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.

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.

Selective Access to Functional Fluoroenones via Palladium-Catalyzed Selenofluoroalkylacylation of Terminal Alkynes.

The trifluoromethylacyl group (-COCF3) is an important motif and widely studied in catalysis, medicinal chemistry, and materials science. Herein, a novel palladium-catalyzed selenofluoroalkylacylation of terminal alkynes with commercially available fluoroalkyl anhydride and diorganyl diselenides to afford ß-seleno and aryl/alkyl disubstituted enones under mild conditions is disclosed. In addition, selenodifluoroacetylations and selenoperfluoroacetylations are also suitable for this reaction. Mechanistic studies reveal that this reaction proceeds via an oxidative radical-polar crossover process.

Efficacy and safety of thrombopoietin receptor agonists in solid tumors with chemotherapy-induced thrombocytopenia: a meta-analysis.

OBJECTIVE: To evaluate the efficacy and safety of thrombopoietin receptor agonists (TPO-RAs) in solid tumors with chemotherapy-induced thrombocytopenia (CIT). METHODS: We conducted a comprehensive search of PubMed, FMRS, Cochrane Library, Web of Science, EMBASE, and ClinicalTrials.gov for randomized controlled trials (RCTs) reporting the efficacy and safety of TPO-RAs in solid tumors with CIT. The search was limited to articles published before April 30, 2022. Primary outcomes included chemotherapy dose reduction or delays, platelet transfusion, the incidence of grade 3 or 4 thrombocytopenia, and bleeding events. Secondary outcomes encompassed the incidence of platelet count > 400 × 109/L, adverse events (AEs), serious AEs, thrombosis, and mortality. RESULTS: Our analysis encompassed six studies: five rigorous RCTs and one unique study comparing romiplostim to an observation group, involving a total of 489 patients. For primary outcomes, TPO-RAs significantly reduced the incidence of grade 3 or 4 thrombocytopenia (RR = 0.69, 95% CI: 0.52-0.91). After applying the Bonferroni correction for multiple comparisons, the significance of the reduction in grade 3 or 4 thrombocytopenia incidence persisted (P = 0.008). TPO-RAs showed no significant impact on chemotherapy dose reduction or delays (RR = 0.81, 95% CI: 0.65-1.01), platelet transfusion (RR = 1.04, 95% CI: 0.48-2.27), or bleeding events (RR = 0.50, 95% CI: 0.23-1.10). In terms of safety, there were no significant difference in the incidence of any AEs (RR = 0.98, 95% CI:0.92-1.04), serious AEs (RR = 0.79, 95% CI:0.45-1.40), thrombotic events (RR = 1.20, 95% CI:0.51-2.84) and mortality (RR = 1.15, 95% CI:0.55-2.41). CONCLUSIONS: This meta-analysis suggests that TPO-RAs are generally well-tolerated. However, their efficacy in solid tumors with CIT appears limited, as they only demonstrate a reduction in the incidence of grade 3 or 4 thrombocytopenia.

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 real-world analysis of survival and cost-effectiveness of sintilimab plus bevacizumab biosimilar regimen in patients with advanced hepatocellular carcinoma.

PURPOSE: Programmed death-1 (PD-1) inhibitor sintilimab plus bevacizumab has been approved as the first-line treatment for patients with advanced hepatocellular carcinoma (aHCC). However, the clinical benefits of sintilimab plus bevacizumab in a real-world setting in China is insufficiently defined to date. This study aims to evaluate the efficacy and cost-effectiveness of sintilimab plus bevacizumab biosimilar in a real-word cohort of patients with aHCC from China. METHODS: We reviewed the clinical data of 112 consecutive patients with aHCC who received sintilimab plus bevacizumab as a first-line treatment in Chongqing University Cancer hospital between July, 2021 and December, 2022. Overall survival, progression-free survival, overall response rate, and adverse event rates were assessed based on the RECIST 1.1. The survival curves were grafted by Kaplan-Meier method. RESULTS: Sixty-eight patients with aHCC were included our study. Efficacy evaluation results showed that 8 patients were partial remission, 51 patients were stable and 9 patients showed progression disease. Median overall survival and progression-free survival were 344.00 (168.77-419.23) days and 238.00 (174.56-301.44) days, respectively. Adverse events occurred in 35 patients (51.5%), including 9 patients with grade ≥ 3. The life-year (LY) and quality-adjusted LY (QALY) were 1.97 and 2.92, respectively, with a cost of $35,018. CONCLUSION: Our data confirmed the promising efficacy, tolerable toxicity and cost-effectiveness in Chinese patients with aHCC who received sintilimab plus bevacizumab as the first-line therapy regimen in real-world practice.

