In Situ Photodeposition of Gold Nanoparticles with Exposed High-Activity Crystal Facets under Different Sacrificial Agents.

In situ photodeposition presents a powerful approach for integrating noble metal co-catalysts onto semiconductor surfaces. However, achieving precise control over the microstructure of the deposited co-catalyst remains a major challenge. Au nanoparticles (NPs) are deposited onto H-KCNO using HAuCl4 in the presence of various sacrificial agents in this study. Notably, the choice of sacrificial agent decisively influences the exposed crystal facets, loaded content, and particle size of the deposited Au NPs. Importantly, in situ photodeposition under an ethanol solution facilitates the exposure of the highly active (111) and (220) crystal facets of Au. The introduction of Au NPs significantly enhances photocatalytic hydrogen evolution, achieving rates of 4.93, 57.88, and 15.44 µmol/h for H-KCNO/Au-(water, ethanol, and lactic acid), respectively. The observed photocatalytic activity for hydrogen evolution indicates that the exposure of the highly active planes emerges as critical for significant performance enhancement. Photoelectrochemical and photoluminescence measurements suggest that the highly active (111) and (220) crystal facets effectively segregate sites for redox reactions, thereby impeding the recombination of photogenerated electron-hole pairs.

Epidemiologic characteristics of high-risk HPV and the correlation between multiple infections and cervical lesions.

BACKGROUND: The aim of this study was to determine the prevalence of high-risk human papillomavirus (HR-HPV) and the correlation between multiple infections and cervical lesions. METHODS: The current study involved population-based sample of 20,059 women who underwent cervical screening for 15 HR-HPV genotypes with ThinPrep cytologic test (TCT) results. The correlation between multiple HPV genotype infections and cervical lesions was also determined. The odds ratios (ORs) were calculated to assess co-infection patterns for each genotype with 15 other genotypes and the additive statistical interactions were evaluated. RESULTS: There was a bimodal pattern among multiple HPV infections, with a peak in the younger group and a second peak in the elderly group. Indeed, most multiple HPV genotypes exhibited a bimodal pattern. The most common HPV type in patients with high-grade squamous intraepithelial lesions (HSILs) was HPV-16, followed by HPV-52, HPV-58, and HPV-33. The most frequent HPV type in patients with cervical cancer was HPV-16, followed by HPV-58 and HPV-33. Women with multiple infections were at a increased risk of low-grade squamous intraepithelial lesions [LSIL] (OR = 2.01; 95% CI 1.38-2.93) and HSIL (OR 2.28; 95% CI 1.36-3.81) when compared to women with single infections. patients with cervical cancer had the higher percentage of multiple HPV infections. Based on the data herein, we suggest that HPV-33 and HPV-58 may also be high-risk HPV types worthy of increased surveillance and follow-up. CONCLUSION: Our findings suggested that the association between multiple HPV infections and HSIL and LSIL are stronger compared to single HPV infections. There may be some specific combinations that synergistically affected the risk of HSIL and LSIL.

A Nanocrystal Catalyst Incorporating a Surface Bound Transition Metal to Induce Photocatalytic Sequential Electron Transfer Events.

Heterogeneous photocatalysis is less common but can provide unique avenues for inducing novel chemical transformations and can also be utilized for energy transductions, i.e., the energy in the photons can be captured in chemical bonds. Here, we developed a novel heterogeneous photocatalytic system that employs a lead-halide perovskite nanocrystal (NC) to capture photons and direct photogenerated holes to a surface bound transition metal Cu-site, resulting in a N-N heterocyclization reaction. The reaction starts from surface coordinated diamine substrates and requires two subsequent photo-oxidation events per reaction cycle. We establish a photocatalytic pathway that incorporates sequential inner sphere electron transfer events, photons absorbed by the NC generate holes that are sequentially funneled to the Cu-surface site to perform the reaction. The photocatalyst is readily prepared via a controlled cation-exchange reaction and provides new opportunities in photodriven heterogeneous catalysis.

Dual-cation-doped MoS2nanosheets accelerating tandem alkaline hydrogen evolution reaction.

