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1.
Chemistry ; 28(68): e202202621, 2022 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-36005885

RESUMEN

An important aspect within zeolite synthesis is to make fully tunable framework materials with controlled aluminium distribution. A major challenge in characterising these zeolites at operating conditions is the presence of water. In this work, we investigate the effect of hydration on the 27 Al NMR parameters of the ultracrystalline K,Na-compensated aluminosilicate JBW zeolite using experimental and computational techniques. The JBW framework, with Si/Al ratio of 1, is an ideal benchmark system as a stepping stone towards more complicated zeolites. The presence and mobility of water and extraframework species directly affect NMR fingerprints. Excellent agreement between theoretical and experimental spectra is obtained provided dynamic methods are employed with hydrated structural models. This work shows how NMR is instrumental in characterising aluminium distributions in zeolites at operating conditions.

2.
Phys Rev Lett ; 127(3): 033602, 2021 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-34328761

RESUMEN

We propose a single-atom, cavity quantum electrodynamics system, compatible with recently demonstrated, fiber-integrated micro- and nanocavity setups, for the on-demand production of optical number-state, 0N-state, and binomial-code-state pulses. The scheme makes use of Raman transitions within an entire atomic ground-state hyperfine level and operates with laser and cavity fields detuned from the atomic transition by much more than the excited-state hyperfine splitting. This enables reduction of the dynamics to that of a simple, cavity-damped Tavis-Cummings model with the collective spin determined by the total angular momentum of the ground hyperfine level.

3.
Faraday Discuss ; 225: 301-323, 2021 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-33118592

RESUMEN

To exploit the full potential of metal-organic frameworks as solid adsorbents in water-adsorption applications, many challenges remain to be solved. A more fundamental insight into the properties of the host material and the influence that water exerts on them can be obtained by performing molecular simulations. In this work, the prototypical flexible MIL-53(Al) framework is modelled using advanced molecular dynamics simulations. For different water loadings, the presence of water is shown to affect the relative stability of MIL-53(Al), triggering a phase transition from the narrow-pore to the large-pore phase at the highest considered loading. Furthermore, the effect of confinement on the structural organisation of the water molecules is also examined for different pore volumes of MIL-53(Al). For the framework itself, we focus on the thermal conductivity, as this property plays a decisive role in the efficiency of adsorption-based technologies, due to the energy-intensive adsorption and desorption cycles. To this end, the heat transfer characteristics of both phases of MIL-53(Al) are studied, demonstrating a strong directional dependence for the thermal conductivity.

4.
J Am Chem Soc ; 142(6): 3174-3183, 2020 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-31971786

RESUMEN

The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of α-pinene oxide. This reaction is particularly sensitive to the Brønsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Brønsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Brønsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity.

5.
J Am Chem Soc ; 141(37): 14823-14842, 2019 09 18.
Artículo en Inglés | MEDLINE | ID: mdl-31464134

RESUMEN

A systematic molecular level and spectroscopic investigation is presented to show the cooperative role of Brønsted acid and Lewis acid sites in zeolites for the conversion of methanol. Extra-framework alkaline-earth metal containing species and aluminum species decrease the number of Brønsted acid sites, as protonated metal clusters are formed. A combined experimental and theoretical effort shows that postsynthetically modified ZSM-5 zeolites, by incorporation of extra-framework alkaline-earth metals or by demetalation with dealuminating agents, contain both mononuclear [MOH]+ and double protonated binuclear metal clusters [M(µ-OH)2M]2+ (M = Mg, Ca, Sr, Ba, and HOAl). The metal in the extra-framework clusters has a Lewis acid character, which is confirmed experimentally and theoretically by IR spectra of adsorbed pyridine. The strength of the Lewis acid sites (Mg > Ca > Sr > Ba) was characterized by a blue shift of characteristic IR peaks, thus offering a tool to sample Lewis acidity experimentally. The incorporation of extra-framework Lewis acid sites has a substantial influence on the reactivity of propene and benzene methylations. Alkaline-earth Lewis acid sites yield increased benzene methylation barriers and destabilization of typical aromatic intermediates, whereas propene methylation routes are less affected. The effect on the catalytic function is especially induced by the double protonated binuclear species. Overall, the extra-framework metal clusters have a dual effect on the catalytic function. By reducing the number of Brønsted acid sites and suppressing typical catalytic reactions in which aromatics are involved, an optimal propene selectivity and increased lifetime for methanol conversion over zeolites is obtained. The combined experimental and theoretical approach gives a unique insight into the nature of the supramolecular zeolite catalyst for methanol conversion which can be meticulously tuned by subtle interplay of Brønsted and Lewis acid sites.

