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1.
Ann Vasc Surg ; 89: 153-160, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36126835

RESUMO

BACKGROUND: Vascular disease is a common cause of death and disability in our growing elderly population and the demand for vascular procedures is increasing worldwide. Workforce planning is essential to meet future demand and provide safe vascular services. Our aim was to evaluate the current workforce in the United Kingdom and estimate future demand for vascular surgeons. METHODS: From November 2020 to January 2021, we surveyed UK vascular surgeons for information on their work patterns. We estimated current vascular surgery (VS) workforce using the National Vascular Registry (NVR) data and population data from the Office for National Statistics. To estimate future demand, we interrogated Hospital Episode Statistic (HES) data using Hospital Admitted Patient Care Activity (HAPCA) and linear trend analysis. RESULTS: NVR data estimate that currently there are 518 consultant VS in the United Kingdom, or 1 per 128,951 population, lower than international comparisons. HAPCA data (2012-2020) suggests VS Finished Consultant Episodes (FCE), admissions, and waiting lists are growing by approximately 2% per year, and we estimate the workforce will need to grow by more than 50% over the next 10 years to meet this demand and Vascular Society of Great Britain and Ireland recommendation. CONCLUSIONS: The UK has a shortage of vascular surgeons at a time when vascular activity is increasing. The VS workforce, both VS consultant and vascular surgeons in training numbers need to expand to address the ongoing shortage and maintain a safe level of service.


Assuntos
Cirurgiões , Idoso , Humanos , Resultado do Tratamento , Procedimentos Cirúrgicos Vasculares , Recursos Humanos , Reino Unido , Necessidades e Demandas de Serviços de Saúde
2.
Med Teach ; 45(1): 40-48, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36214365

RESUMO

BACKGROUND: Medical students have reported high prevalence of mental health difficulties and burnout. However, there are limited investigations examining the association between resilience and these difficulties. We investigated: (1) depression, anxiety, personal and professional burnout, and comorbidity; (2) demographic and education characteristics associated with these outcomes; (3) the association between resilience and these outcomes; and (4) whether these results were attributable to sampling bias. METHODS: Participants were n = 521 medical students from RCSI University of Medicine and Health Sciences. Outcomes were measured using validated scales. We report descriptive statistics, and risk factors for the difficulties were investigated using generalized linear modelling. RESULTS: One-in-three students reported incidence of depression or anxiety (24.5% co-morbidity). 8.9% of students reported all four difficulties. Difficulties were more common in female students and those in middle years of the programme. Resilience was negatively correlated with all outcomes and stable across demographic and educational variables. Weighting the data for sampling bias did not affect these results. CONCLUSIONS: Our results emphasise the high incidence of depression, anxiety, burnout, and comorbidity in students. We advocate for further investigation into the role of resilience as a modifiable factor that may ameliorate the incidence of depression, anxiety, and burnout in medical students.


Assuntos
Esgotamento Profissional , Estudantes de Medicina , Humanos , Feminino , Estudantes de Medicina/psicologia , Saúde Mental , Estudos Transversais , Depressão/epidemiologia , Ansiedade/epidemiologia , Esgotamento Profissional/epidemiologia
3.
Ann Vasc Surg ; 84: 169-178, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35248742

