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1.
BMC Palliat Care ; 19(1): 117, 2020 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-32746825

RESUMO

BACKGROUND: General Practitioners (GPs) are the main providers of primary palliative care (PPC). At the same time they are the main initiators of specialised palliative homecare (SPHC). In Germany, little is known about factors which influence GPs in their involvement of SPHC. Aim of our study is to identify factors that drive GPs to give value to and involve SPHC. METHODS: A cross-sectional survey was performed. In 2018, questionnaires were mailed to 6000 randomly selected GPs from eight German federal states, focusing on the extent of GPs' palliative care activities and their involvement of SPHC. RESULTS: With a response rate of 19.4% and exclusion of GPs working in SPHC-teams, n = 1026 questionnaires were appropriate for analysis. GPs valued SPHC support as the most "important/very important" for both "technical/invasive treatment measures" (95%) and availability outside practice opening hours (92%). The most relevant factor influencing perceived SPHC-importance was GPs' self-reported extent of engagement in palliative care (ß = - 0.283; CI 95% = - 0.384;-0.182), followed by the perceived quality of utilised SPHC (ß = 0.119; CI 95% = 0.048;0.190), involvement in treatment of palliative patients after SPHC initiation (ß = 0.088; CI 95% = 0.042;0.134), and conviction that palliative care should be a central part of GPs' work (ß = - 0.062; CI 95% = - 0.116;-0.008). Perceived SPHC-importance is also associated with SPHC-referrals (ß =0.138; p < 0.001). The lower the engagement of GPs in palliative care, the more they involve SPHC and vice versa. CONCLUSIONS: GPs with low reported activity in palliative care are more likely to initialise SPHC for palliative care activities they do not deliver themselves for various reasons, which might mean that the involvement of SPHC is substitutive instead of complementary to primary palliative care. This finding and its interpretation should be given more attention in the future policy framework for (specialised) palliative homecare. TRIAL REGISTRATION: German Clinical Trials Register DRKS00014726 , 14.05.2018.


Assuntos
Clínicos Gerais/psicologia , Cuidados Paliativos/normas , Percepção , Adulto , Idoso , Estudos Transversais , Feminino , Clínicos Gerais/normas , Clínicos Gerais/estatística & dados numéricos , Alemanha , Humanos , Masculino , Pessoa de Meia-Idade , Cuidados Paliativos/tendências , Inquéritos e Questionários
2.
J Intern Med ; 287(1): 2-18, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31858669

RESUMO

There is compelling evidence that the elevated plasma lipoprotein(a) [Lp(a)] levels increase the risk of atherosclerotic cardiovascular disease (ASCVD) in the general population. Like low-density lipoprotein (LDL) particles, Lp(a) particles contain cholesterol and promote atherosclerosis. In addition, Lp(a) particles contain strongly proinflammatory oxidized phospholipids and a unique apoprotein, apo(a), which promotes the growth of an arterial thrombus. At least one in 250 individuals worldwide suffer from the heterozygous form of familial hypercholesterolemia (HeFH), a condition in which LDL-cholesterol (LDL-C) is significantly elevated since birth. FH-causing mutations in the LDL receptor gene demonstrate a clear gene-dosage effect on Lp(a) plasma concentrations and elevated Lp(a) levels are present in 30-50% of patients with HeFH. The cumulative burden of two genetically determined pro-atherogenic lipoproteins, LDL and Lp(a), is a potent driver of ASCVD in HeFH patients. Statins are the cornerstone of treatment of HeFH, but they do not lower the plasma concentrations of Lp(a). Emerging therapies effectively lower Lp(a) by as much as 90% using RNA-based approaches that target the transcriptional product of the LPA gene. We are now approaching the dawn of an era, in which permanent and significant lowering of the high cholesterol burden of HeFH patients can be achieved. If outcome trials of novel Lp(a)-lowering therapies prove to be safe and cost-effective, they will provide additional risk reduction needed to effectively treat HeFH and potentially lower the CVD risk in these high-risk patients even more than currently achieved with LDL-C lowering alone.