Molybdenum disulfide (MoS2) nanosheets are promising candidates as earth-abundant and low-cost catalyst for hydrogen evolution reaction (HER). Nevertheless, compared with the benchmark Pt/C catalyst, the application of MoS2nanosheets is limited to its relatively low catalytic activity, especially in alkaline environments. Here, we developed a dual-cation doping strategy to improve the alkaline HER performance of MoS2nanosheets. The designed Ni, Co co-doped MoS2nanosheets can promote the tandem HER steps simultaneously, thus leading to a much enhanced catalytic activity in alkaline solution. Density functional theory calculations revealed the individual roles of Ni and Co dopants in the catalytic process. The doped Ni is uncovered to be the active site for the initial water-cleaving step, while the Co dopant is conducive to the H desorbing by regulating the electronic structure of neighboring edge-S in MoS2. The synergistic effect resulted by the dual-cation doping thus facilitates the tandem HER steps, providing an effective route to raise the catalytic performance of MoS2materials in alkaline solution.

Optimization of aperiodic 3D optical phased arrays based on multilayer Si3N4/SiO2 platforms.

Silicon-based optical phased arrays (OPAs) have been widely explored, while the design of the structure with high sidelobe level reduction, remains a big challenge. This work investigated the optimization of the optical path-modulated 3D OPAs with Si3N4 as the core layer and SiO2 as the cladding layer. We used the particle swarm optimization algorithm to optimize high-performance random distributed OPAs. Our study provides an effective pathway to optimize the random distributed OPAs within a controllable time frame among a vast number of parameters.

Stable Pb(II) ion-selective electrodes with a low detection limit using silver nanoparticles/polyaniline as the solid contact.

Solid contact-based ion-selective electrodes (SC-ISEs) based on silver nanoparticles/polyaniline (Ag@PANI) as the solid contact (SC) were successfully prepared. The Ag@PANI SC showed high capacitance and excellent electron transport performance. Owing to the synergetic effects of the Ag nanoparticles and PANI, a GC/Ag@PANI-II/Pb2+-ISE (where II refers to a Ag content of 0.01 wt% in the SC layer) showed a low Pb2+ detection limit (6.31 × 10-10 M) with a slope of 29.1 ± 0.3 mV/dec, a fast response (< 5 s), and high stability. GC/Ag@PANI-II/Pb2+-ISE exhibited a Nernstian response for Pb2+ ions over a wide concentration range (10-3 to 10-9 M). After a 3-week operation, GC/Ag@PANI-II/Pb2+-ISE responded linearly to Pb2+ over the range of 10-7-10-3 M, demonstrating good long-term potential stability. Furthermore, the electrode showed excellent reproducibility and repeatability of the potential values and was successfully applied to detect the Pb2+ concentration in real samples with a recovery of 97 - 109%. Results suggest that Ag@PANI composites offer good transducer performance in trace ion detection sensors.

Rationally designed C/Co9S8@SnS2 nanocomposite as a highly efficient anode for lithium-ion batteries.

Nanostructured transition metal sulfides are promising anode materials for lithium-ion batteries. Nevertheless, it is still a great challenge to prepare capacity-improved electrodes without reducing their rate capability and cycle stability. In this paper, we present a C/Co9S8@SnS2 composite material by loading SnS2 nanocrystals onto MOF-derived C/Co9S8 nanostructures. The C/Co9S8@SnS2 composite has multiple active sites to store lithium ions. The specific capacity reaches 3.1 mAh cm-2 when the current density is 0.224 mA cm-2. The asynchronous electrochemical reaction between Co9S8 and SnS2 offsets the volume expansion of the anode material. Meanwhile, the compact adhesion of carbon layers on the interfaces suppresses the destruction of the anode during the charging-discharging processes. Consequently, the synthesized electrode presents favorable capacity with high current density or under long-term cycling conditions. The prepared battery has a reversible specific capacity of 0.452 mAh cm-2 and a coulomb efficiency of 99.7% after 500 cycles with a high current density of 2.24 mA cm-2. The research results obtained in this work provides a feasible strategy to improve the performance of electrodes systematically.

Effect of bandgap alignment on the photoreduction of CO2 into methane based on Cu2O-decorated CuO microspheres.

