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1.
MCN Am J Matern Child Nurs ; 47(4): 213-219, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35352688

RESUMO

PURPOSE: Pregnancy-related anxiety may increase the risk of preterm birth. Effective coping strategies and social support may help minimize pregnancy-related anxiety. STUDY DESIGN: Secondary analysis of cross-sectional data. METHODS: A sample of 408 pregnant non-Hispanic Black women completed questionnaires between 19 and 31 weeks gestation. Mediation analysis with structural equation modeling was used to explore effects of the relationship with the father of the baby on pregnancy-related anxiety. RESULTS: Support from the father of the baby was negatively associated with avoidance coping ( r = -.22, p < .001) and pregnancy-related anxiety ( r = - .17, p < .001), whereas conflict with the father of the baby was positively associated with avoidance coping ( r = .37, p < .001) and pregnancy-related anxiety ( r = .29, p < .001). Avoidance coping was positively associated with pregnancy-related anxiety ( r = .34, p < .001). After adjustment, avoidance coping partially mediated the effect of conflict with the father of the baby on pregnancy-related anxiety. CLINICAL IMPLICATIONS: Discussions with women about management of pregnancy-related anxiety should consider her current social support and coping mechanisms. Providers should offer support and resources on adaptive coping strategies.


Assuntos
Nascimento Prematuro , Adaptação Psicológica , Ansiedade/etiologia , Estudos Transversais , Feminino , Humanos , Recém-Nascido , Gravidez , Gestantes , Apoio Social , Inquéritos e Questionários
2.
J Nurs Adm ; 52(1): 42-50, 2022 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-34897206

RESUMO

OBJECTIVE: The aim of this study was to describe the current state of the interim manager (IM) role and the impact of the role on job performance. BACKGROUND: Interim managers provide leadership during organizational change, yet little is known about the role and its impact on outcomes. METHODS: An electronic survey was completed by 179 IMs working in acute care hospitals. Instruments included the Nurse Manager Practice Environment Scale, Decision Involvement Scale, Subjective Stress Scale, Maslach Burnout Inventory, and Brief Resilience Scale. RESULTS: The average tenure for IMs was 10 months. Despite moderately high levels of stress and exhaustion, IMs were resilient, positively viewed their work environment, and perceived their job performance as positively impacting nurse and patient outcomes. Interim managers were generally satisfied in their roles and likely to pursue nursing leadership as a career. CONCLUSION: Interim managers desire permanent leadership opportunities providing a pool for replacing exiting nurse managers. Support is needed to be successful.


Assuntos
Esgotamento Profissional , Enfermeiros Administradores/psicologia , Avaliação de Resultados da Assistência ao Paciente , Desempenho Profissional , Local de Trabalho/psicologia , Feminino , Humanos , Masculino , Inovação Organizacional , Inquéritos e Questionários
3.
Int J Mol Sci ; 20(9)2019 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-31060272

RESUMO

The basic leucine zipper (bZIP) transcription factor (TF) family is one of the largest gene families, and play crucial roles in many processes, including stress responses, hormone effects. The TF family also participates in plant growth and development. However, limited information is available for these genes in moso bamboo (Phyllostachys edulis), one of the most important non-timber forest products in the world. In the present study, 154 putative PhebZIP genes were identified in the moso bamboo genome. The phylogenetic analyses indicate that the PhebZIP gene proteins classify into 9 subfamilies and the gene structures and conserved motifs that analyses identified among all PhebZIP proteins suggested a high group-specificity. Microsynteny and evolutionary patterns analyses of the non-synonymous (Ka) and synonymous (Ks) substitution rates and their ratios indicated that paralogous pairs of PhebZIP genes in moso bamboo underwent a large-scale genome duplication event that occurred 7-15 million years ago (MYA). According to promoter sequence analysis, we further selected 18 genes which contain the higher number of cis-regulatory elements for expression analysis. The result showed that these genes are extensively involved in GA-, ABA- and MeJA-responses, with possibly different mechanisms. The tissue-specific expression profiles of PhebZIP genes in five plant tissues/organs/developmental stages suggested that these genes are involved in moso bamboo organ development, especially seed development. Subcellular localization and transactivation activity analysis showed that PhebZIP47 and PhebZIP126 were localized in the nucleus and PhebZIP47 with no transcriptional activation in yeast. Our research provides a comprehensive understanding of PhebZIP genes and may aid in the selection of appropriate candidate genes for further cloning and functional analysis in moso bamboo growth and development, and improve their resistance to stress during their life.


