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1.
Nano Lett ; 23(11): 4837-4843, 2023 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-37191568

RESUMO

Energy transfer processes may be engineered in van der Waals heterostructures by taking advantage of the atomically abrupt, Å-scale, and topologically tailorable interfaces within them. Here, we prepare heterostructures comprised of 2D WSe2 monolayers interfaced with dibenzotetraphenylperiflanthene (DBP)-doped rubrene, an organic semiconductor capable of triplet fusion. We fabricate these heterostructures entirely through vapor deposition methods. Time-resolved and steady-state photoluminescence measurements reveal rapid subnanosecond quenching of WSe2 emission by rubrene and fluorescence from guest DBP molecules at 612 nm (λexc = 730 nm), thus providing clear evidence of photon upconversion. The dependence of the upconversion emission on excitation intensity is consistent with a triplet fusion mechanism, and maximum efficiency (linear regime) of this process occurs at threshold intensities as low as 110 mW/cm2, which is comparable to the integrated solar irradiance. This study highlights the potential for advanced optoelectronic applications employing vdWHs which leverage strongly bound excitons in monolayer TMDs and organic semiconductors.

2.
J Am Chem Soc ; 145(43): 23519-23526, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37862238

RESUMO

Conjugated macromolecules have a rich history in chemistry, owing to their chemical arrangements that intertwine physical and electronic properties. The continuing study and application of these systems, however, necessitates the development of atomically precise models that bridge the gap between molecules, polymers, and/or their blends. One class of conjugated polymers that have facilitated the advancement of structure-property relationships is discrete, precision oligomers that have remained an outstanding synthetic challenge with only a handful of reported examples. Here we show the first synthesis of molecular dyads featuring sequence-defined oligothiophene donors covalently linked a to small-molecule acceptor. These dyads serve as a platform for probing complex photophysical interactions involving sequence-defined oligomers. This assessment is facilitated through the unprecedented control of oligothiophene length- and sequence-dependent arrangement relative to the acceptor unit, made possible by the incorporation of hydroxyl-containing side chains at precise positions along the backbone through sequence-defined oligomerizations. We show that both the oligothiophene sequence and length play complementary roles in determining the transfer efficiency of photoexcited states. Overall, the work highlights the importance of the spatial arrangement of donor-acceptor systems that are commonly studied for a range of uses, including light harvesting and photocatalysis.

3.
Small ; 19(36): e2302173, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37116124

RESUMO

The tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4 TBAPy) along with rare-earth (RE) ions is used for the synthesis of 9 isostructures of a metal-organic framework (MOF) with shp topology, named RE-CU-10 (RE = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III)). The synthesis of each RE-CU-10 analogue requires different reaction conditions to achieve phase pure products. Single crystal X-ray diffraction indicates the presence of a RE9 -cluster in Y- to Tm-CU-10, while a RE11 -cluster is observed for Yb- and Lu-CU-10. The photooxidation performance of RE-CU-10 analogues is evaluated, observing competition between linker-to-metal energy transfer versus the generation of singlet oxygen. The singlet oxygen produced is used to detoxify a mustard gas simulant 2-chloroethylethyl sulfide, with half-lives ranging from 4.0 to 5.8 min, some of the fastest reported to date using UV-irradiation and < 1 mol% catalyst, in methanol under O2 saturation.

4.
J Chem Phys ; 159(7)2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37602803

RESUMO

PbS semiconductor nanocrystals (NCs) have been heavily explored for infrared optoelectronics but can exhibit visible-wavelength quantum-confined optical gaps when sufficiently small (⌀ = 1.8-2.7 nm). However, small PbS NCs traditionally exhibited very broad ensemble absorption linewidths, attributed to poor size-heterogeneity. Here, harnessing recent synthetic advances, we report photophysical measurements on PbS ensembles that span this underexplored size range. We observe that the smallest PbS NCs pervasively exhibit lower brightness and anomalously accelerated photoluminescence decays-relative to the idealized photophysical models that successfully describe larger NCs. We find that effects of residual ensemble size-heterogeneity are insufficient to explain our observations, so we explore plausible processes that are intrinsic to individual nanocrystals. Notably, the anomalous decay kinetics unfold, surprisingly, over hundreds-of-nanosecond timescales. These are poorly matched to effects of direct carrier trapping or fine-structure thermalization but are consistent with non-radiative recombination linked to a dynamic surface. Thus, the progressive enhancement of anomalous decay in the smallest particles supports predictions that the surface plays an outsized role in exciton-phonon coupling. We corroborate this claim by showing that the anomalous decay is significantly remedied by the installation of a rigidifying shell. Intriguingly, our measurements show that the anomalous aspect of these kinetics is insensitive to temperature between T = 298 and 77 K, offering important experimental constraint on possible mechanisms involving structural fluctuations. Thus, our findings identify and map the anomalous photoluminescence kinetics that become pervasive in the smallest PbS NCs and call for targeted experiments and theory to disentangle their origin.