Semiconductors' band gap alignment is important for the photoreduction of CO2 to methane. In the paper, two kinds of Cu2O-decorated CuO microspheres composed with nanoflakes were prepared by using two different methods. Their electron behaviors were studied from the XPS spectra and photoelectrochemical measurements. Both samples are p-type CuO covered with an amount of Cu2O nanoparticles on their surface. Combined with their bandgaps and flat band potentials, CuO-Mic has a well-matched bandgap alignment between Cu2O and CuO, which is favorable for the separation of photogenerated electron-hole pairs. Those photogenerated carriers are beneficial for the conversion of CO2 to CH4, as an 8-electron process for the conversion of CO2 to CH4 will consume more photogenerated electrons for the chemical reactions than that of the 2-electron process for CO2 reduction to CO. Therefore, CuO-Mic has much better photocatalytic activity for CO2 reduction to CH4 with a CH4 yield ten times higher than that of CuO-Hyd under a visible light irradiation, the CO yields of the CO2 reduction are identical.

Effect of Comorbidity on Outcomes of Patients with Advanced Non-Small Cell Lung Cancer Undergoing Anti-PD1 Immunotherapy.

BACKGROUND Comorbidities are reportedly related to the survival of patients with non-small cell lung cancer (NSCLC). The purpose of this study was to explore the impact of comorbidity, assessed by the Charlson comorbidity index (CCI) and the simplified comorbidity scores (SCS) on clinical outcomes of patients with NSCLC treated with immune checkpoint inhibitors. MATERIAL AND METHODS Sixty-six patients with NSCLC who received programmed cell death protein 1 (PD1) inhibitors in our institution in the past 2 years were enrolled in this retrospective study. Data on comorbidity (CCI and SCS) and clinical outcomes, including progression-free survival (PFS), immunotherapy responses, and immunotherapy-related adverse events, were analyzed. RESULTS The disease control rate was obviously higher among patients in the CCI <1 group than the CCI ≥1 group (P<0.001), but were similar between the SCS <8 group and SCS ≥8 group (P=0.585). The median PFS in the CCI <1 group was 271.0 days (95% CI: 214.3-327.7 days) compared with 232.0 days (95% CI: 66.2-397.8 days) for the CCI ≥1 group (P=0.0084). However, the median PFS showed no difference between the groups with SCS <8 at 271.0 days (95% CI: 138.7-403.3 days) versus SCS ≥8 at 222.0 days (95% CI: 196.2-247.8 days), P=0.2106). The incidence of adverse events was similar among patients with high versus low comorbidity indexes (CCI: 35.8% versus 23.6%, P=0.286, respectively; and SCS: 28.0% versus 29.3%, respectively, P=0.912). CONCLUSIONS The comorbidity burden might be a predictor for survival in patients with NSCLC undergoing PD1 inhibitor immunotherapy.

Influence of Hypertension on the Survival of Non-Small Cell Lung Cancer Patients with Type 2 Diabetes Mellitus.

BACKGROUND Hypertension and diabetes mellitus (DM) are both the risk factors for cancer. This study aimed to explore the prognostic value of fasting blood glucose (FBG) and hypertension in type 2 DM (T2DM) patients with advanced non-small cell lung cancer (NSCLC) who had received chemotherapy treatment. MATERIAL AND METHODS There were 181 advanced NSCLC patients with T2DM between 2010 and 2019 included in this study. Their laboratory and clinical data were retrospectively analyzed. The predictive value of FBG and hypertension was evaluated. The Kaplan-Meier method was used to evaluate progression-free survival (PFS). RESULTS The median PFS was 168.0 days (95% CI: 137.9-198.7 days) in patients with FBG ≥7 mmol/L compared to 154.0 days (95% CI: 126.7-181.3 days) for patients with FBG <7 mmol/L (hazard ratio [HR]=1.054; 95% CI: 0.7669-1.452; P=0.7447). Median PFS was longer in non-hypertensive patients than in hypertensive patients [179.0 days (95% CI: 137.3-220.7 days) versus 128.0 days (95% CI: 96.3-159.7 days); P=0.0189]. The existence of hypertension (HR=1.478; 95% CI: 1.063-2.055; P=0.020) was an independent predictor for shorter PFS in the multivariate analysis. Decreased hemoglobin was the major adverse event (over 95% patients). The incidence of all grades of adverse reactions was similar between hypertensive and non-hypertensive patients (all P>0.05) except diarrhea (P=0.020). CONCLUSIONS Complication of hypertension might confer a poor survival for advanced NSCLC patients with T2DM. Further prospective research is needed to confirm these findings.