RESUMO

BACKGROUND: Occupational burnout is a growing concern in frontline roles such as vascular surgery, and is associated with medical errors and shortened careers. Our aim is to measure burnout, resilience, and associated risk factors among vascular surgeons (VS) in the United Kingdom (UK). METHODS: We carried out an electronic survey of active VS in the UK using validated self-report questionnaires, including the following: Copenhagen Burnout Inventory (CBI), Brief Resilience Scale (BRS), and information on job characteristics, health, and well-being. Univariate regression analysis looked at potential risk factors. RESULTS: One hundred forty-eight VS responded (49% participation rate), and after excluding retirees and nonconsultants, 133 VS practicing in the UK were analyzed. Mean age was 49.9 ± 7.19 years; the majority (83.5%) were male. In total, 81.3% recorded ethnic identity as White. In addition, 93.2% worked full time; 74.8% were contracted above 10 programmed activities and 87.9% worked more than 40 hr/week. On-call was 1 in 6, or above, for 87.4%. Overall, 38.4% of VS had high burnout on the CBI. Resilience was also high, with BRS mean (standard deviation) of 3.6 (0.69) and median (interquartile range) of 3.7 (3-4). Univariate regression analysis found no significant risk factor associated with high burnout or resilience. CONCLUSIONS: VS in the UK have high levels of burnout and work long hours. Resilience levels were also high, which may offer some protection. However, policymakers and our surgical leaders should address contributing factors and excessive working hours and establish measures to identify and support surgeon well-being for optimal surgeon and patient safety.


Assuntos
Esgotamento Profissional , Cirurgiões , Adulto , Esgotamento Profissional/diagnóstico , Esgotamento Psicológico , Estudos Transversais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Inquéritos e Questionários , Resultado do Tratamento , Reino Unido , Recursos Humanos
4.
Health Qual Life Outcomes ; 13: 168, 2015 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-26467295

RESUMO

BACKGROUND: Multimorbidity affects up to one quarter of primary care populations. It is associated with reduced quality of life, an increased risk of mental health difficulties and increased healthcare utilisation. Functional decline is defined as developing difficulties with activities of daily living and is independently associated with poorer health outcomes. The aim of this systematic review was to examine the association between multimorbidity and functional decline and to what extent multimorbidity predicts future functional decline. METHODS: A systematic literature search (1990-2014) and narrative analysis was conducted. INCLUSION CRITERIA: Population; Community-dwelling adults (≥18 years), Risk; Multimorbidity defined as the presence of ≥2 chronic medical conditions in an individual, Primary outcome; Physical functional decline measured using a validated instrument, Study design; cross-sectional or cohort studies. The following databases were included: PubMed, EMBASE, CINAHL, the Cochrane Library and the International Research Community on Multimorbidity (IRCMo) publication list. Methodological quality assessment of included studies was conducted with a suitable risk of bias tool. RESULTS: A total of 37 studies were eligible for inclusion (28 cross-sectional studies and 9 cohort studies). The majority of cross-sectional studies (n = 24/28) demonstrated a consistent association between multimorbidity and functional decline. Twelve of these studies reported that increasing numbers of chronic condition counts were associated with worsening functional decline. Nine cohort studies included 14,133 study participants with follow-up periods ranging from one to six years. The majority (n = 5) found that multimorbidity predicted functional decline. Of the five studies that reported the impact of increasing numbers of conditions, all reported greater functional decline with increasing numbers of conditions. One study examined disease severity and found that this also predicted greater functional decline. Overall, cohort studies were of good methodological quality but were mixed in terms of participants, multimorbidity definitions, follow-up duration, and outcome measures. CONCLUSIONS: The available evidence indicates that multimorbidity predicts future functional decline, with greater decline in patients with higher numbers of conditions and greater disease severity. This review highlights the importance of considering physical functioning when designing interventions and systems of care for patients with multimorbidity, particularly for patients with higher numbers of conditions and greater disease severity.


Assuntos
Doença Crônica/epidemiologia , Pessoas com Deficiência/estatística & dados numéricos , Nível de Saúde , Qualidade de Vida , Adulto , Idoso , Comorbidade , Estudos Transversais , Feminino , Avaliação Geriátrica/métodos , Humanos , Masculino , Saúde Mental/estatística & dados numéricos , Pessoa de Meia-Idade , Avaliação de Resultados em Cuidados de Saúde
5.
Front Med (Lausanne) ; 11: 1385489, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38938377

