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1.
Angew Chem Int Ed Engl ; 62(34): e202307009, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37378955

RESUMO

Pressure-sensitive adhesives (PSAs) are made from soft, irreversibly lightly crosslinked polymers. Even after removal from surfaces, they retain insoluble networks which pose problems during the recycling of glass and cardboard. Herein, degradable PSAs are presented that provide the required performance in use but have networks that can be degraded after use. A series of copolymers was prepared through radical copolymerization of n-butyl acrylate, 4-acryloyloxy benzophenone (ABP) photo-crosslinker, and dibenzo[c,e]oxepin-5(7H)-thione (DOT) to provide degradable backbone thioesters. The optimum tack and peel strengths were found for molar contents of 0.05 mol% ABP and 0.25 mol% DOT. Degradation of the backbone thioesters through aminolysis or thiolysis led to the full dissolution of the networks, loss of adhesive properties of films (decreases in the measured tack and peel strengths), and the quick detachment of model labels from a substrate. Inclusion of DOT into PSAs offers a viable route toward degradable and recyclable packaging labels.

2.
J Exp Bot ; 73(15): 5170-5198, 2022 09 03.
Artigo em Inglês | MEDLINE | ID: mdl-35675172

RESUMO

High-throughput profiling of key enzyme activities of carbon, nitrogen, and antioxidant metabolism is emerging as a valuable approach to integrate cell physiological phenotyping into a holistic functional phenomics approach. However, the analyses of the large datasets generated by this method represent a bottleneck, often keeping researchers from exploiting the full potential of their studies. We address these limitations through the exemplary application of a set of data evaluation and visualization tools within a case study. This includes the introduction of multivariate statistical analyses that can easily be implemented in similar studies, allowing researchers to extract more valuable information to identify enzymatic biosignatures. Through a literature meta-analysis, we demonstrate how enzyme activity profiling has already provided functional information on the mechanisms regulating plant development and response mechanisms to abiotic stress and pathogen attack. The high robustness of the distinct enzymatic biosignatures observed during developmental processes and under stress conditions underpins the enormous potential of enzyme activity profiling for future applications in both basic and applied research. Enzyme activity profiling will complement molecular -omics approaches to contribute to the mechanistic understanding required to narrow the genotype-to-phenotype knowledge gap and to identify predictive biomarkers for plant breeding to develop climate-resilient crops.


Assuntos
Fenômica , Melhoramento Vegetal , Produtos Agrícolas/genética , Fenótipo , Desenvolvimento Vegetal/genética , Estresse Fisiológico/genética
3.
Biomacromolecules ; 23(5): 2031-2039, 2022 05 09.
Artigo em Inglês | MEDLINE | ID: mdl-35472265

RESUMO

Being nondegradable, vinyl polymers have limited biomedical applicability. Unfortunately, backbone esters incorporated through conventional radical ring-opening methods do not undergo appreciable abiotic hydrolysis under physiologically relevant conditions. Here, PEG acrylate and di(ethylene glycol) acrylamide-based copolymers containing backbone thioesters were prepared through the radical ring-opening copolymerization of the thionolactone dibenzo[c,e]oxepin-5(7H)-thione. The thioesters degraded fully in the presence of 10 mM cysteine at pH 7.4, with the mechanism presumed to involve an irreversible S-N switch. Degradations with N-acetylcysteine and glutathione were reversible through the thiol-thioester exchange polycondensation of R-SC(═O)-polymer-SH fragments with full degradation relying on an increased thiolate/thioester ratio. Treatment with 10 mM glutathione at pH 7.2 (mimicking intracellular conditions) triggered an insoluble-soluble switch of a temperature-responsive copolymer at 37 °C and the release of encapsulated Nile Red (as a drug model) from core-degradable diblock copolymer micelles. Copolymers and their cysteinolytic degradation products were found to be noncytotoxic, making thioester backbone-functional polymers promising for drug delivery applications.


