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1.
J Chem Phys ; 141(21): 214307, 2014 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-25481144

RESUMO

Hydrated Fe(+) ions are produced in a laser-vaporization cluster source of a triple quadrupole mass spectrometer. The Fe(+)(H2O)n (n = 3-8) complexes are mass-selected and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region. Density functional theory (DFT) calculations are also carried out for analyzing the experimental IR spectra and for evaluating thermodynamic quantities of low-lying isomers. Solvation through H-bonding instead of direct coordination to Fe(+) is observed already at n = 3, indicating the completion of the first hydration shell with two H2O molecules. Size dependent variations in the spectra for n = 5-7 provide evidence for the second-shell completion at n = 6, where a linearly coordinated Fe(+)(H2O)2 subunit is solvated with four H2O molecules. Overall spectral features for n = 3-8 agree well with those predicted for 2-coordinated structures. DFT calculations predict that such 2-coordinated structures are lowest in energy for smaller n. However, 4-coordinated isomers are predicted to be more stable for n = 7 and 8; the energy ordering is in conflict with the IR spectroscopic observation. Examination of free energy as a function of temperature suggests that the ordering of the isomers at warmer temperatures can be different from the ordering near 0 K. For n = 7 and 8, the 4-coordinated isomers should be observed at low temperatures because they are lowest in enthalpy. Meanwhile, outer-shell waters in the 2-coordinated structures are bound less rigidly; their contribution to entropy is rather large. The 2-coordinated structures become abundant at warmer temperatures, owing to the entropy effect.

2.
Inorg Chem ; 50(8): 3464-70, 2011 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-21395239

RESUMO

A new chromium complex with ethynyltetrathiafulvalene (TTF)-type ligands, [CrCyclam(C≡C-5-methyl-4'5'-ethylenedithio-TTF)(2)]OTf ([1]OTf), was synthesized. The cyclic voltammetry of the complex shows two reversible oxidation waves owing to the first and second oxidation of the TTF unit. The electrochemical oxidation of [1]OTf in a Bu(4)NClO(4) or Bu(4)NBF(4) solution of a 1:1 acetonitrile-chlorobenzene mixture gave isostructural crystals of [1][ClO(4)](2)(PhCl)(2)(MeCN) and [1][BF(4)](2)(PhCl)(2)(MeCN), where two mixed-valence TTF units of adjacent complexes form a dimer radical cation. The crystal structures are characterized by an alternating chain of S = 3/2 Cr(3+)Cyclam units and S = ½ (TTF)(2)(+) dimers. These two paramagnetic components are connected directly by an ethynyl group, resulting in a strong intrachain spin-spin interaction of 2J/k(B) = -30 and -28 K for [ClO(4)](-) and [BF(4)](-) salts, respectively (H = -2J∑(i)S(i)·S(i+1)). Both salts show a weak ferromagnetic transition at 23 K thanks to interchain antiferromagnetic interaction between TTF dimers. The remanent magnetizations and coercive forces of nonoriented samples at 1.8 K are 0.016 µ(B) and 90 mT for the [ClO(4)](-) salt and 0.010 µ(B) and 50 mT Oe for the [BF(4)](-) salt, respectively. The weak ferromagnetism is attributed to the Dzyaloshinsky-Moriya interaction between adjacent TTF dimers and/or the single-ion anisotropy of [1](2+).