5.
J Urol ; 207(5): 1077-1085, 2022 05.
Artigo em Inglês | MEDLINE | ID: mdl-34981946

RESUMO

PURPOSE: We evaluated angioembolization (AE) use for high-grade renal trauma (HGRT) management and compared AE vs surgical repair (SR) in requiring nephrectomy. MATERIALS AND METHODS: Using National Trauma Data Bank® 2013-2018, we identified patients with HGRT who underwent AE or SR as initial management. Therapy failure was defined as performing subsequent nephrectomy, partial nephrectomy, SR or AE. Logistic regression was performed to assess the association between intervention type (AE vs SR) and nephrectomy. Analysis was repeated in a propensity score-matched cohort constructed by matching AE to SR patients on American Association for the Surgery of Trauma (AAST) grade, injury mechanism (blunt vs penetrating) and hemodynamic instability (systolic blood pressure <90 mmHg). RESULTS: There were 266 patients in the AE group and 215 in the SR group. Median age was 29.5 years and 212 patients (44.1%) had penetrating injuries. AE was successful in 94.2% and 85.3% of grade IV and V injuries, respectively, whereas SR was successful in 82.1% and 56%, respectively. Grade V injury was associated with AE failure in the adjusted analysis (OR 3.55, 95% CI 1.22-10.2, p=0.02). Nephrectomy was less likely to be performed after AE vs after SR in HGRT (6.4% vs 17.2%, p=0.01), AAST grade IV (4.2% vs 13.7%, p=0.001) and AAST grade V (12% vs 44%, p=0.001). The matched cohort comprised 528 patients. In post-match regression, AE, compared to SR, was associated with lower odds of nephrectomy (OR 0.18, 95% CI 0.04-0.70, p=0.013). CONCLUSIONS: AE achieved superior kidney salvage compared to SR in this observational cohort. These results inform both clinical practice and future prospective trials.


Assuntos
Rim , Ferimentos não Penetrantes , Adulto , Hospitais , Humanos , Escala de Gravidade do Ferimento , Rim/lesões , Rim/cirurgia , Sistema de Registros , Estudos Retrospectivos , Ferimentos não Penetrantes/cirurgia
6.
J Vasc Interv Radiol ; 33(6): 687-694, 2022 06.
Artigo em Inglês | MEDLINE | ID: mdl-35301127

RESUMO

PURPOSE: To evaluate radiolabeled doxorubicin (Dox) analogs as tracers of baseline Dox biodistribution in vivo during hepatic intra-arterial chemotherapy and to assess the efficacy of ChemoFilter devices to bind Dox in vitro. MATERIALS AND METHODS: In an in vitro static experiment, [fluorine-18]N-succinimidyl 4-fluorobenzoate ([18F]SFB) and [fluorine-18]fluorobenzoyl-doxorubicin ([18F]FB-Dox) were added to a beaker containing a filter material (Dowex cation exchange resin, single-stranded DNA (ssDNA) resin, or sulfonated polymer coated mesh). In an in vitro flow model, [18F]FB-Dox was added into a Dox solution in phosphate-buffered saline, and the solution flowed via a syringe column containing the filter materials. In an in vitro flow experiment, using micro-positron emission tomography (PET), images were taken as [18F]SFB and [18F]FB-Dox moved through a phantom. For in vivo biodistribution testing, a catheter was placed into the common hepatic artery of a swine, and [18F]FB-Dox was infused over 30 seconds. A 10-minute dynamic image and three 20-minute static images were acquired using 3T PET/MR imaging. RESULTS: In the in vitro static experiment, [18F]FB-Dox demonstrated 76.7%, 88.0%, and 52.4% binding to the Dowex resin, ssDNA resin, and coated mesh, respectively. In the in vitro flow model, the first-pass binding of [18F]FB-Dox to the Dowex resin, ssDNA resin, and coated mesh was 76.7%, 74.2%, and 76.2%, respectively, and the total bound fraction was 80.9%, 84.6%, and 79.9%, respectively. In the in vitro flow experiment using micro-PET, the phantom demonstrated a greater amount of [18F]FB-Dox bound to both filter cartridges than of the control [18F]SFB. In in vivo biodistribution testing, the first 10 minutes depicted [18F]FB-Dox moving through the right upper quadrant of the abdomen. A region-of-interest analysis showed that the relative amount increased by 2.97 times in the gallbladder and 1.08 times in the kidney. The amount decreased by 0.74 times in the brain and 0.57 times in the heart. CONCLUSIONS: [18F]FB-Dox can be used to assess Dox binding to ChemoFilters as well as in vivo biodistribution. This sets the stage for the evaluation of ChemoFilter effectiveness in reducing systemic toxicity from intra-arterial chemotherapy.