Assuntos
Polietilenoglicóis , Polímeros , Portadores de Fármacos , Liberação Controlada de Fármacos , Glutationa , Micelas
4.
Thorac Cardiovasc Surg ; 69(2): 124-132, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-31604356

RESUMO

BACKGROUND: Different ablation devices deliver the same type of energy but use individual control mechanisms to estimate efficacy. We compared patient outcome after the application of radiofrequency ablation systems, using temperature- or resistance-control in paroxysmal and persistent atrial fibrillation (AF). METHODS: This is an unselected all-comers study. Patients underwent standardized left atrial (paroxysmal atrial fibrillation, [PAF] n = 31) or biatrial ablation (persistent atrial fibrillation [persAF] n = 61) with bipolar RF from October 2010 to June 2013. Patients with left atrial dilatation (up to 57 mm), reduced left ventricular (LV) function, and elderly were included. We used resistance-controlled (RC) or temperature-controlled (TC) devices. We amputated atrial appendices and checked intraoperatively for completeness of pulmonary vein exit block. All patients received implantable loop recorders. Follow-up interval was every 6 months. Antiarrhythmic medical treatment endured up to month 6. RESULTS: We reached 100% freedom from atrial fibrillation (FAF) in PAF. In perAF 19% of the RC but 82% of the TC patients reached FAF (12 months; p < 0.05). TC patients exhibited higher creatine kinase-muscle/brain (CK-MB) peak values. In persAF, CK-MB-levels correlated to FAF. No and no mortality (30 days) was evident. Twelve-month mortality did not correlate to AF type, AF duration, LV dimension, or function and age. Prolonged need of oral anticoagulants was 90.1% (RC) and 4.5% (TC). CONCLUSION: In patients with persAF undergoing RF ablation, TC reached higher FAF than RC. Medical devices are not "the same" regarding effectiveness even if used according to manufacturer's instructions. Thus, putative application of "the same" energy is not always "the same" efficacy.


Assuntos
Fibrilação Atrial/cirurgia , Cateteres Cardíacos , Ablação por Cateter/instrumentação , Veias Pulmonares/cirurgia , Potenciais de Ação , Idoso , Apêndice Atrial/fisiopatologia , Apêndice Atrial/cirurgia , Fibrilação Atrial/diagnóstico , Fibrilação Atrial/fisiopatologia , Ablação por Cateter/efeitos adversos , Impedância Elétrica , Desenho de Equipamento , Feminino , Frequência Cardíaca , Humanos , Masculino , Veias Pulmonares/fisiopatologia , Recidiva , Temperatura , Fatores de Tempo , Resultado do Tratamento
5.
Entropy (Basel) ; 23(6)2021 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-34205211

RESUMO

Information plane analysis, describing the mutual information between the input and a hidden layer and between a hidden layer and the target over time, has recently been proposed to analyze the training of neural networks. Since the activations of a hidden layer are typically continuous-valued, this mutual information cannot be computed analytically and must thus be estimated, resulting in apparently inconsistent or even contradicting results in the literature. The goal of this paper is to demonstrate how information plane analysis can still be a valuable tool for analyzing neural network training. To this end, we complement the prevailing binning estimator for mutual information with a geometric interpretation. With this geometric interpretation in mind, we evaluate the impact of regularization and interpret phenomena such as underfitting and overfitting. In addition, we investigate neural network learning in the presence of noisy data and noisy labels.

6.
Bioinformatics ; 35(21): 4522-4524, 2019 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-30989173

RESUMO

MOTIVATION: Image augmentation is a frequently used technique in computer vision and has been seeing increased interest since the popularity of deep learning. Its usefulness is becoming more and more recognized due to deep neural networks requiring larger amounts of data to train, and because in certain fields, such as biomedical imaging, large amounts of labelled data are difficult to come by or expensive to produce. In biomedical imaging, features specific to this domain need to be addressed. RESULTS: Here we present the Augmentor software package for image augmentation. It provides a stochastic, pipeline-based approach to image augmentation with a number of features that are relevant to biomedical imaging, such as z-stack augmentation and randomized elastic distortions. The software has been designed to be highly extensible meaning an operation that might be specific to a highly specialized task can easily be added to the library, even at runtime. Although it has been designed as a general software library, it has features that are particularly relevant to biomedical imaging and the techniques required for this domain. AVAILABILITY AND IMPLEMENTATION: Augmentor is a Python package made available under the terms of the MIT licence. Source code can be found on GitHub under https://github.com/mdbloice/Augmentor and installation is via the pip package manager (A Julia version of the package, developed in parallel by Christof Stocker, is also available under https://github.com/Evizero/Augmentor.jl).