6.
Foot Ankle Surg ; 20(3): 166-9, 2014 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-25103702

RESUMEN

BACKGROUND: Reconstruction in the foot and ankle region is challenging. This study aimed to quantify objective sensation return when a sensate medial plantar flap is used for like-for-like reconstruction of foot and ankle defects. METHODS: Two-point discrimination (2PD) was assessed in flap and normal tissue at a minimum of 1 year post-operatively. A paired T-test assessed for significance. RESULTS: 8 patients were included. Mean 2PD in normal tissue and flap was 29 mm (SD: 11.9) and 33 mm (SD: 9.97) respectively with no statistically significant difference between the two (two-tailed p-value: 0.1898). Mean age was 53.2 years (range: 15-84). There was no statistically significant correlation between age and 2PD in flap tissue (r=0.6, p=0.15). CONCLUSIONS: This is the largest case series of its kind. Our results suggest that sensation in medial plantar flaps can return to near normal and demonstrate the important role the medial plantar flap plays in soft tissue reconstruction in this region.


Asunto(s)
Enfermedades del Pie/patología , Enfermedades del Pie/cirugía , Procedimientos de Cirugía Plástica , Sensación , Colgajos Quirúrgicos , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Femenino , Estudios de Seguimiento , Enfermedades del Pie/fisiopatología , Humanos , Masculino , Persona de Mediana Edad , Recuperación de la Función , Estudios Retrospectivos , Factores de Tiempo , Resultado del Tratamiento , Soporte de Peso , Adulto Joven
7.
J Chem Theory Comput ; 20(2): 513-531, 2024 Jan 23.
Artículo en Inglés | MEDLINE | ID: mdl-38157404

RESUMEN

Vibrational spectroscopy is an omnipresent spectroscopic technique to characterize functional nanostructured materials such as zeolites, metal-organic frameworks (MOFs), and metal-halide perovskites (MHPs). The resulting experimental spectra are usually complex, with both low-frequency framework modes and high-frequency functional group vibrations. Therefore, theoretically calculated spectra are often an essential element to elucidate the vibrational fingerprint. In principle, there are two possible approaches to calculate vibrational spectra: (i) a static approach that approximates the potential energy surface (PES) as a set of independent harmonic oscillators and (ii) a dynamic approach that explicitly samples the PES around equilibrium by integrating Newton's equations of motions. The dynamic approach considers anharmonic and temperature effects and provides a more genuine representation of materials at true operating conditions; however, such simulations come at a substantially increased computational cost. This is certainly true when forces and energy evaluations are performed at the quantum mechanical level. Molecular dynamics (MD) techniques have become more established within the field of computational chemistry. Yet, for the prediction of infrared (IR) and Raman spectra of nanostructured materials, their usage has been less explored and remain restricted to some isolated successes. Therefore, it is currently not a priori clear which methodology should be used to accurately predict vibrational spectra for a given system. A comprehensive comparative study between various theoretical methods and experimental spectra for a broad set of nanostructured materials is so far lacking. To fill this gap, we herein present a concise overview on which methodology is suited to accurately predict vibrational spectra for a broad range of nanostructured materials and formulate a series of theoretical guidelines to this purpose. To this end, four different case studies are considered, each treating a particular material aspect, namely breathing in flexible MOFs, characterization of defects in the rigid MOF UiO-66, anharmonic vibrations in the metal-halide perovskite CsPbBr3, and guest adsorption on the pores of the zeolite H-SSZ-13. For all four materials, in their guest- and defect-free state and at sufficiently low temperatures, both the static and dynamic approach yield qualitatively similar spectra in agreement with experimental results. When the temperature is increased, the harmonic approximation starts to fail for CsPbBr3 due to the presence of anharmonic phonon modes. Also, the spectroscopic fingerprints of defects and guest species are insufficiently well predicted by a simple harmonic model. Both phenomena flatten the potential energy surface (PES), which facilitates the transitions between metastable states, necessitating dynamic sampling. On the basis of the four case studies treated in this Review, we can propose the following theoretical guidelines to simulate accurate vibrational spectra of functional solid-state materials: (i) For nanostructured crystalline framework materials at low temperature, insights into the lattice dynamics can be obtained using a static approach relying on a few points on the PES and an independent set of harmonic oscillators. (ii) When the material is evaluated at higher temperatures or when additional complexity enters the system, e.g., strong anharmonicity, defects, or guest species, the harmonic regime breaks down and dynamic sampling is required for a correct prediction of the phonon spectrum. These guidelines and their illustrations for prototype material classes can help experimental and theoretical researchers to enhance the knowledge obtained from a lattice dynamics study.

