aluminum.
Measurement of the saturation magnetostriction constant of amorphous wire
International Nuclear Information System (INIS)
Mitra, A.; Vazquez, M.
1990-01-01
Measurement of the magnetostriction constant of amorphous wire by conventional techniques is very difficult because of its small diameter. However, accurate determination of the magnetostriction constant is important in the study of amorphous wires. Here the saturation magnetostriction constant (λ s ) for a low-magnetostriction amorphous wire of nominal composition (Fe 6.3 Co 92.7 Nb 1 ) 77.5 Si 7.5 B 15 has been determined by means of the small-angle magnetization-rotation method. λ s has been evaluated to be 2.1x10 -7 for its as-received state. The dependence of thermal treatment is also reported
Directory of Open Access Journals (Sweden)
Ostojić Vladimir B.
2015-01-01
Full Text Available The paper discusses the evolutive aspects of short “jat” following the sonant r usage during the formation of the modern Serbian literary language and its treatment in the Serbo-Croatistic and the Serbistic descriptive and normative literature. In addition to the basic issue of the distribution of the short “jat’s” substituent following the sonant r in dialects of Montenegro, particularly in the native dialect of Vuk Karadžić’s ancestors, the author also addresses the question related to the mechanisms that cause short “jat” following the sonant r in ijekavian dialects to be reduced sometimes to e, and sometimes to je. Substitution of short “jat” following the sonant r in Jezera-Šarani dialect had important evolution from the times of “classical Vukovian ijekavism”. In this dialect, forms with rje do not occur, except in the word starješina. Here, r and j remained in the same syllable, which set the stage for iotization and depalatalization. The analysis of the paper describes the situation in Jezera-Šarani dialect as well as the situation in other Montenegrian dialects of the older and newer Eastern-Herzegovian type. The author as well takes into consideration that our Pravopis has already disregarded the Vukovian tradition with omitting j that follows sonant r in the examples pogreška and greška. In order to eliminate the disunity, the author concludes that the status of the group re should not be questioned from the aspect of literary language standards.
Directory of Open Access Journals (Sweden)
Yong Hu
2016-06-01
Full Text Available The electronic structures and charge transport properties of 1,3,5-tripyrrolebenzene (TPB and its substituted derivatives with –F and –CN groups have been investigated by DFT calculations in combination with the Marcus hopping model. The dimer geometry was optimized by density functional theory method with dispersion force correction being included (DFT-D. Consequently, the charge transfer integral was evaluated. The calculation results show that the introduction of electron-withdrawing substituents does not significantly change the bond lengths and molecular symmetry of TPB, but lower the coplanarity between the pyrrole and benzene rings, especially in the case of CN substitution. Meanwhile, the introduction of electron-withdrawing groups can decrease the energy of the frontier molecular orbital and enhance the air stability. Fluorination makes the λe increase obviously while cyanation dose not. Generally speaking, the λe values of the title compounds are larger than their λh. Except for compounds 6 and 9, all others keep the face to face packing or have a slight slip in dimers, but the center of mass distances increase after fluorination or cyanation due to the distortion of the monomer’s coplanarity. The predicted quasi-one-dimensional electron mobility of the dimers is up to 0.433 cm2 V-1 s-1 at 298.15 K. The electron injection barriers of 2 and 7 are lower than that of TPB. The TPB derivatives of 1, 2, and 7 are potential n-channel materials with the high electron mobility. This work is licensed under a Creative Commons Attribution 4.0 International License.