Assuntos
Redes Neurais de Computação , Software , Bases de Dados Factuais , Aprendizado Profundo
7.
Soft Matter ; 16(36): 8453-8461, 2020 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-32812973

RESUMO

In this work, we synthesize a polydisperse aqueous colloidal system composed of small and large zwitterionic particles, as well as medium sized standard acrylic particles. By assembling these dispersions into films by drying, we show using atomic force microscopy (AFM) how their top surfaces can be mostly covered by zwitterionic groups for a wide range of evaporation rates. We probe underneath the top film surface using Fourier-transform infrared (FTIR) spectroscopy - attenuated total reflection (ATR), observing that the content in zwitterionic particles of the film upper layer increases for faster evaporation rates. We show how polydisperse systems hold great potential to overcome the evaporation rate dependence of size segregation processes in drying colloidal blends, and we provide further insights into the assembly mechanisms involved. Polydisperse blends enhance the robustness of such processes for application in coatings and other soft products where evaporation rate can not be tuned.

8.
Thorac Cardiovasc Surg ; 68(8): 737-742, 2020 12.
Artigo em Inglês | MEDLINE | ID: mdl-30153697

RESUMO

BACKGROUND: To examine if fibrin-coated collagen fleece (Tachosil) interferes with bone and wound healing when it is used on the cut surface of the sternum after median sternotomy. METHODS: A total of 25 patients with osteoporotic sternal disorders were treated with fibrin-coated collagen fleece at the cut surface of the sternum after median sternotomy (therapy group). We compared the occurrence of impaired wound healing and sternal instability, reoperation rate, and 30-day mortality with a control group of 25 case-matched patients. After matching for age, gender, and risk factors for sternal instability (diabetes mellitus, osteoporosis, body mass index, nicotine consumption), both groups were comparable. RESULTS: Sternal instability occurred in one (4%) patient in the study group and in five (20%) patients in the control group. Impaired wound healing occurred in one (4%) patient in the therapy group and two (8%) patients in the control group. Reoperation was necessary in four (16%) patients in the therapy group and 6 (24%) patients in the control group. The 30-day mortality occurred in six (24%) patients in the therapy group and four (16%) patients in the control group. CONCLUSIONS: The use of fibrin-coated collagen fleece on the cut surface of the sternum in patients with osteoporosis does not impair bone and wound healing. Furthermore, it seems to result in less sternal instability. A larger prospective study is necessary to verify the results of this explorative study.


Assuntos
Remodelação Óssea , Procedimentos Cirúrgicos Cardíacos , Colágeno/uso terapêutico , Osteoporose/fisiopatologia , Complicações Pós-Operatórias/prevenção & controle , Esternotomia , Cicatrização , Idoso , Procedimentos Cirúrgicos Cardíacos/efeitos adversos , Procedimentos Cirúrgicos Cardíacos/mortalidade , Colágeno/efeitos adversos , Feminino , Humanos , Masculino , Análise por Pareamento , Osteoporose/complicações , Osteoporose/diagnóstico , Complicações Pós-Operatórias/mortalidade , Complicações Pós-Operatórias/fisiopatologia , Estudos Retrospectivos , Fatores de Risco , Esternotomia/efeitos adversos , Esternotomia/mortalidade , Fatores de Tempo , Resultado do Tratamento
9.
Thorac Cardiovasc Surg ; 68(5): 389-400, 2020 08.
Artigo em Inglês | MEDLINE | ID: mdl-30743275

