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1.
Nat Commun ; 14(1): 7273, 2023 Nov 10.
Article in English | MEDLINE | ID: mdl-37949848

ABSTRACT

Vertical heterostructures of transition metal dichalcogenides (TMDs) host interlayer excitons with electrons and holes residing in different layers. With respect to their intralayer counterparts, interlayer excitons feature longer lifetimes and diffusion lengths, paving the way for room temperature excitonic optoelectronic devices. The interlayer exciton formation process and its underlying physical mechanisms are largely unexplored. Here we use ultrafast transient absorption spectroscopy with a broadband white-light probe to simultaneously resolve interlayer charge transfer and interlayer exciton formation dynamics in a MoSe2/WSe2 heterostructure. We observe an interlayer exciton formation timescale nearly an order of magnitude (~1 ps) longer than the interlayer charge transfer time (~100 fs). Microscopic calculations attribute this relative delay to an interplay of a phonon-assisted interlayer exciton cascade and thermalization, and excitonic wave-function overlap. Our results may explain the efficient photocurrent generation observed in optoelectronic devices based on TMD heterostructures, as the interlayer excitons are able to dissociate during thermalization.

2.
J Phys Chem Lett ; 13(42): 9903-9909, 2022 Oct 27.
Article in English | MEDLINE | ID: mdl-36256582

ABSTRACT

In this work, we observe plasmon-induced hot electron extraction in a heterojunction between indium tin oxide nanocrystals and monolayer molybdenum disulfide. We study the sample with ultrafast differential transmission, exciting the sample at 1750 nm where the intense localized plasmon surface resonance of the indium tin oxide nanocrystals is and where the monolayer molybdenum disulfide does not absorb light. With the excitation at 1750 nm, we observe the excitonic features of molybdenum disulfide in the visible range, close to the exciton of molybdenum disulfide. Such a phenomenon can be ascribed to a charge transfer between indium tin oxide nanocrystals and monolayer molybdenum disulfide upon plasmon excitation. These results are a first step toward the implementation of near-infrared plasmonic materials for photoconversion.

3.
Pediatr Surg Int ; 38(9): 1335-1340, 2022 Sep.
Article in English | MEDLINE | ID: mdl-35849175

ABSTRACT

PURPOSE: Placement of a central venous catheter (CVC) is the most commonly performed pediatric procedure. This study aims to develop simple formulas to calculate intravascular length of CVCs prior to insertion to minimize reliance on fluoroscopic and radiographic imaging, which may not be uniformly available. METHODS: We performed a single-institution, retrospective review of 115 pediatric patients who received both CVC placement and computed tomography (CT) imaging of the chest within 3 months of the procedure. Using measurements from the CT imaging, formulas calculating the length of the intravascular component of the CVC based on height and insertion laterality were developed and compared to previously published formulas. These formulas were then trialed prospectively to validate reliability and application. RESULTS: Formulas were developed for right-sided and left subclavian insertion. The right-side formula accurately predicted CVC length in 52.6% of patients, compared to 47.4% by the Andropoulos formula. The left subclavian formula accurately estimated 62.5%, compared to 34.5% by the Stroud formula. CONCLUSIONS: The optimal intravascular length of central venous catheters may be determined by simple formulas based on patient height and insertion site. LEVEL OF EVIDENCE: III.


Subject(s)
Catheterization, Central Venous , Central Venous Catheters , Catheterization, Central Venous/methods , Child , Humans , Reproducibility of Results , Retrospective Studies , Tomography, X-Ray Computed
4.
J Phys Chem C Nanomater Interfaces ; 126(7): 3569-3581, 2022 Feb 24.
Article in English | MEDLINE | ID: mdl-35242271