Directory of Open Access Journals (Sweden)
Wasinee Phonsri
2017-08-01
Full Text Available The structural and magnetic properties of a range of new iron(III bis-tridentate Schiff base complexes are described with emphasis on how intermolecular structural interactions influence spin states and spin crossover (SCO in these d5 materials. Three pairs of complexes were investigated. The first pair are the neutral, heteroleptic complexes [Fe(3-OMe-SalEen(thsa] 1 and [Fe(3-MeOSalEen(3-EtOthsa] 2, where 3-R-HSalEen = (E-2-(((2-(ethylaminoethyliminomethyl-6-R-phenol and 3-R-H2thsa = thiosemicarbazone-3-R-salicylaldimine. They display spin transitions above room temperature. However, 2 shows incomplete and gradual change, while SCO in 1 is complete and more abrupt. Lower cooperativity in 2 is ascribed to the lack of π–π interactions, compared to 1. The second pair, cationic species [Fe(3-EtOSalEen2]NO3 3 and [Fe(3-EtOSalEen2]Cl 4 differ only in the counter-anion. They show partial SCO above room temperature with 3 displaying a sharp transition at 343 K. Weak hydrogen bonds from cation to Cl− probably lead to weaker cooperativity in 4. The last pair, CsH2O[Fe(3-MeO-thsa2] 5 and Cs(H2O2[Fe(5-NO2-thsa2] 6, are anionic homoleptic chelates that have different substituents on the salicylaldiminate rings of thsa2−. The Cs cations bond to O atoms of water and the ligands, in unusual ways thus forming attractive 1D and 3D networks in 5 and 6, respectively, and 5 remains HS (high spin at all temperatures while 6 remains LS (low spin. Comparisons are made to other literature examples of Cs salts of [Fe(5-R-thsa2]− (R = H and Br.
Pylina, Yana I; Shadrin, Dmitry M; Shevchenko, Oksana G; Startseva, Olga M; Velegzhaninov, Igor O; Belykh, Dmitry V; Velegzhaninov, Ilya O
2017-01-05
In the present work, we investigated the dark and photoinduced cytotoxic activity of the new chlorophyll-a derivatives which contain the substituents of oligoethylene glycol on the periphery of their macrocycles. These compounds were tested using human cell lines to estimate their potential as photosensitizers for photodynamic therapy of cancer. It was shown that all the tested compounds have expressed photoinduced cytotoxic activity in vitro. Detailed study of the biological activity of one of the most perspective compound in this series-pyropheophorbide-a 17-diethylene glycol ester (Compound 21 ) was performed. This new compound is characterized by lower dark cytotoxicity and higher photoinduced cytotoxicity than previously described in a similar compound (DH-I-180-3) and clinically used Photolon TM . Using fluorescent microscopy, it was shown that Compound 21 quickly penetrates the cells. Analysis of caspase-3 activity indicated an apoptosis induction 40 min after exposure to red light (λ = 660 nm). The induction of DNA damages and apoptosis was shown using Comet assay. The results of expression analysis of the stress-response genes indicate an activation of the genes which control the cell cycle and detoxification of the free radicals after an exposure of HeLa cells to Compound 21 and to red light. High photodynamic activity of this compound and the ability to oxidize biomolecules was demonstrated on nuclear-free mice erythrocytes. In addition, it was shown that Compound 21 is effectively activated with low energy 700 nm light, which can penetrate deep into the tissue. Thus, Compound 21 is a prospective substance for development of the new drugs for photodynamic therapy of cancer.
Directory of Open Access Journals (Sweden)
Yana I. Pylina
2017-01-01
Full Text Available In the present work, we investigated the dark and photoinduced cytotoxic activity of the new chlorophyll-a derivatives which contain the substituents of oligoethylene glycol on the periphery of their macrocycles. These compounds were tested using human cell lines to estimate their potential as photosensitizers for photodynamic therapy of cancer. It was shown that all the tested compounds have expressed photoinduced cytotoxic activity in vitro. Detailed study of the biological activity of one of the most perspective compound in this series—pyropheophorbide-a 17-diethylene glycol ester (Compound 21 was performed. This new compound is characterized by lower dark cytotoxicity and higher photoinduced cytotoxicity than previously described in a similar compound (DH-I-180-3 and clinically used PhotolonTM. Using fluorescent microscopy, it was shown that Compound 21 quickly penetrates the cells. Analysis of caspase-3 activity indicated an apoptosis induction 40 min after exposure to red light (λ = 660 nm. The induction of DNA damages and apoptosis was shown using Comet assay. The results of expression analysis of the stress-response genes indicate an activation of the genes which control the cell cycle and detoxification of the free radicals after an exposure of HeLa cells to Compound 21 and to red light. High photodynamic activity of this compound and the ability to oxidize biomolecules was demonstrated on nuclear-free mice erythrocytes. In addition, it was shown that Compound 21 is effectively activated with low energy 700 nm light, which can penetrate deep into the tissue. Thus, Compound 21 is a prospective substance for development of the new drugs for photodynamic therapy of cancer.