Assuntos
Doença da Artéria Coronariana/prevenção & controle , Hiperlipoproteinemia Tipo II/terapia , Lipoproteína(a)/sangue , Valva Aórtica , Remoção de Componentes Sanguíneos , LDL-Colesterol/sangue , Doença da Artéria Coronariana/etiologia , Doenças das Valvas Cardíacas/etiologia , Doenças das Valvas Cardíacas/prevenção & controle , Humanos , Inibidores de Hidroximetilglutaril-CoA Redutases/uso terapêutico , Hiperlipoproteinemia Tipo II/sangue , Hipolipemiantes/uso terapêutico , Oligonucleotídeos Antissenso/uso terapêutico , Inibidores de PCSK9 , Guias de Prática Clínica como Assunto , Receptores de LDL/genética , Fatores de Risco , Calcificação Vascular/etiologia , Calcificação Vascular/prevenção & controle
5.
Gesundheitswesen ; 77(3): 219-24, 2015 Mar.
Artigo em Alemão | MEDLINE | ID: mdl-25137307

RESUMO

Empirical indications show that specialised out-patient palliative care (SAPV), introduced in Germany in 2007, allows critically ill and dying patients to pass away within their own home even under complex symptoms. SAPV avoids emergency and hospital interferences, and the patient's wish to stay at home until the very end can be respected in most cases. The performance of SAPV is not solely focused on medical and patient-care aspects. It includes consulting and coordination work and also psycho-social support both of patients and family members. Within this framework, different active factors could be identified that are essential for high-quality care. Furthermore, the results show that the general ambulant care commodities on site determine the need, the extent and even the efficiency of SAPV. At the same time, SAPV changes also the respective care environment: it changes the roles of previous care providers and offers new resources, though not all existing resources (e. g., hospice services) are taken into account.


Assuntos
Assistência Ambulatorial/organização & administração , Modelos Organizacionais , Cuidados Paliativos/organização & administração , Avaliação de Processos em Cuidados de Saúde , Serviços de Saúde Rural/organização & administração , Assistência Terminal/organização & administração , Eficiência Organizacional , Alemanha
6.
Zentralbl Chir ; 139(1): 83-8, 2014 Feb.
Artigo em Alemão | MEDLINE | ID: mdl-21598203

RESUMO

INTRODUCTION: Extravasal application of chemo-therapeutic agents may cause necrosis of surrounding tissue. Often tendons, nerves and muscles are destroyed. In some cases a surgical excision with an additional coverage is indicated. PATIENTS AND METHODS: In the last ten years we have treated 44  patients with necrosis after extravasation. The defects were mostly localised at the hand or distal forearm, but the cubital fossa and the thorax were affected, too. Excision of the infiltrated tissue was performed and the defect covered with local or free flaps, split skin graft or primary closure. RESULTS: In nearly all cases a stable coverage was achieved. An amputation of the hand was never necessary. Patients with immunosuppression or comorbidity sometimes had wound-healing difficulties that in some cases necessitated further operations. Serious complications were in one case a flap necrosis and another patient died 2  days after the operation because of his nephrotic syndrome. CONCLUSION: Chemotherapy extravasation is an important oncological complication that may cause permanent functional disability of the anatomic region. A variety of free and local flaps with tolerable donor site morbidity can be used for -coverage. We prefer a two-step procedure with radical resection of the area and conditioning of the wound with vacuum therapy or temporary wound coverage and in the next step the definitive wound closure. Conservative treatment is -often followed by a high rate of complications. Early radical debridement and coverage with an adequate flap offers a cure with good functional results.