Assuntos
Fatores de Transcrição de Zíper de Leucina Básica/genética , Regulação da Expressão Gênica de Plantas , Genoma de Planta , Estudo de Associação Genômica Ampla , Sasa/genética , Motivos de Aminoácidos , Sequência de Aminoácidos , Fatores de Transcrição de Zíper de Leucina Básica/química , Fatores de Transcrição de Zíper de Leucina Básica/metabolismo , Mapeamento Cromossômico , Biologia Computacional , Sequência Conservada , Evolução Molecular , Perfilação da Expressão Gênica , Filogenia , Sequências Reguladoras de Ácido Nucleico , Sasa/classificação , Sasa/metabolismo , Transcriptoma
4.
Plant Physiol Biochem ; 128: 50-65, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-29758473

RESUMO

Small auxin-up RNA (SAUR) proteins play an important role in the regulation of plant growth and development. Here, we identified 105 SAUR genes and comprehensively analyzed them in Populus trichocarpa. Based on the phylogenetic relationships, the PtSAURs were classified into ten subfamilies. Of the 105 PtSAURs, 100 were randomly distributed along the nineteen chromosomes, while the remaining genes were located along unassigned scafoolds. These genes mainly evolved through segmental duplications. In total, 94 PtSAURs contained no introns, and each group had a similar conserved motif structure. A promoter analysis revealed various cis-elements related to growth, development and stress responses, and a synteny analysis established orthologous relationships among SAURs in Arabidopsis, rice, grape and poplar. The qRT-PCR and tissue expression analyses indicated that PtSAURs show different expression levels in various tissues in response to different treatments. PtSAUR53 was located on the nuclear and plasma membrane by conducting subcellular localization analysis. This study provides a comprehensive overview of poplar SAUR proteins and a foundation for further investigations for functional analysis of SAURs in poplar growth and development. At the same time, it will be valuable to further study the poplar SAUR genes to reveal their biological effects.


Assuntos
Temperatura Baixa , Regulação da Expressão Gênica de Plantas/efeitos dos fármacos , Ácidos Indolacéticos/farmacologia , Família Multigênica , Proteínas de Plantas , Polietilenoglicóis/farmacologia , Populus , Animais , Perfilação da Expressão Gênica , Estudo de Associação Genômica Ampla , Proteínas de Plantas/biossíntese , Proteínas de Plantas/genética , Populus/genética , Populus/metabolismo
5.
Planta ; 247(5): 1133-1148, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29383450

RESUMO

MAIN CONCLUSION: 74 phytocyanin genes were identified in the Populus trichocarpa genome. Phylogenetic analysis grouped the PC proteins into four subfamilies (UCs, PLCs, SCs, and ENODLs). Closely related PC proteins share similar motifs, implying similar functions. Expression profiles of PtPC genes were analyzed in response to drought and salt-stress. Phytocyanins (PCs) are blue copper proteins associated with electron carrier activity that have a large influence on plant growth and resistance. The majority of PCs are chimeric arabinogalactan proteins (AGPs). In this work, we identified 74 PC genes in Populus trichocarpa and analyzed them comprehensively. Based on the ligands composition of copper-binding sites, glycosylation state, the domain structure and spectral characteristics of PC genes, PCs were divided into four subfamilies [uclacyanins (UCs), plantacyanins (PLCs), stellacyanins (SCs) and early nodulin-like proteins (ENODLs)], and phylogenetic relationship analysis classified them into seven groups. All PtPCs are randomly distributed on 17 of the 19 poplar chromosomes, and they appear to have undergone expansion via segmental duplication. Eight PtPCs do not contain introns, and each group has a similar conserved motif structure. Promoter analysis revealed cis-elements related to growth, development and stress responses, and established orthology relationships of PCs between Arabidopsis and poplar by synteny analysis. Expression profile analysis and qRT-PCR analysis showed that PtPCs were expressed widely in various tissues. Quantitative real-time RT-PCR analysis of PC genes expression in response to salt and drought stress revealed their stress-responses profiles. This work provides a theoretical basis for a further study of stress resistance mechanisms and the function of PC genes in poplar growth and development.