8.
Inorg Chem ; 49(1): 157-73, 2010 Jan 04.
Artículo en Inglés | MEDLINE | ID: mdl-19957927

RESUMEN

Synthetic approaches based on the direct borylation of ferrocene by BBr(3), followed by boryl substituent modification, or on the lithiation of ferrocene derivatives and subsequent quenching with the electrophile FBMes(2), have given access to a range of ferrocene derivatized Lewis acids with which to conduct a systematic study of fluoride and cyanide binding. In particular, the effects of borane electrophilicity, net charge, and ancillary ligand electronics/cooperativity on the binding affinities for these anions have been probed by a combination of NMR, IR, mass spectrometric, electrochemical, crystallographic, and UV-vis titration measurements. In this respect, modifications made at the para position of the boron-bound aromatic substituents exert a relatively minor influence on the binding constants for both fluoride and cyanide, as do the electronic properties of peripheral substituents at the 1'- position (even for cationic groups). By contrast, the influence of a CH(2)NMe(3)(+) substituent in the 2- position is found to be much more pronounced (by >3 orders of magnitude), reflecting, at least in part, the possibility in solution for an additional binding component utilizing the hydrogen bond donor capabilities of the methylene CH(2) group. While none of the systems examined in the current study display any great differentiation between the binding of F(-) and CN(-) (and indeed some, such as FcBMes(2), bind both anions with equal affinity within experimental error), much weaker boronic ester Lewis acids will bind fluoride (but give a negative response for cyanide). Thus, by the incorporation of an irreversible redox-matched organic dye, a two-component [BMes(2)/B(OR)(2)] dosimeter system can be developed capable of colorimetrically signaling the presence of fluoride and cyanide in organic solution by Boolean AND/NOT logic.

9.
J Burn Care Res ; 41(6): 1240-1252, 2020 11 30.
Artículo en Inglés | MEDLINE | ID: mdl-32479625

RESUMEN

Although many reviews describe significant advances in burn care, no studies have yet examined why these papers had such profound impact. Our objective was to identify the most highly cited, as well as the most clinically influential studies in burns, and describe their characteristics, to inform future research in the field. Web of Science was searched using keywords related to burns to identify the 100 most-cited burns papers. Study design, year and journal of publication, and subject of the paper were recorded. A mixed-methods approach was used to identify papers in burn research leading to change in clinical practice. Characteristics of these papers were compared with identify any factors predictive of future citations or clinical influence. The 100 highly cited papers were cited between 159 and 907 times. There was no correlation between total citations and journal impact factor, year of publication, or subject area. Level of evidence did not predict future citations or influence, but may be influenced by evolving research standards. Of 23 clinically influential studies, 6 were not among 100 most-cited. Using papers only from the 100 most-cited list was not sufficient to identify leading researchers in burns. Citation analysis is a beneficial, however not alone sufficient to identify landmark papers, particularly for multidisciplinary fields such as burns.


Asunto(s)
Bibliometría , Investigación Biomédica , Quemaduras/terapia , Publicaciones Periódicas como Asunto , Humanos
10.
J Phys Chem Lett ; 11(23): 10060-10066, 2020 Dec 03.
Artículo en Inglés | MEDLINE | ID: mdl-33179925

RESUMEN

The dynamic nature of the copper cations acting as active sites for selective catalytic reduction of nitrogen oxides with ammonia is investigated using a combined theoretical and spectroscopic approach. Ab initio molecular dynamics simulations of Cu-CHA catalysts in contact with reactants and intermediates at realistic operating conditions show that only ammonia is able to release Cu+ and Cu2+ cations from their positions coordinated to the zeolite framework, forming mobile Cu+(NH3)2 and Cu2+(NH3)4 complexes that migrate to the center of the cavity. Herein, we give evidence that such mobilization of copper cations modifies the vibrational fingerprint in the 800-1000 cm-1 region of the IR spectra. Bands associated with the lattice asymmetric T-O-T vibrations are perturbed by the presence of coordinated cations, and allow one to experimentally follow the dynamic reorganization of the active sites at operating conditions.