Assuntos
Doxorrubicina , Tomografia por Emissão de Pósitrons , Animais , Artéria Hepática , Humanos , Imageamento por Ressonância Magnética , Tomografia por Emissão de Pósitrons/métodos , Suínos , Distribuição Tecidual
7.
Radiology ; 299(1): 167-176, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33560189

RESUMO

Background For patients with acute ischemic stroke undergoing endovascular mechanical thrombectomy with x-ray angiography, the use of adjuncts to maintain vessel patency, such as stents or antiplatelet medications, can increase risk of periprocedural complications. Criteria for using these adjuncts are not well defined. Purpose To evaluate use of MRI to guide critical decision making by using a combined biplane x-ray neuroangiography 3.0-T MRI suite during acute ischemic stroke intervention. Materials and Methods This retrospective observational study evaluated consecutive patients undergoing endovascular intervention for acute ischemic stroke between July 2019 and May 2020 who underwent either angiography with MRI or angiography alone. Cerebral tissue viability was assessed by using MRI as the reference standard. For statistical analysis, Fisher exact test and Student t test were used to compare groups. Results Of 47 patients undergoing acute stroke intervention, 12 patients (median age, 69 years; interquartile range, 60-77 years; nine men) underwent x-ray angiography with MRI whereas the remaining 35 patients (median age, 80 years; interquartile range, 68-86 years; 22 men) underwent angiography alone. MRI results influenced clinical decision making in one of three ways: whether or not to perform initial or additional mechanical thrombectomy, whether or not to place an intracranial stent, and administration of antithrombotic or blood pressure medications. In this initial experience, decision making during endovascular acute stroke intervention in the combined angiography-MRI suite was better informed at MRI, such that therapy was guided in real time by the viability of the at-risk cerebral tissue. Conclusion Integrating intraprocedural 3.0-T MRI into acute ischemic stroke treatment was feasible and guided decisions of whether or not to continue thrombectomy, to place stents, or to administer antithrombotic medication or provide blood pressure medications. © RSNA, 2021 Online supplemental material is available for this article. See also the editorial by Lev and Leslie-Mazwi in this issue.


Assuntos
Angiografia Cerebral/métodos , Tomada de Decisões , AVC Isquêmico/diagnóstico por imagem , AVC Isquêmico/cirurgia , Imageamento por Ressonância Magnética/métodos , Acidente Vascular Cerebral/diagnóstico por imagem , Acidente Vascular Cerebral/cirurgia , Trombectomia/métodos , Idoso , Feminino , Humanos , Recém-Nascido , Período Intraoperatório , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos
8.
J Vasc Interv Radiol ; 30(4): 589-593.e3, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30910181

RESUMO

Opportunities for interventional radiology (IR) education and exposure remain limited at medical institutions without a local IR presence, thereby excluding a medical student population with potential to pursue careers in IR or become referring providers to IR. The purpose of this study was to evaluate the efficacy of a Webinar-based IR elective as an educational tool for outreach to US medical schools lacking local preclinical IR exposure. Our early results indicate that a Webinar-based IR lecture series can serve as an effective method for educating future physicians about the field of IR and when to consult IR for patient management.


Assuntos
Escolha da Profissão , Instrução por Computador/métodos , Educação de Graduação em Medicina/métodos , Internet , Radiologistas/educação , Radiologia Intervencionista/educação , Especialização , Estudantes de Medicina , Currículo , Feminino , Humanos , Masculino
9.
Conserv Biol ; 33(2): 413-422, 2019 04.
Artigo em Inglês | MEDLINE | ID: mdl-30346052

RESUMO

Wind energy development is the most recent of many pressures on upland bird communities and their habitats. Studies of birds in relation to wind energy development have focused on effects of direct mortality, but the importance of indirect effects (e.g., displacement, habitat loss) on avian community diversity and stability is increasingly being recognized. We used a control-impact study in combination with a gradient design to assess the effects of wind farms on upland bird densities and on bird species grouped by habitat association (forest and open-habitat species). We conducted 506 point count surveys at 12 wind-farm and 12 control sites in Ireland during 2 breeding seasons (2012 and 2013). Total bird densities were lower at wind farms than at control sites, and the greatest differences occurred close to turbines. Densities of forest species were significantly lower within 100 m of turbines than at greater distances, and this difference was mediated by habitat modifications associated with wind-farm development. In particular, reductions in forest cover adjacent to turbines was linked to the observed decrease in densities of forest species. Open-habitat species' densities were lower at wind farms but were not related to distance from turbines and were negatively related to size of the wind farm. This suggests that, for these species, wind-farm effects may occur at a landscape scale. Our findings indicate that the scale and intensity of the displacement effects of wind farms on upland birds depends on bird species' habitat associations and that the observed effects are mediated by changes in land use associated with wind-farm construction. This highlights the importance of construction effects and siting of turbines, tracks, and other infrastructure in understanding the impacts of wind farms on biodiversity.