RESUMO

BACKGROUND: Prediction, early diagnosis, and therapy of cardiac surgery-associated acute kidney injury (CSA-AKI) are challenging. We prospectively tested a staged approach to identify patients at high risk for CSA-AKI combining clinical risk stratification and early postoperative quantification of urinary biomarkers for AKI. METHODS: All patients, excluding those on chronic hemodialysis, undergoing scheduled surgery with cardiopulmonary bypass between August 2015 and July 2016 were included. First, patients were stratified by calculating the Cleveland clinic score (CCS) and the Leicester score (LS). In high-risk patients (defined as LS > 25 or CCS > 6), urinary concentrations of biomarkers for AKI ([TIMP-2]*[IGFBP-7]) were evaluated 4 hours postoperatively. CSA-AKI was observed until postoperative day 6 and classified using the Kidney Disease: Improving Global Outcomes criteria. RESULTS: AKI occurred in 352 of613 patients (54%). In high-risk patients, AKI occurred more frequently than in low-risk patients (66 vs. 49%; p = 0.001). In-hospital mortality after AKI stage 2 (15%) or AKI stage 3 (49%) compared with patients without AKI (1.8%; p = 0.001) was increased. LS was predictive for all stages of AKI (area under the curve [AUC] 0.601; p < 0.001) with a poor or fair accuracy, while CCS was only predictive for stage 2 or 3 AKI (AUC 0.669; p < 0.001) with fair accuracy. In 133 high-risk patients, urinary [TIMP-2]*[IGFBP-7] was significantly predictive for all-stage AKI within 24 hours postoperatively (AUC 0.63; p = 0.017). However, for the majority of AKI (55%), which occurred beyond 24 hours postoperatively, urinary [TIMP-2]*[IGFBP-7] was not significantly predictive. Sensitivity for all-stage AKI within 24 hours was 0.38 and specificity was 0.81 using a cutoff value of 0.3. CONCLUSION: CSA-AKI is a relevant and frequent complication after cardiac surgery. Patients at high risk for CSA-AKI can be identified using clinical prediction scores, however, with only poor to fair accuracy. Due to its weak test performance, urinary [TIMP-2]*[IGFBP-7] quantification 4 hours postoperatively does not add to the predictive value of clinical scores.


Assuntos
Injúria Renal Aguda/etiologia , Procedimentos Cirúrgicos Cardíacos/efeitos adversos , Regras de Decisão Clínica , Proteínas de Ligação a Fator de Crescimento Semelhante a Insulina/urina , Inibidor Tecidual de Metaloproteinase-2/urina , Injúria Renal Aguda/diagnóstico , Injúria Renal Aguda/mortalidade , Injúria Renal Aguda/urina , Idoso , Idoso de 80 Anos ou mais , Biomarcadores/urina , Procedimentos Cirúrgicos Cardíacos/mortalidade , Feminino , Mortalidade Hospitalar , Humanos , Masculino , Pessoa de Meia-Idade , Valor Preditivo dos Testes , Estudos Prospectivos , Medição de Risco , Fatores de Risco , Fatores de Tempo , Resultado do Tratamento , Urinálise
10.
Macromol Rapid Commun ; 40(2): e1800346, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-29974542

RESUMO

The use of 2,3,4,5,6-pentafluorobenzyl methacrylate (PFBMA) as a core-forming monomer in ethanolic reversible addition-fragmentation chain transfer dispersion polymerization formulations is presented. Poly[poly(ethylene glycol) methyl ether methacrylate] (pPEGMA) macromolecular chain transfer agents were chain-extended with PFBMA leading to nanoparticle formation via polymerization-induced self-assembly (PISA). pPEGMA-pPFBMA particles exhibited the full range of morphologies (spheres, worms, and vesicles), including pure and mixed phases. Worm phases formed gels that underwent a thermo-reversible degelation and morphological transition to spheres (or spheres and vesicles) upon heating. Postsynthesis, the pPFBMA cores were modified through thiol-para-fluoro substitution reactions in ethanol using 1,8-diazabicyclo[5.4.0]undec-7-ene as the base. For monothiols, conversions were 64% (1-octanethiol) and 94% (benzyl mercaptan). Spherical and worm-shaped nano-objects were core cross-linked using 1,8-octanedithiol, which prevented their dissociation in nonselective solvents. For a temperature-responsive worm sample, cross-linking additionally resulted in the loss of the temperature-triggered morphological transition. The use of the reactive monomer PFBMA in PISA formulations presents a simple method to prepare well-defined nano-objects similar to those produced with nonreactive monomers (e.g., benzyl methacrylate) and to retain morphologies independent of solvent and temperature.