3.
Artigo em Inglês | MEDLINE | ID: mdl-34236042

RESUMO

SUMMARY: IgG4-related hypophysitis is an autoimmune hypophysitis associated with IgG4-related disease. Swelling of the pituitary gland is responsive to steroid therapy, but the prognosis of pituitary function after the treatment remains unclear. The present case implies that transiently improved pituitary function can re-worsen during long-term follow-up in IgG4-related hypophysitis. A 71-year-old male patient with IgG4-related hypophysitis visited a nearby hospital with malaise, anorexia, and polyuria. Pituitary dysfunction was suspected, so he was referred to our hospital for further examination. Imaging studies and laboratory data showed swelling of the pituitary gland and panhypopituitarism, which dramatically improved following steroid therapy. There was no evidence of relapsing IgG4-related disease during prednisolone tapering. Pituitary function was examined after 4 years under treatment with low-dose prednisolone; surprisingly, anterior pituitary function had worsened again. Our case suggests a need for continuous monitoring of pituitary function after steroid therapy for IgG4-related hypophysitis. This report illustrates the natural course of pituitary function in IgG4-related hypophysitis and may be informative when considering the introduction of steroid therapy. LEARNING POINTS: Steroid therapy is an effective first-line therapy for pituitary dysfunction and pituitary swelling in IgG4-related hypophysitis. Pituitary function can worsen again during follow-up, despite transient improvement after steroid therapy in IgG4-related hypophysitis. Continuous monitoring of pituitary function is necessary for IgG4-related hypophysitis, regardless of disease activity.

4.
Phys Chem Chem Phys ; 12(37): 11647-56, 2010 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-20714490

RESUMO

Coordination structures of the Co(+)(NH(3))(n) and Ni(+)(NH(3))(n) ions are probed by infrared (IR) photodissociation spectroscopy with the aid of density functional theory (DFT) calculations. The IR spectra of N(2)-tagged Co(+)(NH(3))(n) (n = 1-4) exhibit two distinct bands assignable to the symmetric and antisymmetric NH stretches of the NH(3) molecules binding directly to Co(+). Size-dependent changes in the spectra of Co(+)(NH(3))(n) (n = 4-8) indicate that the first shell of Co(+) is filled with four NH(3) molecules and the resulting 4-coordinated structure forms the central core of further solvation. The spectra of Ni(+)(NH(3))(n) (n = 3-8) suggest that the coordination number of Ni(+) is also four, although a minor 3-coordinated isomer is identified for Ni(+)(NH(3))(4). Despite the same coordination number, the DFT calculations predict a distorted square-planar coordination for Ni(+)(NH(3))(4) and a distorted tetrahedral coordination for Co(+)(NH(3))(4). The coordination of Ni(+)(NH(3))(4) is explainable by using a simple model based on the geometry of a half-filled 3d orbital in Ni(+). This suggests that the Ni(+) ion gives priority to the minimization of the metal-ligand repulsion in accommodating four ligands in the first shell. On the other hand, the same model fails to explain the coordination of Co(+)(NH(3))(4). An interpretation for this is that the Co(+) ion gives priority to the minimization of the ligand-ligand repulsion.


Assuntos
Amônia/química , Cobalto/química , Complexos de Coordenação/química , Níquel/química , Íons/química , Modelos Moleculares , Estrutura Molecular , Processos Fotoquímicos , Espectrofotometria Infravermelho/métodos
5.
Inorg Chem ; 48(19): 9402-8, 2009 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-19746900

RESUMO

The crystal structures and magnetic properties of new molecule-based magnets, [CrCyclam(C[triple bond]C-3-thiophene)(2)][Ni(mdt)(2)] (1) and [CrCyclam(C[triple bond]C-Ph)(2)][Ni(mdt)(2)](H(2)O) (2) (Cyclam = 1,4,8,11-tetraazacyclotetradecane, mdt = 1,3-dithiole-4,5-dithiolate), are reported. The crystal structures of both compounds are characterized by ferrimagnetic chains of alternately stacked [CrCyclam(C[triple bond]C-R)](+) cations and [Ni(mdt)(2)](-) anions with intrachain exchange interactions of 2J = -6.1 K in 1 and -5.7 K in 2 (H = -2J Sigma(i) S(i) x S(i+1)). The material 1 exhibits ferrimagnetic transition at 2.3 K owing to weak interchain antiferromagnetic interactions between cations and anions. In the case of 2, cations in adjacent ferrimagnetic chains are bridged by a water molecule, resulting in an interchain antiferromagnetic coupling. Despite a centrosymmetry of a whole crystal of 2, one bridging water molecule occupies only one of the two centrosymmetric sites and breaks a local centrosymmetry between adjacent cations. The interchain antiferromagnetic interaction and Dzyaloshinsky-Moriya interaction originated from the local symmetry breakdown of 2 bring a weak-ferromagnetic transition at 3.7 K with a coercive force of less than 0.8 mT, followed by the second magnetic phase transition at 2.9 K. Below this temperature, the coercive force rapidly increases from 1 to 11.8 mT as the temperature decreases from 2.9 to 1.8 K, while the remanent magnetization monotonically increases from 0.008 mu(B) at 3.6 K to 0.12 mu(B) at 1.8 K.