Efectos del Desarrollo de la Energía Eólica y los Cambios Asociados al Uso de Suelo sobre las Densidades de Aves en Tierras Altas Resumen El desarrollo de la energía eólica es la más reciente de muchas presiones ejercidas sobre las comunidades de aves de tierras altas y sus hábitats. Los estudios sobre aves en relación con el desarrollo de la energía eólica se han enfocado en los efectos de la mortalidad directa, pero la importancia de los efectos indirectos (p. ej.: desplazamiento, pérdida de hábitat) sobre la diversidad y estabilidad de las comunidades aviares cada vez se reconoce más. Usamos un estudio de control-impacto combinado con un diseño de gradiente para evaluar los efectos de los campos eólicos sobre las densidades de aves de tierras altas y sobre las especies de aves agrupadas por asociación de hábitat (especies de bosque y de hábitat abierto). Realizamos 506 censos de conteo por puntos en 12 sitios de campos eólicos y 12 sitios control en Irlanda durante dos temporadas de reproducción (2012 y 2013). Las densidades de aves totales fueron más bajas en los campos eólicos que en los sitios control, con las diferencias más importantes ocurriendo cerca de las turbinas. Las densidades de las especies de bosque fueron significativamente más bajas a 100 m de las turbinas que a distancias mayores y esta diferencia estuvo mediada por modificaciones asociadas con el desarrollo de campos eólicos. De manera particular, las reducciones en la cobertura de bosque adyacente a las turbinas estuvieron vinculadas con la disminución observada en las densidades de las especies de bosque. Las densidades de las especies de hábitat abierto fueron más bajas en los campos eólicos pero no estuvieron relacionadas con la distancia a las turbinas y tuvieron una relación negativa con el tamaño del campo eólico. Lo anterior sugiere que, para estas especies, los efectos del campo eólico pueden ocurrir a la escala de paisaje. Nuestros hallazgos indican que la escala y la intensidad de los efectos de desplazamiento de los campos eólicos sobre las aves de tierras altas dependen de las asociaciones de hábitat de las especies de aves y que los efectos observados están mediados por cambios en el uso de suelo asociados con la construcción de campos eólicos. Esto remarca la importancia de los efectos de construcción y el sitiado de las turbinas, pistas y demás infraestructura en el entendimiento de los impactos que tienen los campos eólicos sobre la biodiversidad.


Assuntos
Conservação dos Recursos Naturais , Fontes Geradoras de Energia , Animais , Aves , Ecossistema , Vento
10.
Emerg Radiol ; 25(6): 719-722, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30155849

RESUMO

Management of splenic pseudoaneurysms in hemodynamically stable patients has shifted toward nonoperative management, including watchful waiting and endovascular embolization. Standard of treatment does not include percutaneous embolization for splenic pseudoaneurysm repair. In this case report, we document a successful percutaneous embolization of a post traumatic splenic pseudoaneurysm with thrombin. Percutaneous embolization of splenic pseudoaneurysms can be considered a viable technique in patients who fail endovascular embolization or have lesions inaccessible to endovascular repair.


Assuntos
Falso Aneurisma/terapia , Embolização Terapêutica/métodos , Baço/lesões , Ferimentos não Penetrantes/terapia , Acidentes de Trânsito , Falso Aneurisma/diagnóstico por imagem , Angiografia , Humanos , Masculino , Pessoa de Meia-Idade , Motocicletas , Baço/diagnóstico por imagem , Tomografia Computadorizada por Raios X , Ferimentos não Penetrantes/diagnóstico por imagem
11.
Biomed Microdevices ; 19(4): 88, 2017 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-28948399