Assuntos
Antibacterianos/efeitos adversos , Antineoplásicos/administração & dosagem , Antineoplásicos/efeitos adversos , Extravasamento de Materiais Terapêuticos e Diagnósticos/cirurgia , Neoplasias/tratamento farmacológico , Pele/efeitos dos fármacos , Pele/patologia , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Antibacterianos/administração & dosagem , Criança , Pré-Escolar , Extravasamento de Materiais Terapêuticos e Diagnósticos/diagnóstico , Feminino , Humanos , Lactente , Masculino , Microcirurgia , Pessoa de Meia-Idade , Necrose , Tratamento de Ferimentos com Pressão Negativa , Complicações Pós-Operatórias/cirurgia , Reoperação , Transplante de Pele , Retalhos Cirúrgicos/cirurgia , Adulto Jovem
7.
Handchir Mikrochir Plast Chir ; 43(5): 313-6, 2011 Oct.
Artigo em Alemão | MEDLINE | ID: mdl-21850610

RESUMO

A common reason for persisting or new complaints after carpal tunnel surgery is an incomplete release of the retinaculum flexorum. Traction neuropathy, a real recurrent carpal tunnel syndrome and iatrogenic nerve lesions occur less frequently. In the case of an incomplete release of the flexor retinaculum the clinical symptoms in most of the patients can be resolved with revision surgery. Electrodiagnostic testing can only support the indication for a reoperation if a preoperative examination exists but is not able to demonstrate the exact cause of a failed carpal tunnel surgery. The 4 cases presented here show that high resolution ultrasound provides valuable information in addition to electrodiagnostic testing before a reintervention.


Assuntos
Síndrome do Túnel Carpal/diagnóstico por imagem , Síndrome do Túnel Carpal/cirurgia , Nervo Mediano/diagnóstico por imagem , Nervo Mediano/cirurgia , Complicações Pós-Operatórias/diagnóstico por imagem , Complicações Pós-Operatórias/cirurgia , Cicatriz/diagnóstico por imagem , Cicatriz/cirurgia , Eletrodiagnóstico , Feminino , Dedos/inervação , Humanos , Hipestesia/diagnóstico por imagem , Hipestesia/cirurgia , Masculino , Recidiva , Reoperação , Ultrassonografia
8.
Sarcoidosis Vasc Diffuse Lung Dis ; 28(1): 72-4, 2011 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-21796894

RESUMO

BACKGROUND: Sarcoidosis is a systemic disorder with unknown etiology, characterized by non-caseating granulomas in numerous organs and tissues. In 90% of patients lung and lymph nodes are involved. The incidence of sarcoidal granulomas in the upper extremities is low. Here we present the case of a primary hand manifestation of sarcoidosis without clinical systemic involvement. OBJECTIVES: A young woman presented with a painful swelling in her right hand. There were no signs of inflammation. Normal perfusion, mobility and sensibility were found. Magnetic resonance imaging (MRI) revealed a tumour infiltrating the muscles and flexor tendons of the third digit around the metacarpal bone and with pathological signal enhancement after administration of contrast medium. RESULTS: Intraoperatively, nodular masses and fat tissue were seen. Histological examination after radical tumour resection showed sarcoidal granulomas. Postoperative staging diagnostics with computed tomography (CT) demonstrated multiple thoracic lymph node swellings in the mediastinum and bilateral hill. Follow-up after one year we saw normal scars in the palmar hand. There was no sign of local recurrence. The pulmological care is still going on. CONCLUSIONS: Sarcoidosis is a rare, often asymptomatic disease. Patients present with dyspnoe and cough caused by the inflammation of the lung. The first clinical manifestation of sarcoidosis as a tumor in the palmar hand is unusual. Extrapulmonary systemic or progressive sarcoidosis is regarded as an indication for therapy with glucocorticosteroids. This case demonstrates that surgical excision enabled complete local cure without necessity of systemic and/or local treatment with steroids.