6.
BMC Public Health ; 8: 315, 2008 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-18793423

RESUMO

BACKGROUND: To respond to the rapid surge in the incidence of suicide in Japan, which appears to be an ongoing trend, the Japanese Multimodal Intervention Trials for Suicide Prevention (J-MISP) have launched a multimodal community-based suicide prevention program, NOCOMIT-J. The primary aim of this study is to examine whether NOCOMIT-J is effective in reducing suicidal behavior in the community. METHODS/DESIGN: This study is a community intervention trial involving seven intervention regions with accompanying control regions, all with populations of statistically sufficient size. The program focuses on building social support networks in the public health system for suicide prevention and mental health promotion, intending to reinforce human relationships in the community. The intervention program components includes a primary prevention measures of awareness campaign for the public and key personnel, secondary prevention measures for screening of, and assisting, high-risk individuals, after-care for individuals bereaved by suicide, and other measures. The intervention started in July 2006, and will continue for 3.5 years. Participants are Japanese and foreign residents living in the intervention and control regions (a total of population of 2,120,000 individuals). DISCUSSION: The present study is designed to evaluate the effectiveness of the community-based suicide prevention program in the seven participating areas. TRIAL REGISTRATION: UMIN Clinical Trials Registry (UMIN-CTR) UMIN000000460.


Assuntos
Serviços de Saúde Comunitária/métodos , Avaliação de Resultados em Cuidados de Saúde , Prevenção do Suicídio , Tentativa de Suicídio/prevenção & controle , Assistência ao Convalescente/métodos , Relações Comunidade-Instituição , Coleta de Dados/métodos , Feminino , Humanos , Classificação Internacional de Doenças , Japão , Masculino , Avaliação de Resultados em Cuidados de Saúde/métodos , Desenvolvimento de Programas , Análise de Regressão , Comportamento de Redução do Risco , Tamanho da Amostra , Suicídio/estatística & dados numéricos
7.
Jpn J Infect Dis ; 71(3): 225-228, 2018 05 24.
Artigo em Inglês | MEDLINE | ID: mdl-29709983

RESUMO

Severe fever with thrombocytopenia syndrome (SFTS) is a tick-borne infection with a high mortality rate. It is caused by the SFTS virus (SFTSV) and is endemic in some areas in western Japan, including the Kagoshima prefecture. In the present study, healthy individuals living in this prefecture were examined to assess for anti-SFTSV seroprevalence. An initial study was performed using the serum samples collected from a total of 646 individuals living in Kagoshima. At the same time, a questionnaire was used to collect information (such as occupation and a history of tick bite). Enzyme-linked immunosorbent assay and indirect immunofluorescence assay were used for the screening. Finally, the seroprevalence of anti-SFTSV antibodies was confirmed using a neutralization assay. Only 2 (0.3%) out of 646 study participants were positive for anti-SFTSV antibodies. No significant difference was observed between individuals who are at a high or low risk of tick bite in terms of seropositivity. Next, a total of 1,000 serum samples collected from general blood donors by the Japanese Red Cross Kyushu Block Blood Center were tested. None of these samples tested positive for anti-SFTSV antibodies. These results suggest a low seroprevalence of anti-SFTSV antibodies in healthy individuals living in an endemic area in Japan.