Assuntos
Genoma de Planta/genética , Metaloproteínas/genética , Proteínas de Plantas/genética , Populus/genética , Cromossomos de Plantas/genética , Cobre/metabolismo , Genes de Plantas/genética , Metaloproteínas/classificação , Metaloproteínas/metabolismo , Filogenia , Proteínas de Plantas/classificação , Proteínas de Plantas/metabolismo , Populus/metabolismo , Reação em Cadeia da Polimerase em Tempo Real , Transcriptoma/genética
6.
Ecol Evol ; 8(2): 1260-1270, 2018 01.
Artigo em Inglês | MEDLINE | ID: mdl-29375796

RESUMO

Introgression may lead to discordant patterns of variation among loci and traits. For example, previous phylogeographic studies on the genus Quasipaa detected signs of genetic introgression from genetically and morphologically divergent Quasipaa shini or Quasipaa spinosa. In this study, we used mitochondrial and nuclear DNA sequence data to verify the widespread introgressive hybridization in the closely related species of the genus Quasipaa, evaluate the level of genetic diversity, and reveal the formation mechanism of introgressive hybridization. In Longsheng, Guangxi Province, signs of asymmetrical nuclear introgression were detected between Quasipaa boulengeri and Q. shini. Unidirectional mitochondrial introgression was revealed from Q. spinosa to Q. shini. By contrast, bidirectional mitochondrial gene introgression was detected between Q. spinosa and Q. shini in Lushan, Jiangxi Province. Our study also detected ancient hybridizations between a female Q. spinosa and a male Q. jiulongensis in Zhejiang Province. Analyses on mitochondrial and nuclear genes verified three candidate cryptic species in Q. spinosa, and a cryptic species may also exist in Q. boulengeri. However, no evidence of introgressive hybridization was found between Q. spinosa and Q. boulengeri. Quasipaa exilispinosa from all the sampling localities appeared to be deeply divergent from other communities. Our results suggest widespread introgressive hybridization in closely related species of Quasipaa and provide a fundamental basis for illumination of the forming mechanism of introgressive hybridization, classification of species, and biodiversity assessment in Quasipaa.

7.
Nano Lett ; 13(3): 1226-9, 2013 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-23387414

RESUMO

The mechanism of sodium borohydride removal of organothiols from gold nanoparticles (AuNPs) was studied using an experimental investigation and computational modeling. Organothiols and other AuNP surface adsorbates such as thiophene, adenine, rhodamine, small anions (Br(-) and I(-)), and a polymer (PVP, poly(N-vinylpyrrolidone)) can all be rapidly and completely removed from the AuNP surfaces. A computational study showed that hydride derived from sodium borohydride has a higher binding affinity to AuNPs than organothiols. Thus, it can displace organothiols and all the other adsorbates tested from AuNPs. Sodium borohydride may be used as a hazard-free, general-purpose detergent that should find utility in a variety of AuNP applications including catalysis, biosensing, surface enhanced Raman spectroscopy, and AuNP recycle and reuse.

8.
Anal Chem ; 84(20): 8437-41, 2012 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-23025423

RESUMO

Presented herein is a combined experimental and computational study of the gold nanoparticle (AuNP) inner filter effect on surface enhanced Raman spectroscopic (SERS) measurements. Using a bianalyte strategy in which dithiopurine (DTP) and ethanol were employed as the model analytes, we demonstrated that AuNPs enhance DTP's Raman signal but attenuate ethanol's Raman intensity. Combined time-resolved UV-vis and Raman measurements showed that AuNP aggregation has significant and an exactly opposite impact on the AuNP inner filter effect and SERS enhancement. This research provides critical new insights regarding SERS signal variation and offers a simple methodology for reliable determination of the SERS enhancement factors.

