Multiple exciton generation, the creation of two electron-hole pairs from one high-energy photon, is well established in bulk semiconductors, but assessments of the efficiency of this effect remain ...controversial in quantum-confined systems like semiconductor nanocrystals. We used a photoelectrochemical system composed of PbS nanocrystals chemically bound to TiO₂ single crystals to demonstrate the collection of photocurrents with quantum yields greater than one electron per photon. The strong electronic coupling and favorable energy level alignment between PbS nanocrystals and bulk TiO₂ facilitate extraction of multiple excitons more quickly than they recombine, as well as collection of hot electrons from higher quantum dot excited states. Our results have implications for increasing the efficiency of photovoltaic devices by avoiding losses resulting from the thermalization of photogenerated carriers.
The major clinical challenge in the treatment of high-grade serous ovarian cancer (HGSOC) is the development of progressive resistance to platinum-based chemotherapy. The objective of this study was ...to determine whether intra-tumour genetic heterogeneity resulting from clonal evolution and the emergence of subclonal tumour populations in HGSOC was associated with the development of resistant disease.
Evolutionary inference and phylogenetic quantification of heterogeneity was performed using the MEDICC algorithm on high-resolution whole genome copy number profiles and selected genome-wide sequencing of 135 spatially and temporally separated samples from 14 patients with HGSOC who received platinum-based chemotherapy. Samples were obtained from the clinical CTCR-OV03/04 studies, and patients were enrolled between 20 July 2007 and 22 October 2009. Median follow-up of the cohort was 31 mo (interquartile range 22-46 mo), censored after 26 October 2013. Outcome measures were overall survival (OS) and progression-free survival (PFS). There were marked differences in the degree of clonal expansion (CE) between patients (median 0.74, interquartile range 0.66-1.15), and dichotimization by median CE showed worse survival in CE-high cases (PFS 12.7 versus 10.1 mo, p = 0.009; OS 42.6 versus 23.5 mo, p = 0.003). Bootstrap analysis with resampling showed that the 95% confidence intervals for the hazard ratios for PFS and OS in the CE-high group were greater than 1.0. These data support a relationship between heterogeneity and survival but do not precisely determine its effect size. Relapsed tissue was available for two patients in the CE-high group, and phylogenetic analysis showed that the prevalent clonal population at clinical recurrence arose from early divergence events. A subclonal population marked by a NF1 deletion showed a progressive increase in tumour allele fraction during chemotherapy.
This study demonstrates that quantitative measures of intra-tumour heterogeneity may have predictive value for survival after chemotherapy treatment in HGSOC. Subclonal tumour populations are present in pre-treatment biopsies in HGSOC and can undergo expansion during chemotherapy, causing clinical relapse.
Recent advances have been made in thin-film solar cells using CdTe and CuIn1−x Ga x Se2 (CIGS) nanoparticles, which have achieved impressive efficiencies. Despite these efficiencies, CdTe and CIGS ...are not amenable to large-scale production because of the cost and scarcity of Te, In, and Ga. Cu2ZnSnS4 (CZTS), however, is an emerging solar cell material that contains only earth-abundant elements and has a near-optimal direct band gap of 1.45−1.65 eV and a large absorption coefficient. Here we report the direct synthesis of CZTS nanocrystals using the hot-injection method. In-depth characterization indicated that pure stoichiometric CZTS nanocrystals with an average particle size of 12.8 ± 1.8 nm were formed. Optical measurements showed a band gap of 1.5 eV, which is optimal for a single-junction solar device.