11.
Surg J (N Y) ; 6(1): e42-e46, 2020 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-32133414

RESUMEN

Introduction The main postoperative complication of free flaps is perfusion compromise. Urgent intervention is critical to increase the chances of flap survival. Invasive flap perfusion monitoring with direct blood flow feedback through the Cook-Swartz Doppler probe could enable earlier detection of perfusion complications. Materials and Methods Between 2012 and 2016, 35 patients underwent breast reconstruction or defect coverage after trauma with a deep inferior epigastric perforator, anterolateral thigh, transverse musculocutaneous gracilis, gracilis, or latissimus dorsi flap in our department. All flaps were monitored with a Cook-Swartz probe for 10 days postoperatively. The 20 MHz probe was placed around the arterial-venous anastomosis. A flap monitoring protocol was established for standardized surveillance of postoperative perfusion. In the event of probe signal loss, immediate surgical revision was initiated. Results Signal loss was detected in 8 of the 35 cases. On return to the operating room, six were found to be true positives (relevant disruption of flap perfusion) and two were false positives (due to Doppler probe displacement). There were also two false negatives, resulting in a slowly progressive partial flap loss. Flap perfusion was restored in three of the six cases (50%) identified by the probe. Following surgical intervention, three of the six cases had persistent problems with perfusion, resulting in two total flap losses and one partial flap necrosis leading to an overall 5.7% total flap loss. Conclusion Postoperative flap perfusion surveillance is a complex matter. Surgical experience is often helpful but not always reliable. The costs, false-positive, and false-negative rates associated with invasive perfusion monitoring with Cook-Swartz probe make it most appropriate for buried flaps. Level of Evidence This is an original work.

12.
PLoS One ; 14(9): e0222466, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31513671

RESUMEN

The aim of this study was to evaluate the post-activation potentiation (PAP) effects following eccentric overload (EOL) and traditional weightlifting (TW) exercise on standing long jump (SLJ), countermovement jump (CMJ), and 5 m sprint acceleration performance. Ten male athletes were involved in a randomized, crossover study. The subjects performed 3 sets of 6 repetitions of EOL or TW half squat exercise followed by SLJ, CMJ, and 5 m sprint tests at 1 min, 3 min and 7 min, in separate sessions using a randomized order. Bayes factor (BF10) was reported to show the strength of the evidence. Differences were found using EOL for SLJ distance at 3 min (BF10 = 7.24, +8%), and 7 min (BF10 = 19.5, +7%), for CMJ at 3 min (BF10 = 3.25, +9%), and 7 min (BF10 = 4.12, +10.5%). Differences were found using TW exercise for SLJ at 3 min (BF10 = 3.88, +9%), and 7 min (BF10 = 12.4, +9%), CMJ at 3 min (BF10 = 7.42, +9.5%), and 7 min (BF10 = 12.4, +12%). No meaningful differences were found between EOL and TW exercises for SLJ (BF10 = 0.33), CMJ (BF10 = 0.27), and 5 m sprint (BF10 = 0.22). In conclusion, EOL and TW exercises acutely increase SLJ and CMJ, but not 5 m sprint performance. The PAP time window was found between 3 min and 7 min using both protocols. This study did not find differences between EOL and TW exercises, and so both methodologies can be used to stimulate a PAP response.