RESUMO

Introduction: Professional identity formation (PIF) is an ongoing, self-reflective process involving habits of thinking, feeling and acting like a physician and is an integral component of medical education. While qualitative work has suggested that PIF is informed by professionalism, resilience, and leadership, there is a dearth of quantitative work in this area. Multiple methods build rigor and the present study aimed to quantitatively assess the relative psychometric contributions of professionalism, resilience, and leadership constructs to informing PIF, using a latent factor analysis approach. Methods: We analyzed data from the PILLAR study, which is an online cross-sectional assessment of a pre-clinical cohort of medical students in the RCSI University of Medicine and Health Sciences, Dublin, using established and validated quantitative measures in each area of interest: PIF, professionalism, leadership and resilience. A total of 76 items, combining four validated scales, along with a selection of demographic questions, were used. The hypothesis that PIF is informed by, and correlates with, professionalism, resilience and leadership was examined by conducting a confirmatory factor analysis of a proposed three-factor higher-order model. Model estimation used Maximum Likelihood Method (MLM) with geomin rotation. The hypothesized (measurement) model was examined against an alternative (saturated) model, as well as a three-factor model. Results: Latent variable analysis from 1,311 students demonstrated that a three-factor higher-order model best fit the data; suggesting PIF is informed by professionalism, resilience, and leadership, and that these constructs are statistically distinct and account for differential aspects of PIF. This higher-order model of PIF outperformed both the saturated model and the three-factor model. The analysis of which component may be the most or least influential was inconclusive, and the overall model was not influenced by year of training. Discussion: Building upon existing conceptual contentions, our study is the first to quantitatively support the contribution of professionalism, resilience, and leadership to the development of professional identity, and to delineate the inter-relationships between PIF and these constructs. This information can be used by medical educators when designing curricula and educational strategies intended to enhance PIF. Future work should seek to assess the influence of these constructs longitudinally.

6.
Front Med (Lausanne) ; 11: 1382903, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38808142

RESUMO

Introduction: Teaching professionalism is a fundamental aspect of medical undergraduate education, delivering important domains of professional attitudes, ethics, and behaviors. The effects of educational interventions can be assessed by measuring the change in such domains, but validated assessment tools for these professionalism domains are lacking. In this study, we constructed and conducted expert validation of a modified theory of planned behavior (TPB) questionnaire to assess changes in professional behaviors (PBs) in medical students. Methods: To validate that, we modified an existing TPB questionnaire, and an 18-item questionnaire was subjected to expert panel evaluation using the content validation method. The clarity and relevance of items were assessed using a four-point rating scale (i.e., 1 = not relevant to 4 = highly relevant). Ratings of experts and free-text comments were analyzed. Quantitative evaluation of relevance and clarity was undertaken through analyses of the Item-level Content Validity Index (I-CVI) and Scale-level Content Validity Index (S-CVI). A qualitative assessment of the comments of experts was conducted to refine items, any disagreements were discussed, and a consensus decision was developed among authors for item changes. Results: Quantitative evaluation of the Item-level Content Validity Index (I-CVI) scored 0.9-1 for relevance and 0.7-1 for clarity. Qualitative evaluation resulted in (i) changes to the wording of items (e.g., choices such as "worthless/worthwhile" were replaced with "not important/important"); and (ii) suggestion of the addition of social media in the construct of subjective norms. Discussion: The proposed tool exhibits content validity and can assess TPB constructs in professionalism education. This study of content validity may help to ensure the modified TPB questionnaire accurately measures the TPB constructs, ensuring its effectiveness in accurately measuring the TPB constructs for PB in diversified educational medical institutions.