Organo-selenium mediated regio- and stereoselective iodoselenylation of alkynes in an aqueous medium: simple access to (E)-ß-iodoalkenyl selenides.

A method for the simple and efficient iodoselenylation of simple alkynes under mild conditions using commercially available molecular iodine (I2) and diorganoyldiselenides as starting materials has been developed. A broad range of alkynes can be employed to afford (E)-ß-iodoalkenyl selenides in good to excellent yields and with high regio- and stereoselectivity without the need for any protecting groups.

Iodine-mediated regio- and stereoselective iodothiocyanation of alkynes in aqueous ethanol.

Iodothiocyanation of alkynes with ammonium thiocyanate (NH4SCN) and molecular iodine (I2) has been demonstrated in aqueous ethanol, which enables efficient synthesis of a series of functional ß-iodo vinylthiocyanates in good to excellent yields under mild reaction conditions without the need for any protection.

First-Row Transition Metal Based Catalysts for the Oxygen Evolution Reaction under Alkaline Conditions: Basic Principles and Recent Advances.

Owing to its abundance, high gravimetric energy density, and environmental friendliness, hydrogen is a promising renewable energy to replace fossil fuels. One of the most prominent routes toward hydrogen acquisition is water splitting, which is currently bottlenecked by the sluggish kinetics of oxygen evolution reaction (OER). Numerous of electrocatalysts have been developed in the past decades to accelerate the OER process. Up to now, the first-row transition metal based compounds are in pole position under alkaline conditions, which have become subjects of extensive studies. Recently, significant advances in providing compelling catalytic performance as well as exploring their catalytic mechanisms have been achieved in this area. In this review, we summarized the fundamentals and recent progresses in first-row transition metal based OER catalysts, with special emphasis on the pathways of promoting catalytic performance by concrete strategies. New insight into material design, particularly the role of experimental approaches in the electrocatalytic performance and reaction mechanisms of OER are expected to be provided.

CTAB-Assisted Fabrication of Bi2WO6 Thin Nanoplates with High Adsorption and Enhanced Visible Light-Driven Photocatalytic Performance.

Two-dimensional thin Bi2WO6 nanoplates have been fabricated using a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal method. We investigated the proposed formation mechanism based on the crystalline structures of the thin Bi2WO6 nanoplates. The high adsorption ability and excellent visible-light driven photocatalytic activities of the Bi2WO6 nanoplates were illustrated, in view of exposed (001) facets of nanoplates possessing faster separation of photo-generated charge carriers and increased catalytically active sites. Such a cost-effective way to obtain Bi2WO6 nanoplates offers new possibilities for the design of adsorptive semiconductor photocatalysts with strengthened photocatalytic activities.

Green and Tunable Decoration of Graphene with Spherical Nanoparticles Based on Laser Ablation in Water: A Case of Ag Nanoparticle/Graphene Oxide Sheet Composites.

A simple and green strategy is presented to decorate graphene with nanoparticles, based on laser ablation of targets in graphene auqeous solution. Ag and graphene oxide (GO) are chosen as model materials. The surface of GO sheets is strongly anchored with spherical Ag nanoparticles. The density and size of the Ag nanoparticles can be easily tuned by laser ablation conditions. Further, the GO sheets can be decorated with other nanoparticles from simple metals or semiconductors to multicomponent hybrids. Additionally, the Ag nanoparticle/GO sheet colloids can be utilized as blocks to build three-dimensional structures, such as sandwich membranes by evaporation-induced self-assembly. These graphene-based composite materials could be very useful in catalysis, sensors, and nanodevices. Particularly, the Ag nanoparticle/GO sheet sandwich composite membranes exhibit excellent surface-enhanced Raman scattering performance and possess the huge potential in trace-detecting persistent organic pollutants in the environment.

Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behavior on HOPG Surface.

Taking advantage of a continuous-flow apparatus, the iridium(III)-containing polytungstate cluster K12Na2H2[Ir2Cl8P2W20O72]·37H2O (1) was obtained in a reasonable yield (13% based on IrCl3·H2O). Compound 1 was characterized by Fourier transform IR, UV-visible, (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis measurements. (31)P NMR, ESI-MS, and elemental analysis all indicated 1 was a new polytungstate cluster compared with the reported K14[(IrCl4)KP2W20O72] compound. Intriguingly, the successful isolation of 1 relied on the custom-built flow apparatus, demonstrating the uniqueness of continuous-flow chemistry to achieve crystalline materials. The catalytic properties of 1 were assessed by investigating the activity on catalyzing the electro-oxidation of ruthenium tris-2,2'-bipyridine [Ru(bpy)3](2+/3+). The voltammetric behavior suggested a coupled catalytic behavior between [Ru(bpy)3](3+/2+) and 1. Furthermore, on the highly oriented pyrolytic graphite surface, 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) was used as the two-dimensional host network to coassemble cluster 1; the surface morphology was observed by scanning tunneling microscope technique. "S"-shape of 1 was observed, indicating that the cluster could be accommodated in the cavity formed by two TCDB host molecules, leading to a TCDB/cluster binary structure.

sFRP-4, a potential novel serum marker for chronic hepatitis B-related hepatocellular carcinoma.

BACKGROUND: The current methods used for diagnosing hepatocellular carcinoma (HCC) are unsatisfactory. Here, we assessed the serum levels of secreted frizzled related protein 4 (sFRP-4) for diagnosing HCC in patients infected with chronic hepatitis B (CHB). METHODS: In 272 patients with CHB enrolled, 142 were patients with HCC. Thirty-three healthy subjects were recruited as healthy controls. The CHB patients were assigned to a test group or a validation group based on the time of enrollment. Human antibody arrays were used to screen 15 patients (8 CHB-related HCC patients, 7 CHB patients) for serum markers. Four markers and one candidate marker were assessed in the test group and validation group, respectively. RESULTS: Human antibody assays indicated that the serum levels of sFRP-4 in HCC patients were significantly higher than those in CHB patients (P<0.05). Additionally, serum sFRP-4 levels were significantly higher in the HCC patients than those in the non-HCC patients in both test group (79.7 vs 41.3 ng/mL; P<0.001) and validation group (89.0 vs 39.0 ng/mL; P<0.001). Areas under the Receiver Operating Characteristic curves (AUCs) for alpha-fetoprotein (AFP) and sFRP-4 were similar in both test group and validation group. In the test group, the combination of sFRP-4 (a sensitivity of 94.4%, a specificity of 60.5% at 46.4 ng/mL) and AFP (a sensitivity of 75.0%, a specificity of 87.2% at 11.3 ng/mL) showed better performance for diagnosing HCC (a sensitivity of 79.2% and a specificity of 95.3%). The AUC for combined sFRP-4 and AFP increased to 0.941 (95% CI: 0.908-0.975), and similar results were seen in the validation group. CONCLUSION: sFRP-4 is a candidate serum marker for diagnosing HCC in CHB patients, and the combination of sFRP-4 with AFP may improve the diagnostic accuracy of HCC.

Performance of several simple, noninvasive models for assessing significant liver fibrosis in patients with chronic hepatitis B.