Translation of selected papers published in Nuclear Constants 4, 1986
International Nuclear Information System (INIS)
1989-08-01
The document includes the English translation of 7 papers published in the Russian journal Nuclear Constants 4, 1986 and dealing with neutron data evaluations for actinide nuclei and iron. Refs, figs and tab
Density-dependent coupling constants and charge symmetry breaking
International Nuclear Information System (INIS)
Barreiro, L.A.
2001-01-01
The effect of the medium in the coupling constants implicate in a charge symmetry breaking on nuclear interactions. The amount of energy due to this modification can explain the Nolen-Schiffer anomaly. (author)
Low Cost Constant – Head Drip Irrigation Emitter for Climate ...
African Journals Online (AJOL)
Low Cost Constant – Head Drip Irrigation Emitter for Climate Change Adaptation in Nigeria: Engineering Design and Calibration. ... The drip system comprises of abarrel, sub-main line, lateral lines, tubes and emitters, it can irrigate140 crop ...
Dynamics of the cosmological and Newton’s constant
International Nuclear Information System (INIS)
Smolin, Lee
2016-01-01
A modification of general relativity is presented in which Newton’s constant, G, and the cosmological constant, Λ, become a conjugate pair of dynamical variables. These are functions of a global time, hence the theory is presented in the framework of shape dynamics, which trades many-fingered time for a local scale invariance and an overall reparametrization of the global time. As a result, due to the fact that these global dynamical variables are canonically conjugate, the field equations are consistent. The theory predicts a relationship with no free parameters between the rates of change of Newton’s constant and the cosmological constant, in terms of the spatial average of the matter Lagrangian density. (paper)
Determination of the π3He3H coupling constant
International Nuclear Information System (INIS)
Nichitiu, F.; Sapozhnikov, M.G.
1977-01-01
Despersion relations for the real part of the antisymmetric amplitude of the π +-3 He scattering have been used in order to determine the π 3 He 3 H coupling constant. The coupling constant value determined by this method is larger than the elementary pion-nucleon coupling constant, but is in good agreement with the value obtained by another method. The obtained value is f 2 sub(π 3 He 3 H) = 0.12+-0.01. Shown is the importance of using the Coulomb corrections for dispersion relation calculations because the value of π 3 He 3 H coupling constant obtained with corrected total cross sections is larger by about 0.014 than the one obtained without these corrections. The best energy ranges for future π 3 He experiments are commented
Syntheses, Protonation Constants and Antimicrobial Activity of 2 ...
African Journals Online (AJOL)
carboxaldehyde and N-alkylimidazole-2-methanol derivatives [alkyl = benzyl, methyl, ethyl, propyl, butyl, heptyl, octyl and decyl] have been synthesized and the protonation constants determined. The antimicrobial properties of the compounds were tested ...
A constant gradient planar accelerating structure for linac use
International Nuclear Information System (INIS)
Kang, Y.W.; Matthews, P.J.; Kustom, R.L.