Assuntos
Álcoois Benzílicos/química , Técnicas de Química Sintética/métodos , Metacrilatos/química , Nanopartículas/química , Polimerização , Polímeros/química , Compostos de Sulfidrila/química , Compostos Bicíclicos Heterocíclicos com Pontes/química , Microscopia Eletrônica de Transmissão e Varredura , Modelos Químicos , Estrutura Molecular , Nanopartículas/ultraestrutura , Polímeros/síntese química , Temperatura , Temperatura de Transição
11.
J Vasc Surg ; 67(2): 649-655, 2018 02.
Artigo em Inglês | MEDLINE | ID: mdl-29157681

RESUMO

In high-risk patients with diseases of the ascending aorta, endovascular repair might be a therapeutic alternative to surgical repair. We developed a combined access route with transapical and transfemoral externalization of the wire and report the operative technique as well as our initial experience of six patients treated with this method. Improved wire control resulted in precise deployment of endovascular prostheses, respecting the integrity of the coronary ostia and the supra-aortic vessels. Procedural success was 100%, and follow-up until 32 months postoperatively showed no need for reintervention or mortality. However, long-term results of the presented technique are still unknown.


Assuntos
Falso Aneurisma/cirurgia , Aorta/cirurgia , Aneurisma Aórtico/cirurgia , Dissecção Aórtica/cirurgia , Ruptura Aórtica/cirurgia , Implante de Prótese Vascular/métodos , Cateterismo Periférico/métodos , Procedimentos Endovasculares/métodos , Artéria Femoral , Idoso , Dissecção Aórtica/diagnóstico por imagem , Falso Aneurisma/diagnóstico por imagem , Aorta/diagnóstico por imagem , Aneurisma Aórtico/diagnóstico por imagem , Ruptura Aórtica/diagnóstico por imagem , Aortografia/métodos , Prótese Vascular , Implante de Prótese Vascular/efeitos adversos , Implante de Prótese Vascular/instrumentação , Cateterismo Periférico/efeitos adversos , Angiografia por Tomografia Computadorizada , Procedimentos Endovasculares/efeitos adversos , Procedimentos Endovasculares/instrumentação , Feminino , Artéria Femoral/diagnóstico por imagem , Humanos , Masculino , Pessoa de Meia-Idade , Punções , Resultado do Tratamento
12.
Perfusion ; 33(5): 390-400, 2018 07.
Artigo em Inglês | MEDLINE | ID: mdl-29457560

RESUMO

INTRODUCTION: Prophylactic intra-aortic balloon counterpulsation (pIABC) is recommended for high-risk patients undergoing coronary artery bypass grafting (CABG) surgery. Criteria for high-risk patients benefiting from pIABC are unclear. This study aimed to specifically describe the effect of pIABC on outcomes of patients with acute myocardial infarction (AMI) undergoing CABG. METHODS: In 178 of 484 AMI patients (non-ST-segment elevation myocardial infarction [NSTEMI] or ST-segment elevation myocardial infarction [STEMI] ≤5 days before surgery) without cardiogenic shock who underwent CABG between 2008 and 2013, pIABC was initiated preoperatively. After propensity score matching, the outcomes of 400 patients were analyzed (pIABC: 150; Control: 250). RESULTS: After propensity score matching, baseline and operative characteristics were balanced between the groups except for a higher rate of patients with a left ventricular ejection fraction (LVEF)≤30% in the pIABC group (26% vs. Control: 13%; p=0.032). Seven point two percent (7.2%) of the control patients received an IABP intraoperatively or postoperatively. Postoperative extracorporeal life support (ECLS) was only needed in the control group (1.2% vs. 0%; p=0.01). Postoperative plasma curves of troponin I, creatine kinase (CK) and creatine kinase isoform MB (CK-MB) levels were reduced in the pIABC group compared with the control group. In-hospital mortality was reduced in the pIABC group (3.3% vs. control: 6.4%; p=0.18). After multivariate adjustment for other preoperative risk factors, pIABC was significantly protective concerning in-hospital mortality (HR 0.56; 95%-CI 0.023-0.74; p=0.021). Mortality (pIABC vs. control) was more affected in patients with preoperative LVEF≤30% (2/36 (5.6%) vs. 6/31 (19%); heart rate (HR) 0.25; 95%-CI 0.046-1.3; p=0.13) compared with LVEF>30% (3/114 (2.6%) vs. 10/219 (4.6%); HR 0.56; 95%-CI 0.15-2.1; p=0.55). Long-term survival did not differ between the groups. CONCLUSIONS: pIABC in CABG for AMI is associated with reduced perioperative cardiac injury and in-hospital mortality. Long-term survival is not affected.