Assuntos
Anticorpos Antivirais/sangue , Febre por Flebótomos , Phlebovirus/imunologia , Adulto , Idoso , Doadores de Sangue/estatística & dados numéricos , Ensaio de Imunoadsorção Enzimática , Humanos , Japão/epidemiologia , Pessoa de Meia-Idade , Febre por Flebótomos/epidemiologia , Febre por Flebótomos/imunologia , Febre por Flebótomos/virologia , Estudos Soroepidemiológicos , Adulto Jovem
8.
BJPsych Open ; 4(6): 454-460, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30450224

RESUMO

BACKGROUND: Patients with schizophrenia or bipolar disorder have a high risk of developing type 2 diabetes. AIMS: To identify predictive factors for hyperglycaemic progression in individuals with schizophrenia or bipolar disorder and to determine whether hyperglycaemic progression rates differ among antipsychotics in regular clinical practice. METHOD: We recruited 1166 patients who initially had normal or prediabetic glucose levels for a nationwide, multisite, l-year prospective cohort study to determine predictive factors for hyperglycaemic progression. We also examined whether hyperglycaemic progression varied among patients receiving monotherapy with the six most frequently used antipsychotics. RESULTS: High baseline serum triglycerides and coexisting hypertension significantly predicted hyperglycaemic progression. The six most frequently used antipsychotics did not significantly differ in their associated hyperglycaemic progression rates over the 1-year observation period. CONCLUSIONS: Clinicians should carefully evaluate baseline serum triglycerides and coexisting hypertension and perform strict longitudinal monitoring irrespective of the antipsychotic used. DECLARATION OF INTEREST: The authors report no financial or other relationship that is relevant to the subject of this article. Relevant financial activities outside the submitted work are as follows. I.K. has received honoraria from Astellas, Chugai Pharmaceutical, Daiichi Sankyo, Dainippon Sumitomo Pharma, Eisai, Eli Lilly, Janssen Pharmaceutical, Kyowa Hakko Kirin, Meiji Seika Pharma, MSD, Nippon Chemiphar, Novartis Pharma, Ono Pharmaceutical, Otsuka Pharmaceutical, Pfizer, Tanabe Mitsubishi Pharma, Shionogi and Yoshitomiyakuhin; has received research/grant support from AbbVie GK, Asahi Kasei Pharma, Astellas, Boehringer Ingelheim, Chugai Pharmaceutical, Daiichi Sankyo, Dainippon Sumitomo Pharma, Eisai, Eli Lilly, GlaxoSmithKline, Kyowa Hakko Kirin, Meiji Seika Pharma, MSD, Novartis Pharma, Ono Pharmaceutical, Otsuka Pharmaceutical, Pfizer, Takeda Pharmaceutical, Tanabe Mitsubishi Pharma, Shionogi and Yoshitomiyakuhin; and is a member of the advisory boards of Dainippon Sumitomo Pharma and Tanabe Mitsubishi Pharma. Y.T. has received speaker's honoraria from Dainippon-Sumitomo Pharma, Otsuka, Meiji-Seika Pharma, Janssen Pharmaceutical, Daiichi-Sankyo Company, UCB Japan and Ono Pharmaceutical. K.U. has received honoraria from Dainippon Sumitomo Pharma, Eisai, Eli Lilly, Janssen Pharmaceutical, Kyowa Hakko Kirin, Meiji Seika Pharma, MSD, Takeda Pharmaceutical, Hisamitsu Pharmaceutical, Otsuka Pharmaceutical, Pfizer, Tanabe Mitsubishi Pharma, Shionogi and Yoshitomiyakuhin. B.Y. has received speaker's honoraria from Otsuka Pharmaceutical and Janssen Pharmaceutical. J. I. has received honoraria from Dainippon Sumitomo Pharma, Eli Lilly, Janssen Pharmaceutical, Meiji Seika Pharma, MSD, Novartis Pharma, Otsuka Pharmaceutical and Mochida Pharma.