Assuntos
Granuloma/diagnóstico , Mãos , Sarcoidose/diagnóstico , Adulto , Doenças Assintomáticas , Diagnóstico Diferencial , Feminino , Granuloma/cirurgia , Humanos , Imageamento por Ressonância Magnética , Sarcoidose/cirurgia , Tomografia Computadorizada por Raios X
9.
Versicherungsmedizin ; 63(2): 68-75, 2011 Jun 01.
Artigo em Alemão | MEDLINE | ID: mdl-21698942

RESUMO

The limited availability of appropriate methods and criteria makes the assessment of capability by psychic and psychosomatic disorders difficult. This article displays and discusses the standards relating to content and method in capability assessments. The underlying diagnostic model of assessment capability has been conceptualised and tested empirically by a multicentric and interdisciplinary work-group. Different diagnostic levels of the manual are outlined as well as the procedures of operationalisation of the diagnostic categories. Furthermore, first results of empirical analysis are described and important conditions of the application of the diagnostic model are discussed.


Assuntos
Avaliação da Deficiência , Prova Pericial/legislação & jurisprudência , Transtornos Mentais/diagnóstico , Programas Nacionais de Saúde/legislação & jurisprudência , Transtornos Psicofisiológicos/diagnóstico , Previdência Social/legislação & jurisprudência , Adaptação Psicológica , Comportamento Cooperativo , Definição da Elegibilidade/legislação & jurisprudência , Alemanha , Humanos , Comunicação Interdisciplinar , Simulação de Doença/diagnóstico , Simulação de Doença/psicologia , Transtornos Mentais/psicologia , Testes Psicológicos , Transtornos Psicofisiológicos/psicologia
11.
Thorac Cardiovasc Surg ; 59(7): 439-41, 2011 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-21445826

RESUMO

Coronary artery aneurysms (CAA) in adults are rare. However, the natural history of CAA is unknown since in adults it is predominantly atherosclerotic in origin. The clinical presentation, prognosis and management of giant CAA are not well defined due to limited experience and the low incidence of CAA. We present a case of successful exclusion of multiple giant CAA with an interposed reversed saphenous vein graft.


Assuntos
Aneurisma Coronário/cirurgia , Ponte de Artéria Coronária , Veia Safena/transplante , Idoso , Aneurisma Coronário/diagnóstico por imagem , Angiografia Coronária , Humanos , Masculino , Tomografia Computadorizada por Raios X , Resultado do Tratamento
12.
Pneumologie ; 64(1): 37-44, 2010 Jan.
Artigo em Alemão | MEDLINE | ID: mdl-20013607

RESUMO

The increasing use of high-resolution computed tomography in formerly asbestos-exposed workers requires valid diagnostic criteria for the findings which have to be reported as suspicious for being asbestos-related in surveillance programmes and for the assessment of causal relationships between former asbestos exposure and findings in computed tomography. The present article gives examples for asbestos-related findings in HR-CT and discusses the specificity of parenchymal and pleural changes due to asbestos fibres.


Assuntos
Amianto/análise , Asbestose/diagnóstico , Asbestose/epidemiologia , Prova Pericial/estatística & dados numéricos , Pulmão/diagnóstico por imagem , Vigilância da População/métodos , Tomografia Computadorizada por Raios X/estatística & dados numéricos , Causalidade , Alemanha/epidemiologia , Humanos , Programas de Rastreamento/métodos , Programas de Rastreamento/estatística & dados numéricos , Medição de Risco/métodos , Fatores de Risco
13.
Pneumologie ; 63(12): 726-32, 2009 Dec.
Artigo em Alemão | MEDLINE | ID: mdl-19937572

RESUMO

Asbestos-related diseases still play an important role in occupational medicine. The detection of benign asbestos-related diseases is one condition for the compensation of asbestos-related lung cancer in Germany. Due to the increasing use of computed tomography, asbestos-related diseases are more frequently detected in the early stages. The present article proposes recommendations for the findings which have to be reported as suspicious for being asbestos-related based on a) chest X-rays and b) computed tomography using the International Classification System for Occupational and Environmental Respiratory Diseases (ICOERD).