9.
Opt Lett ; 36(22): 4386-8, 2011 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-22089572

RESUMO

Using theoretical tools, we numerically demonstrated Fano line shapes in the scattering spectra of silver rods resulting from different mechanisms. One of the Fano line shapes is due to the coupling of an in-plane quadrupole and a dipole mode in a single rod. Two nodes were observed at the resonance wavelength, each of which is located at a quarter of the rod length from the two ends. The Fano resonance is strengthened when the silver rod is cut at the two nodal positions. The second mechanism that gives rise to a new Fano resonance peak occurs when the symmetry of the rod is broken and is a result of the asymmetric coupling between the two excited dipoles.

10.
J Phys Chem A ; 113(16): 4722-38, 2009 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-19334702

RESUMO

Detailed experimental and theoretical investigations have been carried out for the reaction of O((3)P) with CH(3)CH(3) at collision energies in the range of 80-100 kcal mol(-1). Experiments were performed on a crossed molecular beams apparatus with a laser breakdown source (which produces beams of O((3)P) with average velocities of 6.5 to 8.5 km s(-1)) and a pulsed supersonic source of CH(3)CH(3) having an average velocity of approximately 0.8 km s(-1). A rotatable quadrupole mass spectrometer allowed universal detection, with angular and velocity resolution of products scattering from the crossing region of the two reagent beams. Theoretical calculations were carried out in two stages, (1) electronic structure calculations to characterize the stationary points associated with the title reaction and (2) direct dynamics calculations employing the MSINDO semiempirical Hamiltonian and density functional theory (B3LYP/6-31G**). The dynamics of O-atom inelastic scattering and H-atom abstraction to form OH + C(2)H(5) were clearly revealed by the experiment and were matched well by theory. Both of these processes favor high-impact parameters, with most of the available energy going into translation, indicating a stripping mechanism for H-atom abstraction. H-atom abstraction was the dominant reactive pathway, but H-atom elimination to form OC(2)H(5) + H was also inferred from the experimental results and observed in the theoretical calculations. This reaction proceeds through small-impact-parameter collisions, and most of the available energy goes into internal excitation of the OC(2)H(5) product, which likely leads to secondary dissociation to H(2)CO + CH(3) or CH(3)CHO + H. A relative excitation function for the H-atom elimination channel was also measured and compared to a calculated absolute excitation function. The theoretical calculations also identified several additional reaction pathways with low relative yields, including C-C bond breakage to form OCH(3) + CH(3). Interference from OC(2)H(5) decomposition products in the experiment inhibited the unambiguous observation of the low-yield reaction pathways that were identified by theory, although an upper limit for the relative yield of C-C bond breakage was determined.

11.
J Phys Chem A ; 113(16): 4570-80, 2009 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-19290605

RESUMO

Direct dynamics simulations were performed at the HF/6-31G level of theory to investigate the intramolecular and unimolecuar dynamics of the twist-boat (TB) intermediate on the cyclohexane potential energy surface (PES). Additional calculations were performed at the MP2/aug-cc-pVDZ level of theory to further characterize the PES's stationary points. The trajectories were initiated at the C(1) and C(2) half-chair transition states (TSs) connecting a chair conformer with a TB intermediate, via an intrinsic reaction coordinate (IRC). Energy was added in accord with a microcanonical ensemble at the average energy for experiments at 263 K. Important nontransition state theory (TST), non-IRC, and non-RRKM dynamics were observed in the simulations. Trajectories initially directed toward the chair conformer had a high probability of recrossing the TS, with approximately 30% forming a TB intermediate instead of accessing the potential energy well for the conformer. The TB intermediate initially formed was not necessarily the one connected to the TS via the IRC. Of the trajectories initiated at the C(2) half-chair TS and initially directed toward the chair conformer, 35% formed a TB intermediate instead of the chair conformer. Also, of the trajectories forming a TB intermediate, only 16% formed the TB intermediate connected with the C(2) TS via the IRC. Up to eight consecutive TB --> TB isomerizations were followed, and non-RRKM behavior was observed in their dynamics. A TB can isomerize to two different TBs, one by a clockwise rotation of C-C-C-C dihedral angles and the other by a counterclockwise rotation. In contrast to RRKM theory, which predicts equivalent probabilities for these rotations, the trajectory dynamics show they are not equivalent and depend on whether the C(1) or C(2) half-chair TS is initially excited. Non-RRKM dynamics is also observed in the isomerization of the TB intermediates to the chair conformers. RRKM theory assumes equivalent probabilities for isomerizing to the two chair conformers. In contrast, for the first and following TB intermediate formed, there is a preference to isomerize to the chair conformer connected to the TS at which the trajectories were initiated. For the first TB intermediate formed, approximately 30% of the isomerization is to a chair conformer, but this fraction decreases for the later formed TB intermediates and becomes approximately 10% for the eighth consecutive TB intermediate formed.