7.
J Med Educ Curric Dev ; 10: 23821205231198921, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37692556

RESUMO

Objectives: The fundamental role of medical education is the transformation of students to doctors, through a process of education and professional identity formation (PIF), which can be informed by several educational, behavioural and emotional factors. PIF has been deemed to be of equal importance to the acquisition of clinical knowledge and skills and includes constructs such as professionalism, leadership and resilience. We aimed to assess professional identity formation, professionalism, leadership and resilience (PILLAR) in the junior years of medical school in the 2020/2021 academic year and illustrate the potential role of quantitative assessment to demonstrate progression in these areas. In this research, we provide the methods and baseline results for the PILLAR study. Methods: We implemented a compulsory assessment in pre-clinical years of graduate entry and direct entry medicine at the Royal College of Surgeons in Ireland University of Medicine and Health Sciences, Dublin, Ireland. Validated scales were used to assess students' PILLAR. Descriptive and univariable statistical techniques were used to compare student scores between respective years. Results: A total of 1311 students (92% response rate) provided their consent for research. For the psychometric scales, there were no evident trends among the years on these assessment measures. Results indicated significant differences in all measures, however, these did not correspond to ascending years of seniority. Conclusion: The PILLAR methodology provides important information on the challenges of quantitatively assessing medical students in the four key areas of PIF, professionalism, leadership, and resilience. Our cross-sectional results point to cohort effects, without the expected progression per year in the cross-sectional data, or suggest that the chosen quantitative measures may be problematic for these constructs in pre-clinical students. Therefore, while we believe that PILLAR has potential as a progress test for these constructs, this will only truly be elucidated by repeated measures of each cohort over time.

8.
Med Educ Online ; 28(1): 2235793, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37463323

RESUMO

Medical Professionalism (MP) defined as values, behaviours and attitudes that promote professional relationships, public trust and patient safety is a vital competency in health profession education. MP has a distinctive uniqueness due to cultural, contextual, conceptual, and generational variations. There is no standard instructional strategy to probe the understanding of MP in a cohesive, structured, interactive manner. This study aimed to investigate undergraduate medical students' understanding of MP using express team-based learning (e-TBL) at both campuses of Royal College of Surgeons Ireland (RCSI). Using the key principles of a sociocultural theoretical lens in adult learning theory, we designed e-TBL as a context-learning-based educational strategy. We conducted three e-TBL sessions on cross-cultural communication and health disparities, a reflective report on clinical encounters, and professionalism in practice. We collected, collated, and analyzed the student experiences qualitatively using data gathered from team-based case discussions during e-TBL sessions. A dedicated working group developed very short-answer questions for the individual readiness assurance test (IRAT) and MP-based case scenarios for team discussions. In this adapted 4-step e-TBL session, pre-class material was administered, IRAT was undertaken, and team-based discussions were facilitated, followed by facilitator feedback. A qualitative inductive thematic analysis was performed, which generated subthemes and themes illustrated in excerpts. Our thematic analysis of data from 172 students (101 from Bahrain and 71 from Dublin) yielded four unique themes: incoming professional attitudes, transformative experiences, sociological understanding of professionalism, and new professional identity formation. This qualitative study provides a deeper understanding of medical students' perceptions of medical professionalism. The generated themes resonated with divergent and evolving elements of MP in an era of socioeconomic and cultural diversity, transformative experiences, and professional identity formation. The core elements of these themes can be integrated into the teaching of MP to prepare fit-to-practice future doctors.


Assuntos
Profissionalismo , Estudantes de Medicina , Adulto , Humanos , Aprendizagem , Pesquisa Qualitativa , Retroalimentação , Aprendizagem Baseada em Problemas
9.
J Multimorb Comorb ; 12: 26335565221142350, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36518523