Assuntos
Asbestose/diagnóstico por imagem , Formulário de Reclamação de Seguro/normas , Seguro de Acidentes/normas , Guias de Prática Clínica como Assunto , Radiografia Torácica/normas , Tomografia Computadorizada por Raios X/normas , Alemanha , Humanos
14.
Pneumologie ; 63(11): 664-8, 2009 Nov.
Artigo em Alemão | MEDLINE | ID: mdl-19862671

RESUMO

The classification of pneumoconiosis according to ILO standard - comparing a X-ray of the lung with ILO radiographs - is well established in Germany. The extension of digital imaging is a challenging task in occupational medicine as well as in pneumology. Technical requirements are not known sufficiently and the necessary equipment is not well distributed. This paper describes the current position on recording, assessment and documentation of digital imaging of the lung and pleura.


Assuntos
Pneumoconiose/diagnóstico por imagem , Guias de Prática Clínica como Assunto , Intensificação de Imagem Radiográfica/normas , Radiografia Torácica/normas , Alemanha , Humanos
15.
Orthopade ; 38(11): 1117-26, 2009 Nov.
Artigo em Alemão | MEDLINE | ID: mdl-19730810

RESUMO

Hallux valgus represents a combined deformity with malpositioning of the big toe in the metatarsophalangeal joint and metatarsal splaying due to metatarsus primus varus formation. It is defined on the basis of joint condition of the metatarsophalangeal and tarsometatarsal (TMT) joints, the extent and congruence or incongruence of malposition, mobility of the metatarsophalangeal joint and TMT stability. Basic resection appears to be indicated only in exceptional cases. Depending on the degree of severity, deformities can be corrected by means of distal, diaphyseal or proximal osteotomies and TMT arthrodeses. Any correction requires the use of subtle soft tissue surgery with recentering of the tendon, tightening of the medial capsule and abductor hallucis and releasing the lateral capsule. A check-list-like analysis of hallux valgus deformity helps determine the ideal procedure and avoid over- or under-treatment.


Assuntos
Artrodese/métodos , Hallux Valgus/diagnóstico , Hallux Valgus/cirurgia , Osteotomia/métodos , Procedimentos de Cirurgia Plástica/métodos , Humanos
16.
Dtsch Med Wochenschr ; 134 Suppl Falldatenbank: F3, 2009.
Artigo em Alemão | MEDLINE | ID: mdl-19319790

RESUMO

Thoracic outlet syndrome (TOS) is a broad term for compression of the neurovascular structures in the area of the 1. rib and the clavicle. The cause can be either fibrous bands, cervical ribs, anomalous muscles or posttraumatic changes as well as tumors. Symptoms depend on the affected structure, in most cases (up to 97% of TOS patients) neurologic symptoms are present. In case of an arterial compression, for example due to a cervical rib like in our case, embolism of the arm and finger arteries can occur. For mild or moderate symptoms a conservative approach with physiotherapy can be helpful. For severe cases surgical resection of the compressing structure and the first rib is necessary. In our case, the cervical and first rib were excised after an initial lysis therapy. Furthermore, the aneurysm of the subclavian artery was excised.


Assuntos
Síndrome da Costela Cervical/complicações , Síndrome da Costela Cervical/diagnóstico , Doença de Raynaud/etiologia , Tromboembolia/etiologia , Adulto , Aneurisma/complicações , Aneurisma/cirurgia , Anticoagulantes/administração & dosagem , Aspirina/administração & dosagem , Síndrome da Costela Cervical/cirurgia , Diagnóstico Diferencial , Enoxaparina/administração & dosagem , Feminino , Fibrinolíticos/administração & dosagem , Humanos , Infusões Intra-Arteriais , Inibidores da Agregação Plaquetária/administração & dosagem , Doença de Raynaud/terapia , Costelas/anormalidades , Costelas/cirurgia , Artéria Subclávia , Tromboembolia/terapia , Ativador de Plasminogênio Tipo Uroquinase/administração & dosagem
17.
Chirurg ; 80(5): 448, 450-4, 2009 May.
Artigo em Alemão | MEDLINE | ID: mdl-18682906