1995-01-01
Planar accelerating millimeter-wave structures have been studied during the last few years at Argonne National Laboratory in collaboration with Technical University of Berlin. The cavity structures are intended to be manufactured by using x-ray lithography microfabrication technology. A complete structure consists of two identical planar half structures put together face-to-face. Since microfabrication technology can make a since-depth indentation on a planar substrate, realizing the constant impedance structure was possible but a constant gradient structure was difficult; changing the group velocity along the structure while maintaining the gap and the depth of the indentation constant was difficult. A constant gradient structure has been devised by introducing a cut between the adjacent cavity cells along the beam axis of each half structure. The width of the cut is varied along the longitudinal axis of the structure to have proper coupling between the cells. The result of the computer simulation on such structures is shown
Robust control for constant thrust rendezvous under thrust failure
Directory of Open Access Journals (Sweden)
Qi Yongqiang
2015-04-01
Full Text Available A robust constant thrust rendezvous approach under thrust failure is proposed based on the relative motion dynamic model. Firstly, the design problem is cast into a convex optimization problem by introducing a Lyapunov function subject to linear matrix inequalities. Secondly, the robust controllers satisfying the requirements can be designed by solving this optimization problem. Then, a new algorithm of constant thrust fitting is proposed through the impulse compensation and the fuel consumption under the theoretical continuous thrust and the actual constant thrust is calculated and compared by using the method proposed in this paper. Finally, the proposed method having the advantage of saving fuel is proved and the actual constant thrust switch control laws are obtained through the isochronous interpolation method, meanwhile, an illustrative example is provided to show the effectiveness of the proposed control design method.
National Aeronautics and Space Administration — The MAC0NXASM or const_2d_asm_Nx data product is the MERRA Data Assimilation System 2-Dimensional Constants at native resolution. MERRA, or the Modern Era...
National Aeronautics and Space Administration — The MAC0FXCHM or const_2d_chm_Fx data product is the MERRA Data Assimilation System 2-Dimensional Constants at native Fv resolution. MERRA, or the Modern Era...
Long Pulse Integrator of Variable Integral Time Constant
International Nuclear Information System (INIS)
Wang Yong; Ji Zhenshan; Du Xiaoying; Wu Yichun; Li Shi; Luo Jiarong
2010-01-01
A kind of new long pulse integrator was designed based on the method of variable integral time constant and deducting integral drift by drift slope. The integral time constant can be changed by choosing different integral resistors, in order to improve the signal-to-noise ratio, and avoid output saturation; the slope of integral drift of a certain period of time can be calculated by digital signal processing, which can be used to deduct the drift of original integral signal in real time to reduce the integral drift. The tests show that this kind of long pulse integrator is good at reducing integral drift, which also can eliminate the effects of changing integral time constant. According to experiments, the integral time constant can be changed by remote control and manual adjustment of integral drift is avoided, which can improve the experiment efficiency greatly and can be used for electromagnetic measurement in Tokamak experiment. (authors)
Determination of Biological Oxygen Demand Rate Constant and ...
African Journals Online (AJOL)
Determination of Biological Oxygen Demand Rate Constant and Ultimate Biological Oxygen Demand for Liquid Waste Generated from Student Cafeteria at Jimma University: A Tool for Development of Scientific Criteria to Protect Aquatic Health in the Region.
Constant scalar curvature hypersurfaces in extended Schwarzschild space-time
International Nuclear Information System (INIS)
Pareja, M. J.; Frauendiener, J.
2006-01-01
We present a class of spherically symmetric hypersurfaces in the Kruskal extension of the Schwarzschild space-time. The hypersurfaces have constant negative scalar curvature, so they are hyperboloidal in the regions of space-time which are asymptotically flat
Implications of the Cosmological Constant for Spherically Symmetric Mass Distributions
Zubairi, Omair; Weber, Fridolin
2013-04-01
In recent years, scientists have made the discovery that the expansion rate of the Universe is increasing rather than decreasing. This acceleration leads to an additional term in Albert Einstein's field equations which describe general relativity and is known as the cosmological constant. This work explores the aftermath of a non-vanishing cosmological constant for relativistic spherically symmetric mass distributions, which are susceptible to change against Einstein's field equations. We introduce a stellar structure equation known as the Tolman-Oppenhiemer-Volkoff (TOV) equation modified for a cosmological constant, which is derived from Einstein's modified field equations. We solve this modified TOV equation for these spherically symmetric mass distributions and obtain stellar properties such as mass and radius and investigate changes that may occur depending on the value of the cosmological constant.