11.
PLoS One ; 8(10): e74902, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-24130673

RESUMO

BACKGROUND: Multilevel and multimodal interventions have been suggested for suicide prevention. However, few studies have reported the outcomes of such interventions for suicidal behaviours. METHODS: We examined the effectiveness of a community-based multimodal intervention for suicide prevention in rural areas with high suicide rates, compared with a parallel prevention-as-usual control group, covering a total of 631,133 persons. The effectiveness was also examined in highly populated areas near metropolitan cities (1,319,972 persons). The intervention started in July 2006, and continued for 3.5 years. The primary outcome was the incidence of composite outcome, consisting of completed suicides and suicide attempts requiring admission to an emergency ward for critical care. We compared the rate ratios (RRs) of the outcomes adjusted by sex, age group, region, period and interaction terms. Analyses were performed on an intention-to-treat basis and stratified by sex and age groups. FINDINGS: In the rural areas, the overall median adherence of the intervention was significantly higher. The RR of the composite outcome in the intervention group decreased 7% compared with that of the control group. Subgroup analyses demonstrated heterogeneous effects among subpopulations: the RR of the composite outcome in the intervention group was significantly lower in males (RR = 0.77, 95% CI 0.59-0.998, p = 0.0485) and the RR of suicide attempts was significantly lower in males (RR = 0.39, 95% CI 0.22-0.68, p = 0.001) and the elderly (RR = 0.35, 95% CI 0.17-0.71, p = 0.004). The intervention had no effect on the RR of the composite outcome in the highly populated areas. INTERPRETATION: Our findings suggest that this community-based multimodal intervention for suicide prevention could be implemented in rural areas, but not in highly populated areas. The effectiveness of the intervention was shown for males and for the elderly in rural areas. TRIAL REGISTRATION: ClinicalTrials.gov NCT00737165 UMIN Clinical Trials Registry UMIN000000460.


Assuntos
Prevenção do Suicídio , Tentativa de Suicídio/prevenção & controle , Adulto , Idoso , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Avaliação de Programas e Projetos de Saúde
12.
Phys Chem Chem Phys ; 10(21): 3052-62, 2008 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-18688368

RESUMO

Infrared (IR) spectra are measured for Ag(+)(NH(3))(n) with n = 3-8 in the NH-stretch region using photodissociation spectroscopy. The spectra of n = 3 and 4 exhibit absorption features only near the frequencies of the isolated NH(3), indicating that every NH(3) molecule is coordinated individually to Ag(+). For n >or= 5, the occupation of the second shell is evidenced by lower-frequency features characteristic of hydrogen bonding between NH(3) molecules. Density functional theory and MP2 calculations are carried out in support of the experiments. A detailed comparison of the experimental and theoretical IR spectra reveals the preference for a tetrahedral coordination in the n = 5 and 6 ions. Likewise, most of the features observed in the spectra of n = 7 and 8 can be assigned to isomers containing a tetrahedrally coordinated inner shell as the basic structural motif. These results signify that the ammonia-solvated Ag(+) ion has a propensity toward a coordination number of four and the resulting tetrahedral Ag(+)(NH(3))(4) complex forms the central core of further solvation process.

13.
Phys Chem Chem Phys ; 9(34): 4793-802, 2007 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-17712458

RESUMO

Coordination and solvation structures of the Cu(+)(NH(3))(n) ions with n = 3-8 are studied by infrared photodissociation spectroscopy in the NH-stretch region with the aid of density functional theory calculations. Hydrogen bonding between NH(3) molecules is absent for n = 3, indicating that all NH(3) molecules are bonded directly to Cu(+) in a tri-coordinated form. The first sign of hydrogen bonding is detected at n = 4 through frequency reduction and intensity enhancement of the infrared transitions, implying that at least one NH(3) molecule is placed in the second solvation shell. The spectra of n = 4 and 5 suggest the coexistence of multiple isomers, which have different coordination numbers (2, 3, and 4) or different types of hydrogen-bonding configurations. With increasing n, however, the di-coordinated isomer is of growing importance until becoming predominant at n = 8. These results signify a strong tendency of Cu(+) to adopt the twofold linear coordination, as in the case of Cu(+)(H(2)O)(n).