Existing methods to improve detection of circulating tumor DNA (ctDNA) have focused on genomic alterations but have rarely considered the biological properties of plasma cell-free DNA (cfDNA). We ...hypothesized that differences in fragment lengths of circulating DNA could be exploited to enhance sensitivity for detecting the presence of ctDNA and for noninvasive genomic analysis of cancer. We surveyed ctDNA fragment sizes in 344 plasma samples from 200 patients with cancer using low-pass whole-genome sequencing (0.4×). To establish the size distribution of mutant ctDNA, tumor-guided personalized deep sequencing was performed in 19 patients. We detected enrichment of ctDNA in fragment sizes between 90 and 150 bp and developed methods for in vitro and in silico size selection of these fragments. Selecting fragments between 90 and 150 bp improved detection of tumor DNA, with more than twofold median enrichment in >95% of cases and more than fourfold enrichment in >10% of cases. Analysis of size-selected cfDNA identified clinically actionable mutations and copy number alterations that were otherwise not detected. Identification of plasma samples from patients with advanced cancer was improved by predictive models integrating fragment length and copy number analysis of cfDNA, with area under the curve (AUC) >0.99 compared to AUC <0.80 without fragmentation features. Increased identification of cfDNA from patients with glioma, renal, and pancreatic cancer was achieved with AUC > 0.91 compared to AUC < 0.5 without fragmentation features. Fragment size analysis and selective sequencing of specific fragment sizes can boost ctDNA detection and could complement or provide an alternative to deeper sequencing of cfDNA.
Nanocrystals of multicomponent chalcogenides, such as Cu2ZnSnS4 (CZTS), are potential building blocks for low-cost thin-film photovoltaics (PVs). CZTS PV devices with modest efficiencies have been ...realized through postdeposition annealing at high temperatures in Se vapor. However, little is known about the precise role of Se in the CZTS system. We report the direct solution-phase synthesis and characterization of Cu2ZnSn(S1–x Se x )4 nanocrystals (0 ≤ x ≤ 1) with the aim of probing the role of Se incorporation into CZTS. Our results indicate that increasing the amount of Se increases the lattice parameters, slightly decreases the band gap, and most importantly increases the electrical conductivity of the nanocrystals without a need for annealing.
Circulating tumour DNA (ctDNA) carrying tumour-specific sequence alterations may provide a minimally invasive means to dynamically assess tumour burden and response to treatment in cancer patients. ...Somatic TP53 mutations are a defining feature of high-grade serous ovarian carcinoma (HGSOC). We tested whether these mutations could be used as personalised markers to monitor tumour burden and early changes as a predictor of response and time to progression (TTP).
We performed a retrospective analysis of serial plasma samples collected during routine clinical visits from 40 patients with HGSOC undergoing heterogeneous standard of care treatment. Patient-specific TP53 assays were developed for 31 unique mutations identified in formalin-fixed paraffin-embedded tumour DNA from these patients. These assays were used to quantify ctDNA in 318 plasma samples using microfluidic digital PCR. The TP53 mutant allele fraction (TP53MAF) was compared to serum CA-125, the current gold-standard response marker for HGSOC in blood, as well as to disease volume on computed tomography scans by volumetric analysis. Changes after one cycle of treatment were compared with TTP. The median TP53MAF prior to treatment in 51 relapsed treatment courses was 8% (interquartile range IQR 1.2%-22%) compared to 0.7% (IQR 0.3%-2.0%) for seven untreated newly diagnosed stage IIIC/IV patients. TP53MAF correlated with volumetric measurements (Pearson r = 0.59, p < 0.001), and this correlation improved when patients with ascites were excluded (r = 0.82). The ratio of TP53MAF to volume of disease was higher in relapsed patients (0.04% per cm3) than in untreated patients (0.0008% per cm3, p = 0.004). In nearly all relapsed patients with disease volume > 32 cm3, ctDNA was detected at ≥20 amplifiable copies per millilitre of plasma. In 49 treatment courses for relapsed disease, pre-treatment TP53MAF concentration, but not CA-125, was associated with TTP. Response to chemotherapy was seen earlier with ctDNA, with a median time to nadir of 37 d (IQR 28-54) compared with a median time to nadir of 84 d (IQR 42-116) for CA-125. In 32 relapsed treatment courses evaluable for response after one cycle of chemotherapy, a decrease in TP53MAF of >60% was an independent predictor of TTP in multivariable analysis (hazard ratio 0.22, 95% CI 0.07-0.67, p = 0.008). Conversely, a decrease in TP53MAF of ≤60% was associated with poor response and identified cases with TTP < 6 mo with 71% sensitivity (95% CI 42%-92%) and 88% specificity (95% CI 64%-99%). Specificity was improved when patients with recent drainage of ascites were excluded. Ascites drainage led to a reduction of TP53MAF concentration. The limitations of this study include retrospective design, small sample size, and heterogeneity of treatment within the cohort.