RESUMO

Background: While physical activity is widely recommended for many long-term conditions, it may be difficult to achieve for patients managing multiple conditions. We aimed to determine the feasibility of an inter-agency exercise and education programme for patients with multimorbidity in primary care. Methods: We conducted an uncontrolled pilot study with adults with multimorbidity, recruited in two community healthcare organisations in an urban area in Ireland. The six-week pilot intervention combined an individually tailored gym-based exercise programme and education to support self-management. Feasibility of the Activ8 programme was assessed using a mixed methods process evaluation. Outcome measures at baseline and at 6 weeks included recruitment and retention, gait speed, grip strength, quality of life and self-efficacy. Focus groups and interviews explored participants and facilitators' perceptions of the programme. Results: 19 participants with ≥2 chronic conditions were recruited over three-weeks with similar attrition at both sites (≤40%). Overall, the results indicate that Activ8 was feasible and acceptable to patients and practitioners. Quantitative outcome measures suggested improvements in most outcomes. Qualitative data analysis indicated that Activ8 addressed an overarching concept of patient-centeredness among participants. Three key themes included perceived personal programme impact, the personalised composition of the programme and the evolving nature of primary care practice. Conclusion: While further definitive evidence is needed and attrition from the programme needs to be considered, the Activ8 Programme was acceptable to both patients and professionals in two different primary care areas with the potential for positive impacts for adults living with multimorbidity.

10.
Med Educ Online ; 26(1): 1983926, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34775927

RESUMO

BACKGROUND: Medical professionalism education intends to produce virtuous and humanistic healthcare professionals who demonstrate perseverance and professional integrity. However, today's medicine has embodied a mammoth transformation of medical practice towards sns and the digital realm. Such paradigm shift has challenged the medical professional's values, behaviors, and identities, and the distinct boundaries between personal and professional lives are blurred. This study aims to develop a framework for healthcare professionals coping with the challenges of medical professionalism in the digital realm. METHODS: We followed a systematic approach for the development of a framework about e-professionalism. Qualitative data was collected from a systematic review and a delphi study, while quantitative data was collected by administering a validated questionnaire social networking sites for medical education (snsme). Subsequently, categorization of the selected data and identifying concepts, deconstruction and further categorizing concepts (philosophical triangulation), integration of concepts (theoretical triangulation), and synthesis and resynthesis of concepts were performed. RESULTS: The initial process yielded six overlapping concepts from personal, professional, character (implicit) and characteristic (explicit) domains: environment, behavior, competence, virtues, identity, and mission. Further integration of data was done for the development of the medical education e-professionalism (meep) framework with a central concept of a commitment to mission. The mission showed deep connections with values (conformity, beneficence, universalism, and integrity), behaviours (communication, self-awareness, tolerance, power), and identity (reflection, conscientiousness, self-directed, self-actualization). The data demonstrated that all medical professionals require updated expertise in sns participation. CONCLUSION: The meep framework recognises a mission-based social contract by the medical community. This mission is largely driven by professional values, behaviors and identity. Adherence to digital standards, accountability, empathy, sensitivity, and commitment to society are essential elements of the meep framework.


Assuntos
Educação Médica , Profissionalismo , Comunicação , Pessoal de Saúde , Humanos , Rede Social
11.
J Gerontol A Biol Sci Med Sci ; 73(11): 1538-1544, 2018 10 08.
Artigo em Inglês | MEDLINE | ID: mdl-29346526

RESUMO

Background: Multimorbidity is recognized internationally as having a serious impact on health outcomes. It is associated with reduced quality of life, increased health care utilization, and future functional decline. Physical activity is associated with good health and psychological well-being. The aim of this study was to identify the impact of physical activity and physical function on the development and worsening of multimorbidity over time. Methods: Using The Irish Longitudinal Study on Ageing (TILDA), we analyzed 4,823 participants ≥50 years with and without multimorbidity. Multimorbidity was defined as the presence of ≥2 chronic conditions. Development of multimorbidity was measured as the accrual of additional conditions over a 2-year period. Physical activity and physical function were measured using the International Physical Activity Questionnaire (IPAQ), gait speed (m/sec), and grip strength (kg). Results: Sixteen groups of chronic conditions were included in analyses. 53.7% of included participants had multimorbidity at baseline and 71.7% at follow-up. Six hundred and thirty-eight of 2,092 (30.4%) participants without multimorbidity and 1,005 of 2,415 (41.6%) with existing multimorbidity developed new condition/s. Gait speed (relative risk [RR] = 0.67, confidence interval [CI]: 0.49-0.90), grip strength (RR = 0.98, CI: 0.97-0.99), and age (compared to 50-59 years, 60-69: RR = 1.30, CI: 1.11-1.52; ≥70: RR = 1.35, CI: 1.03-1.77) were significantly associated with the development of multimorbidity and accrual of additional conditions. Conclusion: These results show that physical function is associated with the development and worsening of multimorbidity over time. They support the recent National Institute for Health & Care Excellence (NICE) Guidance on multimorbidity that suggests that patients with multimorbidity and reduced gait speed should be identified and targeted for interventions to improve health outcomes.