RESUMO

To assess the visualization and efficacy of a wireless resonant circuit (wRC) catheter system for carotid artery occlusion and embolectomy under real-time MRI guidance in vivo, and to compare MR imaging modality with x-ray for analysis of qualitative physiological measures of blood flow at baseline and after embolectomy. The wRC catheter system was constructed using a MR compatible PEEK fiber braided catheter (Penumbra, Inc, Alameda, CA) with a single insulated longitudinal copper loop soldered to a printed circuit board embedded within the catheter wall. In concordance with IACUC protocol (AN103047), in vivo carotid artery navigation and embolectomy were performed in four farm pigs (40-45 kg) under real-time MRI at 1.5T. Industry standard clots were introduced in incremental amounts until adequate arterial occlusion was noted in a total of n=13 arteries. Baseline vasculature and restoration of blood flow were confirmed via MR and x-ray imaging, and graded by the Thrombolysis in Cerebral Infarction (TICI) scale. Wilcoxon signed-rank tests were used to analyze differences in recanalization status between DSA and MRA imaging. Successful recanalizations (TICI 2b/3) were compared to clinical rates reported in literature via binomial tests. The wRC catheter system was visible both on 5° sagittal bSSFP and coronal GRE sequence. Successful recanalization was demonstrated in 11 of 13 occluded arteries by DSA analysis and 8 of 13 by MRA. Recanalization rates based on DSA (0.85) and MRA (0.62) were not significantly different from the clinical rate of mechanical aspiration thrombectomy reported in literature. Lastly, a Wilcoxon signed rank test indicated no significant difference between TICI scores analyzed by DSA and MRA. With demonstrated compatibility and visualization under MRI, the wRC catheter system is effective for in vivo endovascular embolectomy, suggesting progress towards clinical endovascular interventional MRI.


Assuntos
Artérias Carótidas/diagnóstico por imagem , Cateterismo , Catéteres , Embolectomia , Imageamento por Ressonância Magnética , Animais , Cateterismo/instrumentação , Cateterismo/métodos , Embolectomia/instrumentação , Embolectomia/métodos , Imageamento por Ressonância Magnética/instrumentação , Imageamento por Ressonância Magnética/métodos , Suínos
12.
Nano Lett ; 16(10): 6070-6077, 2016 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-27627129

RESUMO

Lead chalcogenide colloidal nanocrystals (NCs) are promising materials for solution processable optoelectronics. However, there is little agreement on the identity and character of PbS NC emission for different degrees of quantum confinement-a critical parameter for realizing applications for these nanocrystals. In this work, we combine ensemble and single NC spectroscopies to interrogate preparations of lead sulfide NCs. We use solution photon correlation Fourier spectroscopy (S-PCFS) to measure the average single NC linewidth of near-infrared-emitting PbS quantum dots and find it to be dominated by homogeneous broadening. We further characterize PbS NCs using temperature-dependent linear and time-resolved emission spectroscopy which demonstrate that a kinetically accessed defect state dominates room temperature emission of highly confined emitting NCs. These experiments, taken together, demonstrate that the linewidth and Stokes shift of PbS NCs are the result of emission from two states: a thermally accessed defect-with an energetically pinned charge carrier-and an inhomogeneously broadened band-edge state.

13.
Radiology ; 281(1): 219-28, 2016 10.
Artigo em Inglês | MEDLINE | ID: mdl-27019290

RESUMO

Purpose To assess the feasibility of a magnetically assisted remote-controlled (MARC) catheter system under magnetic resonance (MR) imaging guidance for performing a simple endovascular procedure (ie, renal artery embolization) in vivo and to compare with x-ray guidance to determine the value of MR imaging guidance and the specific areas where the MARC system can be improved. Materials and Methods In concordance with the Institutional Animal Care and Use Committee protocol, in vivo renal artery navigation and embolization were tested in three farm pigs (mean weight 43 kg ± 2 [standard deviation]) under real-time MR imaging at 1.5 T. The MARC catheter device was constructed by using an intramural copper-braided catheter connected to a laser-lithographed saddle coil at the distal tip. Interventionalists controlled an in-room cart that delivered electrical current to deflect the catheter in the MR imager. Contralateral kidneys were similarly embolized under x-ray guidance by using standard clinical catheters and guidewires. Changes in renal artery flow and perfusion were measured before and after embolization by using velocity-encoded and perfusion MR imaging. Catheter navigation times, renal parenchymal perfusion, and renal artery flow rates were measured for MR-guided and x-ray-guided embolization procedures and are presented as means ± standard deviation in this pilot study. Results Embolization was successful in all six kidneys under both x-ray and MR imaging guidance. Mean catheterization time with MR guidance was 93 seconds ± 56, compared with 60 seconds ± 22 for x-ray guidance. Mean changes in perfusion rates were 4.9 au/sec ± 0.8 versus 4.6 au/sec ± 0.6, and mean changes in renal flow rate were 2.1 mL/min/g ± 0.2 versus 1.9 mL/min/g ± 0.2 with MR imaging and x-ray guidance, respectively. Conclusion The MARC catheter system is feasible for renal artery catheterization and embolization under real-time MR imaging in vivo, and quantitative physiologic measures under MR imaging guidance were similar to those measured under x-ray guidance, suggesting that the MARC catheter system could be used for endovascular procedures with interventional MR imaging. (©) RSNA, 2016.