ABSTRACT

The search for synthetic materials that mimic natural photosynthesis by converting solar energy into other more useful forms of energy is an ever-growing research endeavor. Graphene-based materials, with their exceptional electronic and optical properties, are exemplary candidates for high-efficiency solar energy harvesting devices. High photoactivity can be conveniently achieved by functionalizing graphene with small molecule organic semiconductors whose band-gaps can be tuned by structural modification, leading to interactions between the π-conjugated electronic systems in both the semiconductor and graphene. Here we investigate the ultrafast transient optical properties of a cross-linked graphene-dye (diphenyl-dithiophenediketopyrrolopyrrole) nanohybrid material, in which oligomers of the organic semiconductor dye are covalently bound to a random network of few-layer graphene flakes, and compare the results to those obtained for the reference dye monomer. Using a combination of ultrafast transient absorption and two-dimensional electronic spectroscopy, we provide substantial evidence for photoinduced charge transfer that occurs within 18 ps in the nanohybrid system. Notably, subpicosecond photoinduced torsional relaxation observed in the constituent dye monomer is absent in the cross-linked nanohybrid system. Through density functional theory calculations, we compare the competing effects of covalent bonding, increasing conjugation length, and the presence of multiple graphene flakes. We find evidence that the observed ultrafast charge transfer process occurs through a superexchange mechanism in which the oligomeric dye bridge provides virtual states enabling charge transfer between graphene-dye covalent bond sites.

5.
J Pediatr Surg ; 57(10): 463-468, 2022 Oct.
Article in English | MEDLINE | ID: mdl-34991865

ABSTRACT

BACKGROUND: Long term central venous access is necessary for the treatment of several conditions affecting young children. Totally implantable access ports (ports) offer the advantage of containing no external components, thus simplifying their care and maintenance. However, there is no consensus on the safety of port placement in infants (birth to 1-year of age). The aim of this study was to describe complications associated with port placement in infants, including which specific factors may be associated with risk for developing complications among these patients, and thereby assess the safety of port placement in this young population. METHODS: A two-institution, retrospective cohort study identified patients under 1-year old who underwent port placement. Intraoperative, early postoperative (within 30 days), and late postoperative (greater than 30 days) complications were recorded. Multivariate logistic regression models were employed to assess factors associated with port-related complications. RESULTS: Among 121 patients who received a port, 36 (30%) experienced a complication with a median time to complication of 299.5 days [IQR 67.5-440.75]. Of those, 26 required unplanned port removal. Only 3 patients (2.5%) experienced an intraoperative complication, and 3 patients (2.5%) experienced a complication within 30 days of port placement. A diagnosis of cancer was found to be protective against early catheter malfunction (OR=0.31, p = 0.03). A non-statistically significant trend associated with increased complications for large caliber devices (>6.0Fr) and weight <7-kg (OR 2.20, p = 0.06 and OR=2.26, p = 0.11 respectively) was observed. CONCLUSIONS: Port placement appears to be safe for most infants with low or acceptable rates of intra- or post-operative complications. Smaller patient size (< 7 kg) and larger-sized catheters (> 6.0Fr) may be associated with an increased risk for complications among this population. LEVEL OF EVIDENCE: III.


Subject(s)
Catheterization, Central Venous , Neoplasms , Catheterization, Central Venous/adverse effects , Catheters, Indwelling/adverse effects , Child , Child, Preschool , Humans , Infant , Neoplasms/therapy , Postoperative Complications/epidemiology , Postoperative Complications/etiology , Prostheses and Implants , Retrospective Studies
6.
Front Immunol ; 12: 691741, 2021.
Article in English | MEDLINE | ID: mdl-34211478

ABSTRACT

The outcome for metastatic pediatric osteosarcoma (OS) remains poor. Thus, there is an urgent need to develop novel therapies, and immunotherapy with CAR T cells has the potential to meet this challenge. However, there is a lack of preclinical models that mimic salient features of human disease including reliable development of metastatic disease post orthotopic OS cell injection. To overcome this roadblock, and also enable real-time imaging of metastatic disease, we took advantage of LM7 OS cells expressing firefly luciferase (LM7.ffLuc). LM7.ffLuc were implanted in a collagen mesh into the tibia of mice, and mice reliably developed orthotopic tumors and lung metastases as judged by bioluminescence imaging and histopathological analysis. Intratibial implantation also enabled surgical removal by lower leg amputation and monitoring for metastases development post-surgery. We then used this model to evaluate the antitumor activity of CAR T cells targeting B7-H3, an antigen that is expressed in a broad range of solid tumors including OS. B7-H3-CAR T cells had potent antitumor activity in a dose-dependent manner and inhibited the development of pulmonary metastases resulting in a significant survival advantage. In contrast T cells expressing an inactive B7-H3-CAR had no antitumor activity. Using unmodified LM7 cells also enabled us to demonstrate that B7-H3-CAR T cells traffic to orthotopic tumor sites. Hence, we have developed an orthotopic, spontaneously metastasizing OS model. This model may improve our ability not only to predict the safety and efficacy of current and next generation CAR T cell therapies but also other treatment modalities for metastatic OS.