12.
Phys Chem Chem Phys ; 10(31): 4565-72, 2008 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-18665306

RESUMO

To model soft-landing of peptide ions on surfaces, it is important to have accurate intermolecular potentials between these ions and surfaces. As part of this goal, ab initio calculations at the MP2/aug-cc-pVTZ level of theory, with basis set superposition error (BSSE) corrections, were performed to determine both the long-range attractive and short-range repulsive potentials for CH(4) interacting with the -NH(3)(+) group of CH(3)NH(3)(+). Potential energy curves for four different orientations between CH(4) and CH(3)NH(3)(+) were determined from the calculations to obtain accurate descriptions of the interactions between the atoms of CH(4) and those of -NH(3)(+). A universal analytic function was not found that could accurately represent both the long-range and short-range potentials for collision energies as high as those obtained in surface-induced-dissociation (SID) experiments. Instead, long-range and short-range analytic potentials were developed separately, by simultaneously fitting the four ab initio potential energy curves with a sum of two-body interactions between the atoms of CH(4) and -NH(3)(+), and then connecting these long-range and short-range two-body potentials with switching functions. Following a previous work [J. Am. Chem. Soc., 2002, 124, 1524], these two-body potentials may be used to describe the interactions of the N and H atoms of the -NH(3)(+) group of a protonated peptide ion with the H and C atoms of alkane-type surfaces such as alkyl thiol self-assembled monolayers and H-terminated diamond. Accurate short-range and long-range potentials are imperative to model protonated peptide ion soft-landing experiments. The former controls the collision energy transfer, whereas the latter describes the binding of the ion to the surface. A comparison of the ab initio potential energy curves for CH(3)NH(3)(+)/CH(4) with those for NH(4)(+)/CH(4) shows that they give nearly identical two-body interactions between the atoms of -NH(3)(+) and those of CH(4), showing that the smaller NH(4)(+)/CH(4) system may be used to obtain the two-body potentials. A comparison of the four ab initio potential energy curves reported here for CH(3)NH(3)(+)/CH(4), with those given by the AMBER and CHARMM molecular mechanical potentials, show that these latter potentials "roughly" approximate the long-range attractions, but are grossly in error for the short-range repulsions. The work reported here illustrates that high-level ab initio calculations of intermolecular potentials between small model molecules may be used to develop accurate analytical intermolecular potentials between peptide ions and surfaces.

13.
J Phys Chem A ; 112(10): 2093-103, 2008 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-18088105

RESUMO

Spin-orbit coupling (SOC) induced intersystem crossing (ISC) has long been believed to play a crucial role in determining the product distributions in the O(3P) + C2H4 reaction. In this paper, we present the first nonadiabatic dynamics study of the title reaction at two center-of-mass collision energies: 0.56 eV, which is barely above the H-atom abstraction barrier on the triplet surface, and 3.0 eV, which is in the hyperthermal regime. The calculations were performed using a quasiclassical trajectory surface hopping (TSH) method with the potential energy surface generated on the fly at the unrestricted B3LYP/6-31G(d,p) level of theory. To simplify our calculations, nonadiabatic transitions were only considered when the singlet surface intersects the triplet surface. At the crossing points, Landau-Zener transition probabilities were computed assuming a fixed spin-orbit coupling parameter, which was taken to be 70 cm-1 in most calculations. Comparison with a recent crossed molecular beam experiment at 0.56 eV collision energy shows qualitative agreement as to the primary product branching ratios, with the CH3 + CHO and H + CH2CHO channels accounting for over 70% of total product formation. However, our direct dynamics TSH calculations overestimate ISC so that the total triplet/singlet ratio is 25:75, compared to the observed 43:57. Smaller values of SOC reduce ISC, resulting in better agreement with the experimental product relative yields; we demonstrate that these smaller SOC values are close to being consistent with estimates based on CASSCF calculations. As the collision energy increases, ISC becomes much less important and at 3.0 eV, the triplet to singlet branching ratio is 71:29. As a result, the triplet products CH2 + CH2O, H + CH2CHO and OH + C2H3 dominate over the singlet products CH3 + CHO, H2 + CH2CO, etc.