Assuntos
Cateterismo Periférico/instrumentação , Embolização Terapêutica/instrumentação , Procedimentos Endovasculares/instrumentação , Imagem por Ressonância Magnética Intervencionista , Magnetismo , Artéria Renal , Animais , Modelos Animais , Projetos Piloto , Radiografia Intervencionista , Suínos
14.
Chemistry ; 22(8): 2605-10, 2016 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-26866821

RESUMO

Methylammonium lead halide (MAPbX3 ) perovskites exhibit exceptional carrier transport properties. But their commercial deployment as solar absorbers is currently limited by their intrinsic instability in the presence of humidity and their lead content. Guided by our theoretical predictions, we explored the potential of methylammonium bismuth iodide (MBI) as a solar absorber through detailed materials characterization. We synthesized phase-pure MBI by solution and vapor processing. In contrast to MAPbX3, MBI is air stable, forming a surface layer that does not increase the recombination rate. We found that MBI luminesces at room temperature, with the vapor-processed films exhibiting superior photoluminescence (PL) decay times that are promising for photovoltaic applications. The thermodynamic, electronic, and structural features of MBI that are amenable to these properties are also present in other hybrid ternary bismuth halide compounds. Through MBI, we demonstrate a lead-free and stable alternative to MAPbX3 that has a similar electronic structure and nanosecond lifetimes.

15.
Biomed Microdevices ; 18(6): 98, 2016 12.
Artigo em Inglês | MEDLINE | ID: mdl-27778226

RESUMO

To report a novel method using immobilized DNA within mesh to sequester drugs that have intrinsic DNA binding characteristics directly from flowing blood. DNA binding experiments were carried out in vitro with doxorubicin in saline (PBS solution), porcine serum, and porcine blood. Genomic DNA was used to identify the concentration of DNA that shows optimum binding clearance of doxorubicin from solution. Doxorubicin binding kinetics by DNA enclosed within porous mesh bags was evaluated. Flow model simulating blood flow in the inferior vena cava was used to determine in vitro binding kinetics between doxorubicin and DNA. The kinetics of doxorubicin binding to free DNA is dose-dependent and rapid, with 82-96 % decrease in drug concentration from physiologic solutions within 1 min of reaction time. DNA demonstrates faster binding kinetics by doxorubicin as compared to polystyrene resins that use an ion exchange mechanism. DNA contained within mesh yields an approximately 70 % decrease in doxorubicin concentration from solution within 5 min. In the IVC flow model, there is a 70 % drop in doxorubicin concentration at 60 min. A DNA-containing ChemoFilter device can rapidly clear clinical doses of doxorubicin from a flow model in simple and complex physiological solutions, thereby suggesting a novel approach to reduce the toxicity of DNA-binding drugs.


Assuntos
Artérias , DNA/química , Doxorrubicina/química , Doxorrubicina/isolamento & purificação , Filtração/instrumentação , Animais , Doxorrubicina/sangue , Doxorrubicina/uso terapêutico , Desenho de Equipamento , Estudos de Viabilidade , Cinética , Suínos
16.
Acta Radiol ; 57(2): 215-24, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25735621

RESUMO

BACKGROUND: Patients with acute myocardial infarct (MI) show additional damage after coronary interventions. PURPOSE: To longitudinally quantify structural and functional changes in the left ventricle (LV) subjected to microembolized MI using multidisciplinary computed tomography (MDCT) and independent reference methods. MATERIAL AND METHODS: Swine (n = 20) served as controls (group I) or were subjected to a combination of coronary occlusion, microembolization, and reperfusion and imaged at 3 days (group II) or 3 days and 5 weeks (group III). LV volumes, perfusion, and MI mass were quantified on cine, perfusion, and delayed contrast enhancement (DE) MDCT. MRI, cardiac injury biomarkers, histochemical and histopathologic stains were used as independent references. RESULTS: MDCT showed a reduction in ejection fraction and increased end systolic volume (31 ± 2% and 82 ± 3 mL, respectively) of group III compared with I (48 ± 2% and 57 ± 1 mL, respectively). It also demonstrated perfusion deficits in microembolized MI and peri-infarcts. DE-MDCT delineated microvascular obstruction (MVO) zones embedded in acute microembolized MI and microinfarct specks resulting from persistent MVO by deposited microemboli in microvessels of peri-infarct zone. Bland-Altman test showed close agreements between the extents of microembolized MI measured on DE-MDCT, DE-MRI, and histochemical TTC staining, but not between these modalities and microscopy. MI resorption was evident between 3 days and 5 weeks (13.4 ± 0.5 g and 9.8 ± 0.5 g, P < 0.017) and histologic examination revealed incomplete healing. Injury biomarkers were increased after intervention. CONCLUSION: MDCT can longitudinally quantify regional perfusion deficits, LV dysfunction, and resorption of microembolized MI. MDCT or MRI can be used alternatively after coronary interventions in cases of contraindications for one modality or the other.