Asunto(s)
Rendimiento Atlético/fisiología , Ejercicio Pliométrico/métodos , Entrenamiento de Fuerza/métodos , Atletas , Estudios Cruzados , Humanos , Masculino , Fuerza Muscular/fisiología , Músculo Esquelético/fisiología , Carrera/fisiología , Levantamiento de Peso/fisiología , Adulto Joven
13.
J Plast Surg Hand Surg ; 53(2): 97-104, 2019 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-30654678

RESUMEN

Academic output is just one aspect of a successful career as a plastic surgeon. However, for those with a strong interest in academia, the academic output of a department will likely be a key factor when deciding how to rank jobs. The aim of this study was to quantify and rank the academic output of plastic surgery units across the UK and Ireland. The Institute for Scientific Information (ISI) Web of Science Bibliometric analysis tool was used to collate cumulative (1950-2016), 10 year (2006-2016) and 3 years (2013-2015) research output data for plastic surgery units in the UK and Ireland. Sixty-six plastic surgery units were identified. Departments were ranked for each time period according to the number of papers produced, number of citations (Nc) and h-index (a measure of the impact of scientific output). The top 3 departments for number of papers in the last 10 years were The Royal Free Hospital, London (226) Broomfield Hospital, Chelmsford (218), and Morriston Hospital and Swansea (188). The top 3 for h-number were The Royal Free Hospital (21) Wythenshawe Hospital, Manchester (18) and Morriston Hospital (17). Academic output varies across plastic surgery units in the UK and Ireland. A number of departments have consistently maintained high academic outputs across the years and will be of interest to surgeons hoping to pursue a career in academia.


Asunto(s)
Unidades Hospitalarias/estadística & datos numéricos , Edición/estadística & datos numéricos , Cirugía Plástica , Bibliometría , Humanos , Irlanda , Reino Unido
14.
Radiother Oncol ; 141: 181-187, 2019 12.
Artículo en Inglés | MEDLINE | ID: mdl-31493904

RESUMEN

BACKGROUND AND PURPOSE: To assess the diagnostic accuracy and inter-observer agreement of T2-weighted (T2W) and diffusion-weighted (DW) magnetic resonance imaging (MRI) for mapping intra-prostatic tumour lesions (IPLs) for the purpose of focal dose-escalation in prostate cancer radiotherapy. MATERIALS AND METHODS: Twenty-six men selected for radical treatment with radiotherapy were recruited prospectively and underwent pre-treatment T2W+DW-MRI and 5 mm spaced transperineal template-guided mapping prostate biopsies (TTMPB). A 'traffic-light' system was used to score both data sets. Radiologically suspicious lesions measuring ≥0.5 cm3 were classified as red; suspicious lesions 0.2-0.5 cm3 or larger lesions equivocal for tumour were classified as amber. The histopathology assessment combined pathological grade and tumour length on biopsy (red = ≥4 mm primary Gleason grade 4/5 or ≥6 mm primary Gleason grade 3). Two radiologists assessed the MRI data and inter-observer agreement was measured with Cohens' Kappa co-efficient. RESULTS: Twenty-five of 26 men had red image-defined IPLs by both readers, 24 had red pathology-defined lesions. There was a good correlation between lesions ≥0.5 cm3 classified "red" on imaging and "red" histopathology in biopsies (Reader 1: r = 0.61, p < 0.0001, Reader 2: r = 0.44, p = 0.03). Diagnostic accuracy for both readers for red image-defined lesions was sensitivity 85-86%, specificity 93-98%, positive predictive value (PPV) 79-92% and negative predictive value (NPV) 96%. Inter-observer agreement was good (Cohen's Kappa 0.61). CONCLUSIONS: MRI is accurate for mapping clinically significant prostate cancer; diffusion-restricted lesions ≥0.5 cm3 can be confidently identified for radiation dose boosting.


Asunto(s)
Imagen de Difusión por Resonancia Magnética/métodos , Biopsia Guiada por Imagen/métodos , Neoplasias de la Próstata/radioterapia , Radioterapia de Intensidad Modulada/métodos , Anciano , Humanos , Masculino , Persona de Mediana Edad , Estudios Prospectivos , Neoplasias de la Próstata/diagnóstico por imagen , Neoplasias de la Próstata/patología , Dosificación Radioterapéutica
15.
Clin Obes ; 8(3): 184-190, 2018 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-29493116