Assuntos
Envelhecimento , Exercício Físico , Multimorbidade , Desempenho Físico Funcional , Idoso , Estudos de Coortes , Feminino , Força da Mão , Humanos , Irlanda/epidemiologia , Estudos Longitudinais , Masculino , Pessoa de Meia-Idade , Inquéritos e Questionários , Velocidade de Caminhada
12.
Chem Commun (Camb) ; (11): 1210-1, 2002 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-12109086

RESUMO

Reaction of Zn(OAc)(2).2H2O with tmen leads to the formation of [Zn(tmen)(OAc)2] (I) which reacts with benzohydroxamic acid to form Zn(BA)2.H2O (II) and the novel dizinc hydroxamate bridged complex [Zn2(mu-OAc)2(OAc)(mu-BA)(tmen)] (III), which may also be prepared by self-assembly and whose structure closely mimics that of the native hydroxamate inhibited Aeromonas proteolytica aminopeptidase.


Assuntos
Aminopeptidases/química , Ácidos Hidroxâmicos/síntese química , Compostos Organometálicos/síntese química , Inibidores de Proteases/síntese química , Zinco , Aeromonas/enzimologia , Aminopeptidases/antagonistas & inibidores , Mimetismo Molecular , Estrutura Molecular
13.
Dalton Trans ; 41(1): 208-18, 2012 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-22086273

RESUMO

We report the syntheses of imprinted polymers using iron-oxo-hydroxo clusters as templates. Three new iron clusters, [Fe(6)O(2)(OH)(2)(O(2)CC(Cl)=CH(2))(12)(H(2)O)(2)] (1), [{Fe(O(2)CC(Cl)=CH(2))(OMe)(2)}(10)] (2) and [Fe(6)O(2)(OH)(2)(O(2)C-Ph-(CH)=CH(2))(12)(H(2)O)(2)] (3) have been prepared from commercially-available carboxylic acids. Cluster-imprinted-polymers (CIPs) of 1, 2 and 3 were prepared with ethylene glycol dimethacrylate monomer, and of 1 with methyl methacrylate monomer. The imprinted sites within the CIPs were examined using EXAFS and diffuse reflectance UV/vis spectroscopy, demonstrating that the clusters 1, 2 and 3 were incorporated intact within the polymers. Extraction of the clusters from the CIPs imprinted with 1 and 3 gave new polymers that showed evidence of an imprinting effect.