Subject(s)
B7 Antigens/immunology , Bone Neoplasms/therapy , Immunotherapy, Adoptive , Osteosarcoma/therapy , Receptors, Chimeric Antigen/immunology , Animals , Bone Neoplasms/pathology , Cell Line, Tumor , Female , Humans , Lung Neoplasms/secondary , Lung Neoplasms/therapy , Mice , Osteosarcoma/pathology , Tibia/pathology , Treatment Outcome , Xenograft Model Antitumor Assays
7.
Materials (Basel) ; 13(24)2020 Dec 16.
Article in English | MEDLINE | ID: mdl-33339218

ABSTRACT

In this work, studies of the optical constants of monolayer transition metal dichalcogenides and few-layer black phosphorus are briefly reviewed, with particular emphasis on the complex dielectric function and refractive index. Specifically, an estimate of the complex index of refraction of phosphorene and few-layer black phosphorus is given. The complex index of refraction of this material was extracted from differential reflectance data reported in the literature by employing a constrained Kramers-Kronig analysis combined with the transfer matrix method. The reflectance contrast of 1-3 layers of black phosphorus on a silicon dioxide/silicon substrate was then calculated using the extracted complex indices of refraction.

8.
Nanomaterials (Basel) ; 10(8)2020 Aug 04.
Article in English | MEDLINE | ID: mdl-32759768

ABSTRACT

Chemically synthesized zigzag-edged nanographenes (NG) have recently demonstrated great success as the active laser units in solution-processed organic distributed feedback (DFB) lasers. Here, we report the first observation of dual amplified spontaneous emission (ASE) from a large-size NG derivative (with 12 benzenoid rings) dispersed in a polystyrene film. ASE is observed simultaneously at the 685 and 739 nm wavelengths, which correspond to different transitions of the photoluminescence spectrum. Ultrafast pump-probe spectroscopy has been used to ascertain the underlying photophysical processes taking place in the films. DFB lasers, based on these materials and top-layer nanostructured polymeric resonators (i.e., one or two-dimensional surface relief gratings), have been fabricated and characterized. Lasers emitting close to either one of the two possible ASE wavelengths, or simultaneously at both of them, have been prepared by proper selection of the resonator parameters.

9.
Faraday Discuss ; 223(0): 125-135, 2020 10 23.
Article in English | MEDLINE | ID: mdl-32720674

ABSTRACT

The colour purity and versatility of fabrication of one-dimensional photonic crystals (1D PhCs) make them ideal candidates for colorimetric sensing of a variety of analytes. For instance, the detection of bacterial contaminants in food via colorimetric sensors can be highly appealing, as most of the existing detection techniques are in general time-consuming and the read-out requires specialised personnel. Here, we present a colorimetric sensor based on hybrid plasmonic/photonic 1D crystals. We demonstrate that the modification of the silver plasmon resonance brought about by the effective silver/bacterium interaction can be translated into the visible spectral region, producing a change in the structural colour. In addition, we observe a superior colorimetric sensitivity against the Gram negative Escherichia coli compared to the Gram positive Micrococcus luteus, a result that we attribute to the more efficient electrostatic interaction and cellular adhesion between the silver surface and the Gram-negative bacteria outer membrane. This approach demonstrates that in principle an easy colorimetric detection of bacterial contaminants can be achieved through the use of bio-responsive plasmonic materials, such as silver, whose selective electrostatic interaction with bacterial cell wall is well-known and occurs without the need of chemical functionalisation.