RESUMEN

Insulin-like growth factor binding protein 2 (IGFBP-2) may represent a critical link between body composition and insulin sensitivity. We investigated the relationship between circulating IGFBP-2 levels, body composition, insulin sensitivity, energy intake and physical activity in children with obesity. Children were recruited via the Weight Management Service at the Royal Children's Hospital, Melbourne, as part of the Childhood Overweight BioRepository of Australia (COBRA). Comprehensive anthropometric, biochemical and environmental data were collected and compared to serum IGFBP-2 levels (measured by enzyme-linked immunosorbent assay). Multiple regression modelling was used to assess the influence of circulating IGFBP-2 levels on anthropometric and biochemical measures. One hundred and ninety-four children were included in this study (46% male). Circulating IGFBP-2 negatively correlated with age, anthropometric measures, blood pressure and insulin concentration. Positive associations were observed between insulin sensitivity index-homeostasis model assessment (ISI-HOMA) and serum IGFBP-2. In multiple regression modelling, IGFBP-2 significantly contributes to variance in systolic blood pressure (-19%, P < 0.05), circulating triglycerides (-16%, P < 0.05) and ISI-HOMA (18%, P < 0.05). No associations were observed between dietary energy intake or physical activity and IGFBP-2 levels. Circulating IGFBP-2 levels in children with obesity correlate inversely with body mass and markers of metabolic dysfunction, and positively with insulin sensitivity. These findings suggest that reduced levels of IGFBP-2 may play an important role in the pathogenesis of obesity complications in early life.


Asunto(s)
Índice de Masa Corporal , Proteínas Portadoras/sangre , Resistencia a la Insulina , Proteína 2 de Unión a Factor de Crecimiento Similar a la Insulina/sangre , Insulina/metabolismo , Obesidad/complicaciones , Adolescente , Factores de Edad , Australia , Glucemia/metabolismo , Presión Sanguínea , Composición Corporal , Niño , Ensayo de Inmunoadsorción Enzimática , Femenino , Humanos , Proteína 2 de Unión a Factor de Crecimiento Similar a la Insulina/deficiencia , Masculino , Obesidad/sangre , Análisis de Regresión , Factores de Riesgo , Triglicéridos/sangre
16.
J Phys Chem C Nanomater Interfaces ; 122(5): 2734-2746, 2018 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-29449906

RESUMEN

In this work, mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed, allowing for the identification of all IR-active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable determination of the theoretical Raman spectrum of the closed- and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed- and large-pore phases, indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.

18.
J Plast Reconstr Aesthet Surg ; 69(12): 1614-1620, 2016 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-27777176

RESUMEN

BACKGROUND: Despite numerous studies over the past few decades, the optimum strategy for deciding when to remove drains following axillary lymphadenectomy remains unknown. This meta-analysis aims to compare time-limited and volume-controlled strategies for drain removal. METHODS: A total of 584 titles were identified following a systematic literature search of EMBASE, MEDLINE, Cinahl and the Cochrane library; 6 titles met our eligibility criteria. Data were extracted and independently verified by two authors. Time-limited drain removal was defined as drain removal at <5 days; volume-controlled strategies ranged from <20 ml/24 h to <50 ml/24 h. RESULTS: In all the studies, the time-limited approach resulted in earlier drain removal. Development of a seroma is 2.54 times more likely with early drain removal (Mantel-Haenszel Fixed Odds Ratio (OR) 2.54, p < 0.00001). However, there is no difference in infection rates between early and late drain removal (OR = 1.07, p = 0.76). CONCLUSIONS: This meta-analysis demonstrates that a strategy of early drain removal following axillary lymphadenectomy is safe, with no difference in infection rates; however, the incidence of seroma is significantly higher, which may necessitate more demanding outpatient care. There is a need for further well-designed clinical trials to address the clinical equipoise in this common area of surgical practice.


Asunto(s)
Axila , Neoplasias de la Mama , Remoción de Dispositivos , Drenaje , Escisión del Ganglio Linfático , Seroma , Infección de la Herida Quirúrgica , Axila/cirugía , Neoplasias de la Mama/patología , Neoplasias de la Mama/cirugía , Remoción de Dispositivos/efectos adversos , Remoción de Dispositivos/métodos , Drenaje/efectos adversos , Drenaje/instrumentación , Drenaje/métodos , Femenino , Humanos , Escisión del Ganglio Linfático/efectos adversos , Escisión del Ganglio Linfático/métodos , Metástasis Linfática , Seroma/etiología , Seroma/prevención & control , Infección de la Herida Quirúrgica/etiología , Infección de la Herida Quirúrgica/prevención & control , Tiempo de Tratamiento
19.
J Plast Reconstr Aesthet Surg ; 69(8): 1134-40, 2016 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-27268948