AIM: To compare the performance of several simple, noninvasive models comprising various serum markers in diagnosing significant liver fibrosis in the same sample of patients with chronic hepatitis B (CHB) with the same judgment standard. METHODS: A total of 308 patients with CHB who had undergone liver biopsy, laboratory tests, and liver stiffness measurement (LSM) at the Southwest Hospital, Chongqing, China between March 2010 and April 2014 were retrospectively studied. Receiver operating characteristic (ROC) curves and area under ROC curves (AUROCs) were used to analyze the results of the models, which incorporated age-platelet (PLT) index (API model), aspartate transaminase (AST) to alanine aminotransferase (ALT) ratio (AAR model), AST to PLT ratio index (APRI model), γ-glutamyl transpeptidase (GGT) to PLT ratio index (GPRI model), GGT-PLT-albumin index (S index model), age-AST-PLT-ALT index (FIB-4 model), and age-AST-PLT-ALT-international normalized ratio index (Fibro-Q model). RESULTS: The AUROCs of the S index, GPRI, FIB-4, APRI, API, Fibro-Q, AAR, and LSM for predicting significant liver fibrosis were 0.726 (P<0.001), 0.726 (P<0.001), 0.621 (P=0.001), 0.619 (P=0.001), 0.580 (P=0.033), 0.569 (P=0.066), 0.495 (P=0.886), and 0.757 (P<0.001), respectively. The S index and GPRI had the highest correlation with histopathological scores (r=0.373, P<0.001; r=0.372, P<0.001, respectively) and LSM values (r=0.516, P<0.001; r=0.513, P<0.001, respectively). When LSM was combined with S index and GPRI, the AUROCs were 0.753 (P<0.001) and 0.746 (P<0.001), respectively. CONCLUSION: S index and GPRI had the best diagnostic performance for significant liver fibrosis and were robust predictors of significant liver fibrosis in patients with CHB for whom transient elastography was unavailable.

A stretchable wearable sensor with dual working electrodes for reliable detection of uric acid in sweat.

Wearable sweat sensors with stretch capabilities and robust performances are desired for continuous monitoring of human health, and it remains a challenge for sweat sensors to detect targets reliably in both static and dynamic states. Herein, a flexible sweat sensor was created using a cost-effective approach involving the utilization of three-dimensional graphene foam and polydimethylsiloxane (PDMS). The flexible electrochemical sensor was fabricated based on PDMS and Pt/Pd nanoparticles modified 3D graphene foam for the detection of uric acid in sweat. Pt/Pd nanoparticles were electrodeposited on the graphene foam to markedly enhance the electrocatalytic activity for uric acid detection. The graphene foam with excellent electrical property and high porosity, and PDMS with an ideal mechanical property endow the sensing device with high stretchability (tolerable strain up to 110 %), high sensitivity (0.87 µA µM-1 cm-2), and stability (remaining unchanged for more than 5000 cycles) for daily wear. To eliminate possible interferences, the wearable sensor was designed with dual working electrodes, and their response difference ensured reliable and accurate detection of targets. This strategy of constructing sweat sensors with dual working electrodes based on the flexible composite material represents a promising way for the development of robust wearable sensing devices.

An antifouling electrochemical biosensor based on oxidized bacterial cellulose and quaternized chitosan for reliable detection of involucrin in wound exudate.

The monitoring of biomarkers in wound exudate is of great importance for wound care and treatment, and electrochemical biosensors with high sensitivity are potentially useful for this purpose. However, conventional electrochemical biosensors always suffer from severe biofouling when performed in the complex wound exudate. Herein, an antifouling electrochemical biosensor for the detection of involucrin in wound exudate was developed based on a wound dressing, oxidized bacterial cellulose (OxBC) and quaternized chitosan (QCS) composite hydrogel. The OxBC/QCS hydrogel was prepared using an in-situ chemical oxidation and physical blending method, and the proportion of OxBC and QCS was optimized to achieve electrical neutrality and enhanced hydrophilicity, therefore endowing the hydrogel with exceptional antifouling and antimicrobial properties. The involucrin antibody SY5 was covalently bound to the OxBC/QCS hydrogel to construct the biosensor, and it demonstrated a low limit of detection down to 0.45 pg mL-1 and a linear detection range from 1.0 pg mL-1 to 1.0 µg mL-1, and it was capable of detecting targets in wound exudate. Crucially, the unique antifouling and antimicrobial capability of the OxBC/QCS hydrogel not only extends its effective lifespan but also guarantees the sensing performance of the biosensor. The successful application of this wound dressing, OxBC/QCS hydrogel for involucrin detection in wound exudate demonstrates its promising potential in wound healing monitoring.