Assuntos
Embolia/diagnóstico , Imageamento por Ressonância Magnética , Tomografia Computadorizada Multidetectores , Infarto do Miocárdio/diagnóstico , Disfunção Ventricular Esquerda/diagnóstico , Animais , Meios de Contraste , Modelos Animais de Doenças , Embolia/complicações , Coração/diagnóstico por imagem , Coração/fisiopatologia , Ventrículos do Coração/diagnóstico por imagem , Ventrículos do Coração/patologia , Infarto do Miocárdio/complicações , Miocárdio/patologia , Intensificação de Imagem Radiográfica , Suínos , Disfunção Ventricular Esquerda/complicações
17.
Emerg Radiol ; 23(1): 57-61, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26581655

RESUMO

Advances in computed tomography (CT) angiography have increased the sensitivity and specificity of detecting small branch arterial injuries in the extremities of trauma patients. However, it is unclear whether these patients should undergo surgery, angioembolization, or conservative watchful waiting. We hypothesized that uncomplicated small arterial branch injuries can be managed successfully with watchful waiting. A 10-year retrospective review of extremity CT angiograms with search findings of arterial "active extravasation" or "pseudoaneurysm" was performed at a level 1 county trauma center. Subgroup analysis was performed on those with isolated extremity injury and those with concurrent injuries. A total of 31 patients had CT-detected active extravasation (84 %) or pseudoaneurysm (16 %), 71 % of which were isolated vascular injuries. Of the patients evaluated, 71 % (n = 22) were managed with watchful waiting, 19 % (n = 6) with angioembolization, and 10 % (n = 3) with surgery. Watchful waiting complications included progression to alternative treatment (n = 1) and blood transfusions (n = 2). Complications of surgery included the inability to find active bleeding (n = 1) and postoperative psychosis (n = 1). Complications of angioembolization were limited to a postprocedure blood transfusion (n = 1). Patients with isolated vascular injuries had an average length of stay of 2.9 days, with management averages of the following: 2.7 days with watchful waiting (n = 16), 3.3 days with angioembolization (n = 3), and 3.7 days with surgery (n = 3). CT angiography has greatly increased the reported incidence of traumatic arterial injury in the extremity. We propose that small branch arterial injuries in the extremities can be managed successfully with watchful waiting and do not often require immediate embolization.


Assuntos
Traumatismos do Braço/diagnóstico por imagem , Traumatismos da Perna/diagnóstico por imagem , Tomografia Computadorizada por Raios X , Lesões do Sistema Vascular/diagnóstico por imagem , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Traumatismos do Braço/terapia , Tomada de Decisões , Embolização Terapêutica , Feminino , Humanos , Traumatismos da Perna/terapia , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Centros de Traumatologia , Procedimentos Cirúrgicos Vasculares , Lesões do Sistema Vascular/terapia , Conduta Expectante
18.
Radiology ; 274(2): 370-8, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25247406

RESUMO

PURPOSE: To provide proof of concept that expansion of myocardial extracellular volume (MECV), measured at contrast material-enhanced multidetector computed tomography (CT), can be used as a (a) marker for viability based on histologic confirmation and (b) predictor of severity of myocardial injury. MATERIALS AND METHODS: Animals cared for in compliance with Institutional Animal Care and Use Committee served as controls (group 1, n = 6) or were subjected to microinfarction by using 16-mm(3) (60 000 count) microemboli (group 2) and 32-mm(3) (120 000 count) microemboli (group 3), contiguous infarct with left anterior descending artery (LAD) occlusion followed by reperfusion (group 4), or the combination of LAD occlusion and 32-mm(3) microemboli followed by reperfusion (group 5) (n = 7 per group). MECV calculations were based on regional measurements of signal attenuation at contrast-enhanced multidetector CT and counterstaining of infarct at microscopy. Two-way analysis of variance and Student t tests were used to determine significant differences (P < .05). Data were presented as means ± standard deviations. RESULTS: Mean signal attenuation at equilibrium state of contrast media distribution (10 minutes) was significantly different among blood (137 HU ± 10), myocardial muscle (77 HU ± 12, P < .05), and skeletal muscle (35 HU ± 12, P < .05). Patchy microinfarct, contiguous infarct, and microinfarct with preexisting contiguous infarct can be differentiated on the basis of mean MECV (24% ± 3 [group 1] vs 36% ± 3 [group 2], P < .01, and 55% ± 5 [group 4], 56% ± 4 [group 5] vs 41% ± 3 [group 3], P < .05). Microscopy measurements confirmed multidetector CT quantitative measurements and differences in patterns of infarct caused by obstruction of major and minor coronary arteries. Regression analysis revealed excellent correlation between regional MECV using multidetector CT and microscopy (r(2) = 0.92). CONCLUSION: Contrast-enhanced multidetector CT is a suitable noninvasive imaging technique for assessing MECV in acute patchy and contiguous infarct caused by obstruction of major and minor coronary vessels.