RESUMEN

INTRODUCTION: Plastic surgery is a competitive and over-subscribed career choice despite minimal medical school exposure. We quantify factors influencing career interest in plastic surgery, speciality appeal and workforce planning. These findings optimise and refine evidence-based plastic surgery training and postgraduate selection criteria. METHODS: Medical students from two national plastic surgery courses complete a post-course questionnaire. Data categories included past experience and career interest in plastic surgery, sources of exposure, motivational factors, and sub-speciality interest. Data were recorded on modified Likert scales, with linear regression and t-test analyses performed. RESULTS: 175 students completed the questionnaire (81% response). Duration of medical student exposure to plastic surgery was significantly associated with career interest (Linear coefficient 0.12, 95% CI 0.08-0.17, P < 0.0001; r(2) = 0.15). 75 h experience is a significant cut-off to categorise students. Mean (95% CI) career interest is 31 percentage points higher in students with >75 h experience (89.2%, 83.2-95.2) compared to students with ≤75 h experience (58.1%, 52.9-63.3) (P < 0.0001). Influential sources included: (1) Operating Room (2) Consultant/Attending interaction (3) Resident interaction. Motivational factors towards a career in plastic surgery included operative satisfaction (91%), improving patient quality of life (89%), and reconstructive surgery (88%). Sub-speciality interests included: (1) Hand and Upper Limb (28%); (2) Cleft Lip and Palate (26%); (3) Burns (15%). CONCLUSION: This study identified influential and motivational factors upon a career in plastic surgery. Medical student exposure can be tailored to maximise positive educational exposure to optimise evidence-based plastic surgery training and workforce planning.


Asunto(s)
Selección de Profesión , Cirugía Plástica/educación , Adolescente , Adulto , Actitud del Personal de Salud , Competencia Clínica , Femenino , Humanos , Masculino , Persona de Mediana Edad , Motivación , Estudiantes de Medicina/psicología , Encuestas y Cuestionarios , Adulto Joven
20.
Burns ; 42(6): 1241-56, 2016 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-27156791

RESUMEN

INTRODUCTION: There is a paucity of evidence guiding management of small area partial thickness paediatric scalds. This has prevented the development of national management guidelines for these injuries. This research aimed to investigate whether a lack of evidence for national guidelines has resulted in variations in both management and outcomes of paediatric small area scalds across England and Wales (E&W). METHODS: A national survey of initial management of paediatric scalds ≤5% Total Body Surface Area (%TBSA) was sent to 14 burns services in E&W. Skin graft rates of anonymised burns services over seven years were collected from the international Burns Injury Database (iBID). Average skin grafting rates across services were compared. Length of stay and proportion of patients receiving general anaesthesia for dressing application at each service were also compared. RESULTS: All 14 burns services responded to the survey. Only 50% of services had a protocol in place for the management of small area burns. All protocols varied in how partial thickness paediatrics scalds ≤5% TBSA should be managed. There was no consensus as to which scalds should be treated using biosynthetic dressings. Data from iBID for 11,917 patients showed that the average reported skin grafting rate across all burns services was 2.3% (95% CI 2.1, 2.6) but varied from 0.3% to 7.1% (P<0.001). Service provider remained associated with likelihood of skin grafting when variations in the %TBSA case mix seen by each service were controlled for (χ(2)=87.3, P<0.001). The use of general anaesthetics across services varied between 0.6 and 35.5% (P<0.001). The median length of stay across services varied from 1 to 3 days (P<0.001). DISCUSSION: A lack of evidence guiding management of small-area paediatric scalds has resulted in variation in management of these injuries across E&W. There is also significant variation in outcomes for these injuries. Further research is indicated to determine if care pathways and outcomes are linked. An evidence-based national policy for the management of small area paediatric scalds would ensure that high quality, standardised care is delivered throughout E&W and variations in outcome are reduced.


Asunto(s)
Anestésicos Generales/uso terapéutico , Vendajes , Quemaduras/terapia , Vías Clínicas , Pautas de la Práctica en Medicina/estadística & datos numéricos , Trasplante de Piel , Superficie Corporal , Preescolar , Manejo de la Enfermedad , Inglaterra , Femenino , Humanos , Lactante , Recién Nacido , Tiempo de Internación , Masculino , Estándares de Referencia , Índices de Gravedad del Trauma , Reino Unido , Gales
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