Assuntos
Algoritmos , Amônia/química , Cobre/química , Modelos Químicos , Modelos Moleculares , Solventes/química , Espectrofotometria Infravermelho/métodos , Amônia/efeitos da radiação , Simulação por Computador , Cobre/efeitos da radiação , Raios Infravermelhos , Íons , Solventes/efeitos da radiação
14.
J Phys Chem A ; 111(27): 5995-6002, 2007 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-17569510

RESUMO

Infrared photodissociation spectra of Al(+)(CH(3)OH)(n) (n = 1-4) and Al(+)(CH(3)OH)(n)-Ar (n = 1-3) were measured in the OH stretching region, 3000-3800 cm(-1). For n = 1 and 2, sharp absorption bands were observed in the free OH stretching region, all of which were well reproduced by the spectra calculated for the solvated-type geometry with no hydrogen bond. For n = 3 and 4, there were broad vibrational bands in the energy region of hydrogen-bonded OH stretching vibrations, 3000-3500 cm(-1). Energies of possible isomers for the Al(+)(CH(3)OH)(3),4 ions with hydrogen bonds were calculated in order to assign these bands. It was found that the third and fourth methanol molecules form hydrogen bonds with methanol molecules in the first solvation shell, rather than a direct bonding with the Al(+) ion. For the Al(+)(CH(3)OH)(n) clusters with n = 1-4, we obtained no evidence of the insertion reaction, which occurs in Al(+)(H(2)O)(n). One possible explanation of the difference between these two systems is that the potential energy barriers between the solvated and inserted isomers in the Al(+)(CH(3)OH)(n) system is too high to form the inserted-type isomers.

15.
J Chem Phys ; 126(19): 194302, 2007 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-17523799

RESUMO

M(+)(H(2)O)(n) and M(+)(H(2)O)(n)Ar ions (M=Cu and Ag) are studied for exploring coordination and solvation structures of noble-metal ions. These species are produced in a laser-vaporization cluster source and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region using a triple quadrupole mass spectrometer. Density functional theory calculations are also carried out for analyzing the experimental IR spectra. Partially resolved rotational structure observed in the spectrum of Ag(+)(H(2)O)(1) x Ar indicates that the complex is quasilinear in an Ar-Ag(+)-O configuration with the H atoms symmetrically displaced off axis. The spectra of the Ar-tagged M(+)(H(2)O)(2) are consistent with twofold coordination with a linear O-M(+)-O arrangement for these ions, which is stabilized by the s-d hybridization in M(+). Hydrogen bonding between H(2)O molecules is absent in Ag(+)(H(2)O)(3) x Ar but detected in Cu(+)(H(2)O)(3) x Ar through characteristic changes in the position and intensity of the OH-stretch transitions. The third H(2)O attaches directly to Ag(+) in a tricoordinated form, while it occupies a hydrogen-bonding site in the second shell of the dicoordinated Cu(+). The preference of the tricoordination is attributable to the inefficient 5s-4d hybridization in Ag(+), in contrast to the extensive 4s-3d hybridization in Cu(+) which retains the dicoordination. This is most likely because the s-d energy gap of Ag(+) is much larger than that of Cu(+). The fourth H(2)O occupies the second shells of the tricoordinated Ag(+) and the dicoordinated Cu(+), as extensive hydrogen bonding is observed in M(+)(H(2)O)(4) x Ar. Interestingly, the Ag(+)(H(2)O)(4) x Ar ions adopt not only the tricoordinated form but also the dicoordinated forms, which are absent in Ag(+)(H(2)O)(3) x Ar but revived at n=4. Size dependent variations in the spectra of Cu(+)(H(2)O)(n) for n=5-7 provide evidence for the completion of the second shell at n=6, where the dicoordinated Cu(+)(H(2)O)(2) subunit is surrounded by four H(2)O molecules. The gas-phase coordination number of Cu(+) is 2 and the resulting linearly coordinated structure acts as the core of further solvation processes.