Subject(s)
Colorimetry/methods , Escherichia coli/isolation & purification , Micrococcus luteus/isolation & purification , Silver/chemistry , Crystallization , Microscopy, Electron, Scanning , Photons
10.
IEEE Trans Biomed Eng ; 67(8): 2176-2186, 2020 08.
Article in English | MEDLINE | ID: mdl-32673194

ABSTRACT

OBJECTIVE: To evaluate the effect of a closed-loop temperature based feedback algorithm on ablative outcomes for pulsed electric field treatments. METHODS: A 3D tumor model of glioblastoma was used to assess the impact of 2 µs duration bipolar waveforms on viability following exposure to open and closed-loop protocols. Closed-loop treatments evaluated transient temperature increases of 5, 10, 15, or 22 °C above baseline. RESULTS: The temperature controlled ablation diameters were conditionally different than the open-loop treatments and closed-loop treatments generally produced smaller ablations. Closed-loop control enabled the investigation of treatments with steady state 42 °C hyperthermic conditions which were not feasible without active feedback. Baseline closed-loop treatments at 20 °C resulted in ablations measuring 9.9 ± 0.3 mm in diameter while 37 °C treatments were 20% larger (p < 0.0001) measuring 11.8 ± 0.3 mm indicating that this protocol induces a thermally mediated biological response. CONCLUSION: A closed-loop control algorithm which modulated the delay between successive pulse waveforms to achieve stable target temperatures was demonstrated. Algorithmic control enabled the evaluation of specific treatment parameters at physiological temperatures not possible with open-loop systems due to excessive Joule heating. SIGNIFICANCE: Irreversible electroporation is generally considered to be a non-thermal ablation modality and temperature monitoring is not part of the standard clinical practice. The results of this study indicate ablative outcomes due to exposure to pulses on the order of one microsecond may be thermally mediated and dependent on local tissue temperatures. The results of this study set the foundation for experiments in vivo utilizing temperature control algorithms.


Subject(s)
Electroporation , Neoplasms , Electricity , Humans , Models, Theoretical , Temperature
12.
Nat Commun ; 10(1): 1881, 2019 04 23.
Article in English | MEDLINE | ID: mdl-31015438

ABSTRACT

Bromodomain-containing protein 9 (BRD9) is a recently identified subunit of SWI/SNF(BAF) chromatin remodeling complexes, yet its function is poorly understood. Here, using a genome-wide CRISPR-Cas9 screen, we show that BRD9 is a specific vulnerability in pediatric malignant rhabdoid tumors (RTs), which are driven by inactivation of the SMARCB1 subunit of SWI/SNF. We find that BRD9 exists in a unique SWI/SNF sub-complex that lacks SMARCB1, which has been considered a core subunit. While SMARCB1-containing SWI/SNF complexes are bound preferentially at enhancers, we show that BRD9-containing complexes exist at both promoters and enhancers. Mechanistically, we show that SMARCB1 loss causes increased BRD9 incorporation into SWI/SNF thus providing insight into BRD9 vulnerability in RTs. Underlying the dependency, while its bromodomain is dispensable, the DUF3512 domain of BRD9 is essential for SWI/SNF integrity in the absence of SMARCB1. Collectively, our results reveal a BRD9-containing SWI/SNF subcomplex is required for the survival of SMARCB1-mutant RTs.


Subject(s)
Chromatin Assembly and Disassembly , Rhabdoid Tumor/genetics , SMARCB1 Protein/genetics , Transcription Factors/metabolism , CRISPR-Cas Systems/genetics , Cell Line, Tumor , Enhancer Elements, Genetic/genetics , Gene Knockdown Techniques , Gene Knockout Techniques , Humans , Mutation , Promoter Regions, Genetic/genetics , Protein Domains/drug effects , RNA, Small Interfering/metabolism , Rhabdoid Tumor/pathology , SMARCB1 Protein/metabolism , Transcription Factors/antagonists & inhibitors , Transcription Factors/genetics
13.
Phys Rev Lett ; 117(7): 077403, 2016 Aug 12.
Article in English | MEDLINE | ID: mdl-27563998

ABSTRACT

We demonstrate the extension of coherence between all four two-electron spin ground states of an InAs quantum dot molecule (QDM) via nonlocal suppression of nuclear spin fluctuations in two vertically stacked quantum dots (QDs), while optically addressing only the top QD transitions. Long coherence times are revealed through dark-state spectroscopy as resulting from nuclear spin locking mediated by the exchange interaction between the QDs. Line shape analysis provides the first measurement of the quieting of the Overhauser field distribution correlating with reduced nuclear spin fluctuations.

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