Assuntos
Meios de Contraste , Tomografia Computadorizada Multidetectores , Infarto do Miocárdio/diagnóstico por imagem , Infarto do Miocárdio/patologia , Animais , Matriz Extracelular/patologia , Valor Preditivo dos Testes , Índice de Gravidade de Doença , Suínos
19.
Radiology ; 277(3): 842-52, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26030659

RESUMO

PURPOSE: To assess the feasibility of multiplanar vascular navigation with a new magnetically assisted remote-controlled (MARC) catheter with real-time magnetic resonance (MR) imaging at 1.5 T and 3 T and to compare it with standard x-ray guidance in simulated endovascular catheterization procedures. MATERIALS AND METHODS: A 1.6-mm-diameter custom clinical-grade microcatheter prototype with lithographed double-saddle coils at the distal tip was deflected with real-time MR imaging. Two inexperienced operators and two experienced operators catheterized anteroposterior (celiac, superior mesenteric, and inferior mesenteric arteries) and mediolateral (renal arteries) branch vessels in a cryogel abdominal aortic phantom. This was repeated with conventional x-ray fluoroscopy by using clinical catheters and guidewires. Mean procedure times and percentage success data were analyzed with linear mixed-effects regression. RESULTS: The MARC catheter tip was visible at 1.5 T and 3 T. Among inexperienced operators, MARC MR imaging guidance was not statistically different from x-ray guidance at 1.5 T (67% successful vessel selection turns with MR imaging vs 76% with x-ray guidance, P = .157) and at 3 T (75% successful turns with MR imaging vs 76% with x-ray guidance, P = .869). Experienced operators were more successful in catheterizing vessels with x-ray guidance (98% success within 60 seconds) than with 1.5-T (65%, P < .001) or 3-T (75%) MR imaging. Among inexperienced operators, mean procedure time was nearly equivalent by using MR imaging (31 seconds) and x-ray guidance (34 seconds, P = .436). Among experienced operators, catheterization was faster with x-ray guidance (20 seconds) compared with 1.5-T MR imaging (42 seconds, P < .001), but MARC guidance improved at 3 T (31 seconds). MARC MR imaging guidance at 3 T was not significantly different from x-ray guidance for the celiac (P = .755), superior mesenteric (P = .358), and inferior mesenteric (P = .065) arteries. CONCLUSION: Multiplanar navigation with a new MARC catheter with real-time MR imaging at 1.5 T and 3 T is feasible and comparable to x-ray guidance for anteroposterior vessels at 3 T in a vascular phantom.


Assuntos
Cateterismo Periférico/instrumentação , Imagem por Ressonância Magnética Intervencionista/instrumentação , Imagem por Ressonância Magnética Intervencionista/métodos , Cateterismo Periférico/métodos , Difusão , Estudos de Viabilidade , Fluoroscopia , Humanos , Magnetismo , Perfusão , Imagens de Fantasmas
20.
Nat Mater ; 13(11): 1039-43, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-25282507

RESUMO

Triplet excitons are ubiquitous in organic optoelectronics, but they are often an undesirable energy sink because they are spin-forbidden from emitting light and their high binding energy hinders the generation of free electron-hole pairs. Harvesting their energy is consequently an important technological challenge. Here, we demonstrate direct excitonic energy transfer from 'dark' triplets in the organic semiconductor tetracene to colloidal PbS nanocrystals, thereby successfully harnessing molecular triplet excitons in the near infrared. Steady-state excitation spectra, supported by transient photoluminescence studies, demonstrate that the transfer efficiency is at least (90 ± 13)%. The mechanism is a Dexter hopping process consisting of the simultaneous exchange of two electrons. Triplet exciton transfer to nanocrystals is expected to be broadly applicable in solar and near-infrared light-emitting applications, where effective molecular phosphors are lacking at present. In particular, this route to 'brighten' low-energy molecular triplet excitons may permit singlet exciton fission sensitization of conventional silicon solar cells.

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