Number of generations related to coupling constants by confusion
International Nuclear Information System (INIS)
Bennett, D.L.; Nielsen, H.B.
1987-01-01
In the context of random dynamics, the mechanism of confusion is used to obtain a relation between the number of generations and standard model coupling constants. Preliminary results predict the existence of four generations. (orig.)
Convexity and concavity constants in Lorentz and Marcinkiewicz spaces
Kaminska, Anna; Parrish, Anca M.
2008-07-01
We provide here the formulas for the q-convexity and q-concavity constants for function and sequence Lorentz spaces associated to either decreasing or increasing weights. It yields also the formula for the q-convexity constants in function and sequence Marcinkiewicz spaces. In this paper we extent and enhance the results from [G.J.O. Jameson, The q-concavity constants of Lorentz sequence spaces and related inequalities, Math. Z. 227 (1998) 129-142] and [A. Kaminska, A.M. Parrish, The q-concavity and q-convexity constants in Lorentz spaces, in: Banach Spaces and Their Applications in Analysis, Conference in Honor of Nigel Kalton, May 2006, Walter de Gruyter, Berlin, 2007, pp. 357-373].
Computing magnetic anisotropy constants of single molecule magnets
Indian Academy of Sciences (India)
Administrator
Treating the anisotropy Hamiltonian as perturbation, we compute ... The dependence of DM on the energy gap between the ground and the excited states in both the systems has also been studied by using different sets of exchange constants.
computation of the stability constants for the inclusion complexes of
African Journals Online (AJOL)
PrF MU
stability constants of ADA with β-CD with the use of MO as an auxiliary agent were evaluated. ..... The latter statement can also be strengthened by the computed species distribution diagram for .... and 5-position of the adamantyl body.
A Kalman-filter estimate of the tidal harmonic constants
International Nuclear Information System (INIS)
Morsetti, R.
1983-01-01
A Kalman-filter estimate of the tidal harmonic constants is proposed in order to take into account their stochastic behaviour. The filter algorithm has been applied to a state-space model of a stochastic system in which the state is defined by the harmonic constants themselves. The results, analysing Trieste sea-level data, have demonstrated that this approach is very suitable for such a purpose, since good estimates and excellent resolution capabilities have been obtained. Furthermore, this method can be very useful also from a practical point of view because real-time computation of the harmonic constants can be developed where an opportune sea-level data acquisition system is available. In conclusion, this paper has emphasized that tidal harmonic constants have to be treated like random variables and, in consequence, new method of analysis can be used
The Thickness Dependence of Optical Constants of Ultrathin Iron Films
International Nuclear Information System (INIS)
Gao Shang; Lian Jie; Wang Xiao; Li Ping; Sun Xiao-Fen; Li Qing-Hao
2013-01-01
Ultrathin iron films with different thicknesses from 7.1 to 51.7 nm are deposited by magnetron sputtering and covered by tantalum layers protecting them from being oxidized. These ultrathin iron films are studied by spectroscopic ellipsometry and transmittance measurement. An extra tantalum film is deposited under the same sputtering conditions and its optical constants and film thickness are obtained by a combination of ellipsometry and transmission measurement. After introducing these obtained optical constants and film thickness into the tantalum-iron film, the optical constants and film thicknesses of ultrathin iron films with different thicknesses are obtained. The results show that combining ellipsometry and transmission measurement improves the uniqueness of the obtained film thickness. The optical constants of ultrathin iron films depend strongly on film thicknesses. There is a broad absorption peak at about 370 nm and it shifts to 410 nm with film thickness decreasing
Imaging performance of an isotropic negative dielectric constant slab.