14.
J Chem Phys ; 125(13): 132301, 2006 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-17029420

RESUMO

This paper is an overview of the theory of reactive scattering, with emphasis on fully quantum mechanical theories that have been developed to describe simple chemical reactions, especially atom-diatom reactions. We also describe related quasiclassical trajectory applications, and in all of this review the emphasis is on methods and applications concerned with state-resolved reaction dynamics. The review first provides an overview of the development of the theory, including a discussion of computational methods based on coupled channel calculations, variational methods, and wave packet methods. Choices of coordinates, including the use of hyperspherical coordinates are discussed, as are basis set and discrete variational representations. The review also summarizes a number of applications that have been performed, especially the two most comprehensively studied systems, H+H2 and F+H2, along with brief discussions of a large number of other systems, including other hydrogen atom transfer reactions, insertion reactions, electronically nonadiabatic reactions, and reactions involving four or more atoms. For each reaction we describe the method used and important new physical insight extracted from the results.

15.
J Phys Chem A ; 110(9): 3017-27, 2006 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-16509623

RESUMO

This paper presents experimental and theoretical studies of the product energy partitioning associated with the H + CD4 (nu = 0) --> HD + CD3 reaction for the collision energy range 0.5-3.0 eV. The theoretical results are based on quasiclassical trajectories from (1) first principles direct dynamics calculations (B3LYP/6-31G), (2) an empirical surface developed by Espinosa-García [J. Chem. Phys. 2002, 116, 10664] (EG), and (3) two semiempirical surfaces (MSINDO and reparametrized MSINDO). We find that most of the energy appears in product translation at energies just above the reactive threshold; however, HD vibration and rotation become quite important at energies above 1 eV, each accounting for over 20% of the available energy above 1.5 eV, according to the B3LYP calculations. The barrier on the B3LYP surface, though being later than that on EG, predicts significantly higher HD vibrational excitation than EG. This deviation is contradictory to what would be expected on the basis of the Polanyi rules and derives from modest differences in the potential energy surfaces. The CD3 internal energy is generally quite low, and we present detailed rotational state distributions which show that the CD3 rotational distribution is largely independent of collision energy in the 0.75-1.95 eV range. The most populated rotational levels are N = 5 and 6 on B3LYP, with most of that excitation being associated with motion about the C2 axes, rather than C3 axis, of the CD3 product, in good agreement with the experimental results. Through our extensive studies in this and previous work concerning the scattering dynamics, we conclude that B3LYP/6-31G provides the best available description of the overall dynamics for the title reaction at relatively high collision energies.

16.
J Phys Chem A ; 110(2): 677-86, 2006 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-16405340

RESUMO

We compare experimental photoloc measurements and quasi-classical trajectory calculations of the integral cross sections, lab-frame speed distributions, and angular distributions associated with the CD3 products of the H + CD4(nu = 0) --> CD3 + HD reaction at collision energies ranging from 0.5 to 3.0 eV. Of the potential energy surfaces (PES) we explored, the direct dynamics calculations using the B3LYP/6-31G** density functional theory PES provide the best agreement with the experimental measurements. This agreement is likely due to the better overall description that B3LYP provides for geometries well removed from the minimum energy path, even though its barrier height is low by approximately 0.2 eV. In contrast to previous theoretical calculations, the angular distributions on this surface show behavior associated with a stripping mechanism, even at collision energies only approximately 0.1 eV above the reaction barrier. Other potential energy surfaces, which include an analytical potential energy surface from Espinosa-García and a direct dynamics calculation based on the MSINDO semiempirical Hamiltonian, are less accurate and predict more rebound dynamics at these energies than is observed. Reparametrization of the MSINDO surface, though yielding better agreement with the experiment, is not sufficient to capture the observed dynamics. The differences between these surfaces are interpreted using an analysis of the opacity functions, where we find that the wider cone of acceptance on the B3LYP surface plays a crucial role in determining the integral cross sections and angular distributions.