Assuntos
Ponte de Artéria Coronária/efeitos adversos , Balão Intra-Aórtico/métodos , Infarto do Miocárdio/cirurgia , Idoso , Ponte de Artéria Coronária/métodos , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Infarto do Miocárdio/sangue , Revascularização Miocárdica/efeitos adversos , Revascularização Miocárdica/métodos , Cuidados Pré-Operatórios/métodos , Estudos Retrospectivos , Resultado do Tratamento
13.
Perfusion ; 33(1): 53-61, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-28795615

RESUMO

INTRODUCTION: Pulmonary endarterectomy (PEA) is the most effective treatment available for chronic thromboembolic pulmonary hypertension (CTEPH). Patient selection, surgical technique and perioperative management have improved patient outcomes, which are traditionally linked to surgical and center experience. However, optimal perfusion care has not been well defined. The goal of the international survey was to better characterize the contemporary perfusion management of PEA and highlight similarities and controversies. METHOD: The combined caseload of 15 participating centers was 5,066 cases. Topics queried included materials and types of cardiopulmonary bypass (CPB) equipment, choice of prime, fluid management, deep hypothermia strategy, temperature management, treatment of acid-base abnormalities and intraoperative hematocrit as well as anticoagulation management for heparin-induced thrombocytopenia. CONCLUSION: Our assessment could provide a base for further advancement and may help design future studies to elucidate the impact of perfusion in this challenging field.


Assuntos
Endarterectomia/métodos , Pulmão/fisiopatologia , Perfusão/métodos , Humanos , Inquéritos e Questionários , Resultado do Tratamento
14.
Stroke ; 48(10): 2769-2775, 2017 10.
Artigo em Inglês | MEDLINE | ID: mdl-28916664

RESUMO

BACKGROUND AND PURPOSE: The optimal operative strategy in patients with severe carotid artery disease undergoing coronary artery bypass grafting (CABG) is unknown. We sought to investigate the safety and efficacy of synchronous combined carotid endarterectomy and CABG as compared with isolated CABG. METHODS: Patients with asymptomatic high-grade carotid artery stenosis ≥80% according to ECST (European Carotid Surgery Trial) ultrasound criteria (corresponding to ≥70% NASCET [North American Symptomatic Carotid Endarterectomy Trial]) who required CABG surgery were randomly assigned to synchronous carotid endarterectomy+CABG or isolated CABG. To avoid unbalanced prognostic factor distributions, randomization was stratified by center, age, sex, and modified Rankin Scale. The primary composite end point was the rate of stroke or death at 30 days. RESULTS: From 2010 to 2014, a total of 129 patients were enrolled at 17 centers in Germany and the Czech Republic. Because of withdrawal of funding after insufficient recruitment, enrolment was terminated early. At 30 days, the rate of any stroke or death in the intention-to-treat population was 12/65 (18.5%) in patients receiving synchronous carotid endarterectomy+CABG as compared with 6/62 (9.7%) in patients receiving isolated CABG (absolute risk reduction, 8.8%; 95% confidence interval, -3.2% to 20.8%; PWALD=0.12). Also for all secondary end points at 30 days and 1 year, there was no evidence for a significant treatment-group effect although patients undergoing isolated CABG tended to have better outcomes. CONCLUSIONS: Although our results cannot rule out a treatment-group effect because of lack of power, a superiority of the synchronous combined carotid endarterectomy+CABG approach seems unlikely. Five-year follow-up of patients is still ongoing. CLINICAL TRIAL REGISTRATION: URL: https://www.controlled-trials.com. Unique identifier: ISRCTN13486906.