14.
Inorg Chem ; 45(11): 4497-507, 2006 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-16711700

RESUMO

Attempts to produce Zn analogues of the structural model complexes [M2(mu-O2CR)2(O2CR)2(mu-H2O)(tmen)2] (M = Ni, Co, Mn; R = CH(3), C(CH3)3, CF3) by the reaction of a series of zinc carboxylates with N,N,N',N'-tetramethylethylenediamine (tmen), resulted in the mononuclear complexes [Zn(OAc)(2)(tmen)] (1) and [Zn(crot)2(tmen)].(0.5)H2O (2) for R = CH3 and (CH)2CH3, respectively, and the dinuclear complexes [Zn(2)(mu-piv)(2)(piv)(2)(mu-H2O)(tmen)2] (3) and [Zn2(mu-OAc(F))2(OAc(F))2(mu-H2O)(tmen)2] (4) for R = C(CH3)3 and CF3, respectively. In contrast to the analogous imidazole series, i.e., [M2(mu-O2CR)2(O2CR)2(mu-H2O)(Im)4] (M = Ni, Co, Mn; R = CH3, C(CH3)3, CF3), zinc carboxylates react with imidazole to give only the mononuclear complexes [Zn(OAc)2(Im)2] (5), [Zn(crot)2(Im)2].H2O (6), [Zn(piv)2(Im)2].(0.5)H2O (7), and [Zn(OAc(F))2(Im)2] (8). Reaction of 1, 2, and 3 with either acetohydroxamic acid (AHA) or benzohydroxamic acid (BHA) gives the dinuclear complexes [Zn2(O2CR)3(R'A)(tmen)], where R'A = acetohydroxamate (AA) (9, 10, 11) or benzohydroxamate (BA) (13, 14, 15). In these complexes, the zinc atoms are bridged by a single hydroxamate and two carboxylates, with a capping tmen ligand on one zinc and a monodentate carboxylate bonded to the second zinc atom. This composition models closely the observed structure of the active site of the p-iodo-d-phenylalanine hydroxamic acid inhibited Aeromonas proteolyticaaminopeptidase enzyme. In contrast, 4 reacts with AHA to give [Zn2(OAc(F))3(tmen)2(AA)] (12) with an additional tmen ligand so that both Zn atoms are 6-coordinate, whereas reaction with BHA gives the trinuclear complex [Zn3(OAc(F))4(tmen)2(BA)2] (16). Reactions of 3 and 4 with glutarodihydroxamic acid (GluH2A2) produce the tetranuclear complexes [Zn4(piv)6(tmen)4(GluA2)] (18) and [Zn4(OAc(F))6(tmen)4(GluA2)] (19).


Assuntos
Inibidores Enzimáticos/farmacologia , Hidrolases/antagonistas & inibidores , Hidrolases/química , Ácidos Hidroxâmicos/farmacologia , Compostos Organometálicos/síntese química , Compostos Organometálicos/farmacologia , Zinco/química , Aeromonas/química , Cristalografia por Raios X , Hidrogênio/química , Imidazóis/química , Modelos Moleculares , Modelos Estruturais , Hidrocarbonetos Policíclicos Aromáticos/química , Espectrofotometria Infravermelho
15.
Inorg Chem ; 43(1): 297-302, 2004 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-14704080

RESUMO

DFT calculations carried out on zinc acetate and zinc hydroxamates using the Hartree-Fock and B3LYP methods with the 6-311+G basis set give a series of stable pseudotetrahedral chelates (ZnL(2)) (L = OAc, FA, AA, NMeAA, GA, SA). Addition of a water molecule to these chelates gives the hydrates, ZnL(2).H(2)O, which in all cases are energetically more stable than the corresponding chelate. Hydrates formed from O,O coordinated hydroxamate species with a five-membered chelate ring contain water molecules occupying vacant coordination sites of the zinc atom. In contrast, those formed from zinc chelates with four-membered chelate rings contain a water molecule inserted into the chelate ring to give a six-membered ring in which one hydrogen of the water molecule is H-bonded to an oxygen atom of the zinc chelate with the water oxygen strongly bonded to the zinc. A slight lengthening of the H-bonded O-H bond suggests incipient hydroxide activation of water by zinc. In contrast, the O,O bonded hydroxamates do not incorporate water into the chelate ring nor activate the water in accordance with the ability of hydroxamic acids to inhibit zinc containing metalloenzymes.


Assuntos
Inibidores Enzimáticos/farmacologia , Hidrolases/química , Ácidos Hidroxâmicos/farmacologia , Modelos Moleculares , Zinco/química , Quelantes/química , Inibidores Enzimáticos/química , Ligação de Hidrogênio , Hidrolases/antagonistas & inibidores , Ácidos Hidroxâmicos/química
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