Shivanand; Liu, Huikan; Webb, Kevin J
2008-11-01
The influence of material and thickness on the subwavelength imaging performance of a negative dielectric constant slab is studied. Resonance in the plane-wave transfer function produces a high spatial frequency ripple that could be useful in fabricating periodic structures. A cost function based on the plane-wave transfer function provides a useful metric to evaluate the planar slab lens performance, and using this, the optimal slab dielectric constant can be determined.
One-group constant libraries for nuclear equilibrium state
Energy Technology Data Exchange (ETDEWEB)
Mizutani, Akihiko; Sekimoto, Hiroshi [Tokyo Inst. of Tech. (Japan). Research Lab. for Nuclear Reactors
1997-03-01
One-group constant libraries for the nuclear equilibrium state were generated for both liquid sodium cooled MOX fuel type fast reactor and PWR type thermal reactor with Equilibrium Cell Iterative Calculation System (ECICS) using JENDL-3.2, -3, -2 and ENDF/B-VI nuclear data libraries. ECICS produced one-group constant sets for 129 heavy metal nuclides and 1238 fission products. (author)
Selected articles translated from Jadernye Konstanty (Nuclear Constants)
International Nuclear Information System (INIS)
1999-04-01
The document contains the following three papers: 'Evaluation of the decay characteristics of 3 H and 36 Cl', 'Validation of the ABBN/CONSYST constants system. Part 1: Validation through the critical experiments on compact metallic cores', and 'Validation of the ABBN/CONSYST constants system. Part 2: Validation through the critical experiments on cores with uranium solutions'. A separate abstract was prepared for each paper
Elastic constants and internal friction of fiber-reinforced composites
International Nuclear Information System (INIS)
Ledbetter, H.M.
1982-01-01
We review recent experimental studies at NBS on the anisotropic elastic constants and internal friction of fiber-reinforced composites. Materials that were studied include: boron-aluminum, boron-epoxy, graphite-epoxy, glass-epoxy, and aramid-epoxy. In all cases, elastic-constant direction dependence could be described by relationships developed for single crystals of homogeneous materials. Elastic stiffness and internal friction were found to vary inversely
Best constants in a class of polymultiplicative inequalities for derivatives
International Nuclear Information System (INIS)
Ilyin, A A
1998-01-01
Best constants are found in a class of multiplicative inequalities with k factors that give an estimate of the C-norm of a function (in R n or on S n ) in terms of the product of the L 2 -norms of fractional powers of the Laplace operator. Special attention is given to the detection of the cases of equality of the corresponding constants on the sphere and in Euclidean space
Simple Model with Time-Varying Fine-Structure ``Constant''
Berman, M. S.
2009-10-01
Extending the original version written in colaboration with L.A. Trevisan, we study the generalisation of Dirac's LNH, so that time-variation of the fine-structure constant, due to varying electrical and magnetic permittivities is included along with other variations (cosmological and gravitational ``constants''), etc. We consider the present Universe, and also an inflationary scenario. Rotation of the Universe is a given possibility in this model.
Scale solutions and coupling constant in electrodynamics of vector particles
International Nuclear Information System (INIS)
Arbuzov, B.A.; Boos, E.E.; Kurennoy, S.S.
1980-01-01
A new approach in nonrenormalizable gauge theories is studied, the electrodynamics of vector particles being taken as an example. One and two-loop approximations in Schwinger-Dyson set of equations are considered with account for conditions imposed by gauge invariance. It is shown, that solutions with scale asymptotics can occur in this case but only for a particular value of coupling constant. This value in solutions obtained is close to the value of the fine structure constant α=1/137
Experimental determination of third-order elastic constants of diamond.
Lang, J M; Gupta, Y M
2011-03-25
To determine the nonlinear elastic response of diamond, single crystals were shock compressed along the [100], [110], and [111] orientations to 120 GPa peak elastic stresses. Particle velocity histories and elastic wave velocities were measured by using laser interferometry. The measured elastic wave profiles were used, in combination with published acoustic measurements, to determine the complete set of third-order elastic constants. These constants represent the first experimental determination, and several differ significantly from those calculated by using theoretical models.