Assuntos
Estenose das Carótidas/diagnóstico , Estenose das Carótidas/cirurgia , Ponte de Artéria Coronária/normas , Endarterectomia das Carótidas/normas , Segurança do Paciente/normas , Idoso , Estenose das Carótidas/epidemiologia , Ponte de Artéria Coronária/efeitos adversos , Endarterectomia das Carótidas/efeitos adversos , Feminino , Seguimentos , Humanos , Masculino , Pessoa de Meia-Idade , Resultado do Tratamento
15.
Macromol Rapid Commun ; 38(1)2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27900822

RESUMO

Polymerization-induced self-assembly (PISA) is an extremely versatile method for the in situ preparation of soft-matter nanoparticles of defined size and morphologies at high concentrations, suitable for large-scale production. Recently, certain PISA-prepared nanoparticles have been shown to exhibit reversible polymorphism ("shape-shifting"), typically between micellar, worm-like, and vesicular phases (order-order transitions), in response to external stimuli including temperature, pH, electrolytes, and chemical modification. This review summarises the literature to date and describes molecular requirements for the design of stimulus-responsive nano-objects. Reversible pH-responsive behavior is rationalised in terms of increased solvation of reversibly ionized groups. Temperature-triggered order-order transitions, conversely, do not rely on inherently thermo-responsive polymers, but are explained based on interfacial LCST or UCST behavior that affects the volume fractions of the core and stabilizer blocks. Irreversible morphology transitions, on the other hand, can result from chemical post-modification of reactive PISA-made particles. Emerging applications and future research directions of this "smart" nanoparticle behavior are reviewed.


Assuntos
Nanopartículas/química , Polimerização , Polímeros/química , Eletrólitos/química , Concentração de Íons de Hidrogênio , Estrutura Molecular , Polímeros/síntese química , Temperatura
16.
Macromol Rapid Commun ; 38(2)2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27859900

RESUMO

(Co)Polymers containing pentafluorophenylacetylene (F5 PA) have been prepared for the first time mediated by [Rh(nbd)Cl]2 /NEt3 to give materials with properties typical of poly(phenylacetylene)s prepared with this catalyst/co-catalyst combination. It is demonstrated that the F5 PA repeat units in these new (co)polymers serve as convenient reactive species for post-polymerization modification with thiols via para-fluoro aromatic nucleophilic substitution reactions to give an entirely new family of novel thioether-functional polyene materials accompanied by absorption maxima shifts of up to 130 nm. Finally, the electrochemical properties of these new fluorinated polyene materials are briefly examined and the distinct difference in behavior of the F5 PA homopolymer versus polyphenylacetylene, copolymers, and functional derivatives is highlighted.


Assuntos
Técnicas Eletroquímicas , Hidrocarbonetos Fluorados/química , Hidrocarbonetos Fluorados/síntese química , Polienos/química , Polienos/síntese química , Estrutura Molecular , Polimerização
17.
Neurosurg Rev ; 38(2): 273-81; discussion 281, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25516093

RESUMO

The commonly used Borden and Cognard classification systems for the prediction of clinical behavior of cranial dural arteriovenous shunts focus on the venous drainage, particularly the presence of leptomeningeal venous drainage, and on the direction of flow, particularly the presence of retrograde flow. In addition, the latter includes ectasia and spinal drainage as criteria of two distinct grades. However, none of the above classifications (a) differentiates direct from exclusive leptomeningeal venous drainage, (b) considers cortical venous congestion as a factor potentially associated with an aggressive clinical course, and (c) anticipates ectasia in shunts with a mixed dural-cortical venous drainage (type 2). In this study, we analyzed the angiographic images of 107 consecutive patients having a cranial dural arteriovenous fistula with leptomeningeal venous drainage, based on a newly developed scheme. This scheme, symbolized with the acronym "DES," groups the dural shunts according to three factors: directness and exclusivity of leptomeningeal venous drainage and signs of venous strain. According to the combination of the three factors, eight different groups were distinguished. All analyzed cases could be assigned to one of these groups. Directness of leptomeningeal venous drainage expresses the exact site of the shunt (bridging vein vs sinus wall), whereas exclusivity expresses venous outlet restrictions. All bridging vein shunts had a direct leptomeningeal venous drainage. Almost all bridging vein shunts and all "isolated" sinus shunts had an exclusive leptomeningeal venous drainage. Venous strain, manifested as ectasia and/or congestion, denotes the decompensation of the cerebral venous system due to the shunt reflux. The comparison of the presented concept with the currently used classifications highlighted the advantages of the former and the weaknesses of the latter.