17.
J Am Chem Soc ; 127(34): 11898-9, 2005 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-16117502

RESUMO

A comparison between theory and experiment for the benchmark H + CD4 --> HD + CD3 abstraction reaction yields a reinterpretation of the reaction mechanism and highlights the unexpected contribution of a stripping mechanism. Whereas the best analytic surface fails to reproduce experiment, a first-principles direct-dynamics (on the fly) treatment is in good agreement, showing that the H + CD4 reaction exhibits extreme sensitivity to modest differences in the potential energy surface. We find that bent H-D-C transition state geometries play an important role in the dynamics. A simple model that relates the scattering angle impact parameter and cone of acceptance accounts well for the overall reaction dynamics.

18.
Ai Zheng ; 23(9): 1021-5, 2004 Sep.
Artigo em Chinês | MEDLINE | ID: mdl-15363194

RESUMO

BACKGROUND & OBJECTIVE: Tumor suppressor gene p53 and oncogene C-erbB-2 are confirmed to have close relation with endometrioid adenocarcinoma (EC), few documents have been reported about their correlation. Its structural homology to p53, p63 has been considered as a tumor suppressor gene acompany with p53 mutation, but its suppressive nature has not been confirmed yet; reports about p63 expression in EC are rare. This study was designed to investigate the roles of p53, p63, and C-erbB2 in tumorigenesis and development of EC, and their correlation with clinicopathological features of EC. METHODS: Immunohistochemical technique was used to detect P53, P63, and C-erbB2 protein expression in 38 cases of EC, 23 cases of endometrial hyperplasia (EH), and 10 cases of benign proliferative endometrium (BPE). RESULTS: (1) The positive rate of P53 in EC was 31.6%,significantly higher than those in EH and BPE (P < 0.05). P53 expression was associated with surgical pathologic stage, and depth of myometrial invasion in EC (P< 0.005), but was not associated with histological grade (P >0.05). (2) The positive rate of P63 in EC was 81.6%, significantly higher than those in EH and BPE (P < 0.005). P63 expression was not associated with histological grade, surgical pathologic stage, and depth of myometrial invasion in EC (P >0.05). (3) The positive rate of C-erbB-2 in EC was 23.2%, there was no significant difference compared with those in EH or BPE (P >0.05).C-erbB-2 expression was associated with surgical pathologic stage, and depth of myometrial invasion in EC (P< 0.001,P< 0.005),but was not associated with histological grade (P >0.05).(4) There was significantly positive correlation between P53 and P63 (r =0.443,P < 0.01)or C-erbB-2 (r =0.490,P < 0.005). CONCLUSIONS: Both p53 and p63 are involved in carcinogenesis of EC; p63 may act as an oncogene in tumorigenesis of EC. The expression of P53 and C-erbB2 are related to the progression of malignant EC; P53 and C-erbB-2 co-expression may predict poor prognosis.


Assuntos
Carcinoma Endometrioide/metabolismo , Neoplasias do Endométrio/metabolismo , Fosfoproteínas/metabolismo , Receptor ErbB-2/metabolismo , Transativadores/metabolismo , Proteína Supressora de Tumor p53/metabolismo , Adulto , Idoso , Carcinoma Endometrioide/genética , Carcinoma Endometrioide/patologia , Proteínas de Ligação a DNA , Hiperplasia Endometrial/genética , Hiperplasia Endometrial/metabolismo , Hiperplasia Endometrial/patologia , Neoplasias do Endométrio/genética , Neoplasias do Endométrio/patologia , Feminino , Genes Supressores de Tumor , Genes erbB-2 , Genes p53 , Humanos , Pessoa de Meia-Idade , Invasividade Neoplásica , Estadiamento de Neoplasias , Prognóstico , Fatores de Transcrição , Proteínas Supressoras de Tumor
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