Assuntos
Cobre/química , Modelos Químicos , Modelos Moleculares , Prata/química , Solventes/química , Espectrofotometria Infravermelho/métodos , Água/química , Simulação por Computador , Íons , Metais/química , Gases Nobres/química
16.
J Phys Chem A ; 109(24): 5245-7, 2005 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-16839046

RESUMO

The excited-state double-proton-transfer (ESDPT) reaction in the jet-cooled 7-azaindole dimer (7AI2) has been investigated with picosecond time-resolved resonance-enhanced multiphoton ionization spectroscopy. The observed decay profiles of 7AI2 by exciting the origin and the intermolecular stretch fundamental in the S1 state are well reproduced by single-exponential functions with time constants of 1.9 +/- 0.9 ps and 860 +/- 300 fs, respectively. This result provides clear evidence of the concerted mechanism of ESDPT in 7AI2.


Assuntos
Gases/química , Indóis/química , Prótons , Estrutura Molecular , Análise Espectral , Fatores de Tempo
17.
J Chem Phys ; 122(9): 094303, 2005 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-15836124

RESUMO

The infrared photodissociation spectra of [(CO(2))(n)(H(2)O)(m)](-) (n=1-4, m=1, 2) are measured in the 3000-3800 cm(-1) range. The [(CO(2))(n)(H(2)O)(1)](-) spectra are characterized by a sharp band around 3570 cm(-1) except for n=1; [(CO(2))(1)(H(2)O)(1)](-) does not photodissociate in the spectral range studied. The [(CO(2))(n)(H(2)O)(2)](-) (n=1, 2) species have similar spectral features with a broadband at approximately 3340 cm(-1). A drastic change in the spectral features is observed for [(CO(2))(3)(H(2)O)(2)](-), where sharp bands appear at 3224, 3321, 3364, 3438, and 3572 cm(-1). Ab initio calculations are performed at the MP2/6-311++G(**) level to provide structural information such as optimized structures, stabilization energies, and vibrational frequencies of the [(CO(2))(n)(H(2)O)(m)](-) species. Comparison between the experimental and theoretical results reveals rather size- and composition-specific hydration manner in [(CO(2))(n)(H(2)O)(m)](-): (1) the incorporated H(2)O is bonded to either CO(2) (-) or C(2)O(4) (-) through two equivalent OH...O hydrogen bonds to form a ring structure in [(CO(2))(n)(H(2)O)(1)](-); (2) two H(2)O molecules are independently bound to the O atoms of CO(2) (-) in [(CO(2))(n)(H(2)O)(2)](-) (n=1, 2); (3) a cyclic structure composed of CO(2) (-) and two H(2)O molecules is formed in [(CO(2))(3)(H(2)O)(2)](-).

18.
J Chem Phys ; 121(19): 9436-42, 2004 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-15538864

RESUMO

Ultrafast processes in photoexcited N-salicylideneaniline have been investigated with femtosecond time-resolved resonance-enhanced multiphoton ionization spectroscopy. The ion signals via the S(1)(n,pi( *)) state of the enol form as well as the proton-transferred cis-keto form emerge within a few hundred femtoseconds after photoexcitation to the first S(1)(pi,pi( *)) state of the enol form. This reveals that two ultrafast processes, excited-state intramolecular proton transfer (ESIPT) reaction and an internal conversion (IC) to the S(1)(n,pi( *)) state, occur on a time scale less than a few hundred femtoseconds from the S(1)(pi,pi( *)) state of the enol form. The rise time of the transient corresponding to the production of the proton-transferred cis-keto form is within 750 fs when near the red edge of the absorption is excited, indicating that the ESIPT reaction occurs within 750 fs. The decay time of the S(1)(pi,pi( *)) state of the cis-keto form is 8.9 ps by exciting the enol form at 370 nm, but it dramatically decreases to be 1.5-1.6 ps for the excitation at 365-320 nm. The decrease in the decay time has been attributed to the opening of an efficient nonradiative channel; an IC from S(1)(pi,pi( *)) to S(1)(n,pi( *)) of the cis-keto form promotes the production of the trans-keto form as the final photochromic products. The two IC processes may provide opposite effect on the quantum yield of photochromic products: IC in the enol form may substantially reduce the quantum yield, but IC in the cis-keto form increase it.

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