Assuntos
Malformações Vasculares do Sistema Nervoso Central/patologia , Angiografia Cerebral , Veias Cerebrais/patologia , Drenagem , Encéfalo/irrigação sanguínea , Malformações Vasculares do Sistema Nervoso Central/cirurgia , Angiografia Cerebral/métodos , Veias Cerebrais/cirurgia , Cavidades Cranianas/patologia , Feminino , Humanos , Masculino
18.
Neurosurg Rev ; 38(2): 253-63; discussion 263-4, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25468011

RESUMO

We reviewed the anatomy and embryology of the bridging and emissary veins aiming to elucidate aspects related to the cranial dural arteriovenous fistulae. Data from relevant articles on the anatomy and embryology of the bridging and emissary veins were identified using one electronic database, supplemented by data from selected reference texts. Persisting fetal pial-arachnoidal veins correspond to the adult bridging veins. Relevant embryologic descriptions are based on the classic scheme of five divisions of the brain (telencephalon, diencephalon, mesencephalon, metencephalon, myelencephalon). Variation in their exact position and the number of bridging veins is the rule and certain locations, particularly that of the anterior cranial fossa and lower posterior cranial fossa are often neglected in prior descriptions. The distal segment of a bridging vein is part of the dural system and can be primarily involved in cranial dural arteriovenous lesions by constituting the actual site of the shunt. The veins in the lamina cribriformis exhibit a bridging-emissary vein pattern similar to the spinal configuration. The emissary veins connect the dural venous system with the extracranial venous system and are often involved in dural arteriovenous lesions. Cranial dural shunts may develop in three distinct areas of the cranial venous system: the dural sinuses and their interfaces with bridging veins and emissary veins. The exact site of the lesion may dictate the arterial feeders and original venous drainage pattern.


Assuntos
Malformações Vasculares do Sistema Nervoso Central/embriologia , Veias Cerebrais/anatomia & histologia , Fossa Craniana Anterior/anatomia & histologia , Cavidades Cranianas/anatomia & histologia , Dura-Máter/embriologia , Crânio/anatomia & histologia , Malformações Vasculares do Sistema Nervoso Central/patologia , Fossa Craniana Anterior/embriologia , Dura-Máter/anatomia & histologia , Humanos , Crânio/embriologia
19.
Soft Matter ; 10(31): 5787-96, 2014 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-24975501

RESUMO

The direct synthesis of methacrylic-based soft polymeric nanoparticles via reversible addition-fragmentation chain transfer dispersion polymerization (RAFTDP) is described. The use of poly[2-(dimethylamino)ethyl methacrylate]s, of varying average degree of polymerization (X¯n), as the stabilizing blocks for the RAFTDP of 3-phenylpropyl methacrylate (PPMA) in ethanol at 70 °C, at various total solids contents, yielded the full spectrum of self-assembled nanoparticles (spherical and worm aggregates and polymersomes). We also demonstrate that nanoparticle morphology can be tuned simply by controlling temperature. This is especially evident in the case of worm aggregates undergoing a thermoreversible transition to spherical species - a process that is accompanied by a macroscopic degelation-gelation process.

20.
Crit Care ; 18(6): 662, 2014 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-25673235

RESUMO

In the previous issue of Critical Care, Yu and colleagues report increased morbidity and mortality in patients after myocardial infarction undergoing prophylactic intra-aortic balloon pump support before coronary artery bypass graft surgery. The impact of prophylactic intra-aortic balloon pump implantation before coronary artery bypass graft therapy still is controversially debated. However, Yu and colleagues emphasize further discussion and substantiate the need for a prospective randomized controlled trial on this subject.


Assuntos
Ponte de Artéria Coronária , Balão Intra-Aórtico , Infarto do Miocárdio/terapia , Cuidados Pré-Operatórios/métodos , Feminino , Humanos , Masculino
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