RESUMO

Olecranon bursitis has a high prevalence and is commonly treated conservatively. However, in case of bacterial infection and open injuries with chronic courses, surgery is indicated. Despite high surgical standards, soft-tissue defects cannot always be avoided in primary surgery for infectious olecranon bursitis. For complicated courses with persisting defects, standardized closing procedures are available. For maintaining adequate elbow function and avoiding long disease progression, definite closure of the defect should be achieved. Various treatment options exist: VAC therapy and local, island, distant, and free flaps. Between 1996 and 2007, 12 Patients with complicated olecranon bursitis were treated in our institution. Of them, 11 received surgery. In complicated courses of olecranon bursitis with soft-tissue defects, fistulas, or recurrent wound healing disorders, there are several procedures for plastic covering of the elbow.


Assuntos
Bursite/cirurgia , Articulação do Cotovelo/cirurgia , Adulto , Idoso , Algoritmos , Bolsa Sinovial/cirurgia , Bursite/diagnóstico , Fístula Cutânea/cirurgia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Tratamento de Ferimentos com Pressão Negativa , Cuidados Pós-Operatórios , Complicações Pós-Operatórias/cirurgia , Recidiva , Reoperação , Retalhos Cirúrgicos
18.
Handchir Mikrochir Plast Chir ; 40(3): 153-5, 2008 Jun.
Artigo em Alemão | MEDLINE | ID: mdl-18548358

RESUMO

Rupture of the extensor pollicis longus tendon is a frequent complication after distal radius fractures or other traumatic and non-traumatic events. Typical is the loss of the function of extension in the thumb. The extensor indicis transfer is a simple and effective technique for reconstruction of the extension with a low donor-site morbidity. We report on 38 patients with extensor indicis transfer. Postoperatively the patients received a dynamic motion splint for 4 weeks. For evaluation we have done pre- and postoperative ultrasound scans of the thumb, evaluated the DASH score and carried out a clinical examination.


Assuntos
Traumatismos dos Tendões/cirurgia , Transferência Tendinosa/métodos , Polegar/lesões , Adulto , Idoso , Artrite Reumatoide/complicações , Feminino , Seguimentos , Humanos , Masculino , Pessoa de Meia-Idade , Destreza Motora/fisiologia , Osteoartrite/complicações , Cuidados Pós-Operatórios , Fraturas do Rádio/complicações , Amplitude de Movimento Articular/fisiologia , Reoperação , Contenções , Traumatismos dos Tendões/diagnóstico por imagem , Polegar/diagnóstico por imagem , Ultrassonografia
19.
Handchir Mikrochir Plast Chir ; 40(2): 88-93, 2008 Apr.
Artigo em Alemão | MEDLINE | ID: mdl-18437666