In this retrospective study, we demonstrated that ctDNA is correlated with volume of disease at the start of treatment in women with HGSOC and that a decrease of ≤60% in TP53MAF after one cycle of chemotherapy was associated with shorter TTP. These results provide evidence that ctDNA has the potential to be a highly specific early molecular response marker in HGSOC and warrants further investigation in larger cohorts receiving uniform treatment.
Layered metal dichalcogenides have attracted significant interest as a family of single- and few-layer materials that show new physics and are of interest for device applications. Here, we report a ...comprehensive characterization of the properties of tin disulfide (SnS2), an emerging semiconducting metal dichalcogenide, down to the monolayer limit. Using flakes exfoliated from layered bulk crystals, we establish the characteristics of single- and few-layer SnS2 in optical and atomic force microscopy, Raman spectroscopy and transmission electron microscopy. Band structure measurements in conjunction with ab initio calculations and photoluminescence spectroscopy show that SnS2 is an indirect bandgap semiconductor over the entire thickness range from bulk to single-layer. Field effect transport in SnS2 supported by SiO2/Si suggests predominant scattering by centers at the support interface. Ultrathin transistors show on–off current ratios >106, as well as carrier mobilities up to 230 cm2/(V s), minimal hysteresis, and near-ideal subthreshold swing for devices screened by a high-k (deionized water) top gate. SnS2 transistors are efficient photodetectors but, similar to other metal dichalcogenides, show a relatively slow response to pulsed irradiation, likely due to adsorbate-induced long-lived extrinsic trap states.
A new carboxyl-functionalized covalent organic framework (referred to as COF hereafter, unless otherwise noted) contains aromatic backbones and carboxyl-functionalized nanopores has been synthesized ...and used as a two-dimensional (2D) nanofiller in polyacrylonitrile (PAN) polymer matrix of ultrafiltration (UF) membranes. A series of mixed-matrix UF membranes with various concentrations COF ranging from 0 to 0.8 wt% have been investigated using non-solvent induced phase separation (NIPS) method. The effect of COF concentration has been evaluated on the membrane morphology, intrinsic and mechanical properties, separation performance, and fouling propensity. Increasing COF concentration from 0 to 0.8 wt% could significantly enhance the rejection rate from 3.5 to 81.9 wt% for bovine serum albumin (BSA) and 65.0–99.4 wt% for γ-globulin. Moreover, membrane hydrophilicity greatly increased, with the decrease of water contact angle from 64.4° to 45.3°. Overall, compared to the pristine PAN membrane, the mixed-matrix PAN membrane with 0.8 wt% COF demonstrated high water flux of 940 L m−2 h−1 bar−1, better protein retention rate, thermal stability, mechanical properties, and fouling resistance.
•A new 2D COF was synthesized with carboxylated nanopores.•Mixed-matrix COF/PAN UF membranes were fabricated using non-solvent induced phase separation method.•The COF/PAN membranes showed rejection rate of BSA (81.9%) and γ-globulin (99.4%) along with excellent water permeance (940 L m2 h−1 bar−1).•Only 1.8% BSA was adsorbed on COF/PAN membrane with merely 0.8% COF as fillers, compared to 100% of BSA adsorption on pristine PAN membranes.•The COF/PAN membranes showed significantly enhanced thermal stability and mechanical properties.
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