RESUMO

INTRODUCTION: Aggressive fibromatosis, e.g., desmoid tumour, is a rare neoplasm of the connective tissue with local infiltrative growth. Because of the high recurrence rates and destruction of the surrounding tissue, these tumours are classified as semi-malignant. However, desmoid tumors tend not to metastasise. Arising from deep musculoaponeurotic structures, a monoclonal proliferation of fibroblasts occurs. Radical surgical treatment with tumour excision accompanied by radiotherapy is the current standard therapy that can be supplemented by pharmacological treatment in a few cases. PATIENTS AND METHOD: We report on 9 patients (5 males and 4 females) with surgical therapy for aggressive fibromatosis. The neoplasm was located on the extremities in 7 cases (4 x upper extremity, 3 x lower extremity), one tumour was situated in the chin and one in the rectus abdominis muscle. All patients were treated with radical tumour resection. Postoperatively, adjuvant radiotherapy was performed depending on the resection level of each patient. RESULTS: In 6 cases complete tumour resection (R0) was achieved. Following surgery, regular follow-ups with a physical examination and MR images were performed. In 3 cases a total tumour resection was impossible (R1 resection). The aggressive fibromatosis had infiltrated the pelvis in 2 cases implying a hemipelvectomy for R0 resection which was not practicable. Furthermore, diffuse locoregional infiltration of the chin region occurred in one case. In these cases, an adjuvant radiotherapy with 25 x 2 Gy was started postoperatively after the accomplished wound healing. Treatment with chemotherapeutic agents was not necessary. DISCUSSION: Aggressive fibromatosis is a semimalignant neoplasm of the connective tissue with an extremely high recurrence rate. Macroscopically, indistinct solid lesions are found with the destruction of muscles and other surrounding structures. Therapy of choice is the radical surgical resection. Radiotherapy is indicated for patients with non-resectable tumours. Pharmacological treatment should be considered for patients with unsuccessful local therapy.


Assuntos
Fibromatose Agressiva/terapia , Neoplasias de Tecidos Moles/terapia , Adulto , Braço , Queixo , Feminino , Fibromatose Agressiva/diagnóstico , Fibromatose Agressiva/patologia , Fibromatose Agressiva/radioterapia , Fibromatose Agressiva/cirurgia , Seguimentos , Humanos , Perna (Membro) , Imageamento por Ressonância Magnética , Masculino , Pessoa de Meia-Idade , Cuidados Pós-Operatórios , Dosagem Radioterapêutica , Radioterapia Adjuvante , Reto do Abdome , Neoplasias de Tecidos Moles/diagnóstico , Neoplasias de Tecidos Moles/patologia , Neoplasias de Tecidos Moles/radioterapia , Neoplasias de Tecidos Moles/cirurgia , Retalhos Cirúrgicos , Fatores de Tempo
20.
J Phys Chem A ; 112(13): 2773-81, 2008 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-18331013

RESUMO

FTIR smog chamber techniques were used to measure k(Cl+n-C3H7OH) = (1.74 +/- 0.15) x 10-10 and k(Cl+CH2ClCH2CH2OH) = (7.54 +/- 0.73) x 10-11 cm3 molecule-1 s-1 in 700 Torr of N2 at 296 K. The reaction of Cl with n-C3H7OH gives CH3CH2CHOH, CH3CHCH2OH, and CH2CH2CH2OH radicals in yields of 60 +/- 5, 25 +/- 8, and 15 +/- 3%, respectively. Neither CH3CH2CHClOH nor CH3CHClCH2OH is available commercially, and infrared spectra for the three chlorides CH3CH2CHClOH, CH3CHClCH2OH, and CH2ClCH2CH2OH were calibrated experimentally. MP2/6-31G(d,p) calculations were used to corroborate the experimental vibrational assignments. Analysis reveals that each geometric isomer possesses several structurally and spectroscopically distinct conformers arising from intramolecular hydrogen bonding and, in the case of CH3CH2CHClOH, negative hyperconjugation. These conformers interchange slowly enough to be distinguished within the room-temperature vibrational spectrum. The experimentally observed vibrational spectra are well described by a Boltzmann-weighted superposition of the conformer spectra. As is typical of alpha-halogenated alcohols, CH3CH2CHClOH readily decomposes heterogeneously to propanal and HCl.


Assuntos
1-Propanol/química , Físico-Química/métodos , Cloro/química , Cloridrinas/química , Propanóis/química , Conservação de Recursos Energéticos , Transferência de Energia , Isomerismo , Modelos Químicos , Modelos Moleculares , Conformação Molecular , Transição de Fase , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura
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