A low-fouling electrochemical biosensor for biomarker detection in serum based on designed α/ß-peptides with anti-enzymolysis and antifouling capabilities.

The zwitterionic peptides, especially those composed of glutamic (E) and lysine (K) groups have drawn enormous attention as antifouling biomaterials owing to their strong hydration capability and biocompatibility. However, the susceptibility of α-amino acid K to the proteolytic enzymes in human serum limited the broad application of such peptides in biological media. Herein, a new multifunctional peptide with favorable stability in human serum was designed, and it was composed of three sections with immobilizing, recognizing and antifouling capabilities, respectively. The antifouling section was composed of alternating E and K amino acids, but the enzymolysis-susceptive amino acid α-K was replaced by the unnatural ß-K. Compared with the conventional peptide composed of all α-amino acids, the α/ß-peptide exhibited significantly enhanced stability and longer antifouling performance in human serum and blood. The electrochemical biosensor based on the α/ß-peptide showed a favorable sensitivity to its target IgG, with a quite wide linear range from 100 pg mL-1 to 10 µg mL-1 and a low detection limit (33.7 pg mL-1, S/N = 3), and it was promising for the detection of IgG in complex human serum. The tactic of designing antifouling α/ß-peptides offered an efficient way to develop low-fouling biosensors with robust operation in complex body fluids.

Antifouling improvement in Pb2+ ion selective electrodes by using an environmentally friendly capsaicin derivative.

Biofouling is a critical issue for ion selective electrodes (ISE) in complex aqueous systems, seriously compromising the analytical performance of the electrodes (i.e., stability, sensitivity, and lifetime). Herein, an antifouling solid lead ion selective electrode (GC/PANI-PFOA/Pb2+-PISM) was successfully prepared by adding propyl 2-(acrylamidomethyl)-3,4,5-trihydroxy benzoate (PAMTB), an environmentally friendly capsaicin derivative, into the ion-selective membrane (ISM). The presence of PAMTB caused no loss in the detection performance of GC/PANI-PFOA/Pb2+-PISM (e.g., detection limit (1.9 × 10-7 M), response slope (28.5 ± 0.8 mV/decade), the response time (20 s), stability (8.6 ± 2.9 µV/s), selectivity and no water layer), whilst imparting an excellent antifouling effect with an antibacterial rate of 98.1% when the content of PAMTB in the ISM was 2.5 wt%. Further, GC/PANI-PFOA/Pb2+-PISM maintained stable antifouling properties, excellent potential response, and stability even after soaking in a high-concentration bacterial suspension for 7 days.

Antifouling zwitterionic peptide hydrogel based electrochemical biosensor for reliable detection of prostate specific antigen in human serum.

An electrochemical biosensor based on the antifouling zwitterionic peptide hydrogel (CFEFKFC) and the poly(3,4-ethylenedioxythiophene) (PEDOT) was fabricated to accurately detect prostate specific antigen (PSA) in complex human serum. The electrode was modified with the conducting polymer PEDOT and gold nanoparticles (AuNPs) in sequence through electrodeposition, and then the designed zwitterionic peptide hydrogel prepared through self-assembly was immobilized onto the modified electrode surface via the Au-S bond. The zwitterionic peptide hydrogel with cysteine terminal is easy for immobilization onto the gold surface, and it is also suitable for the immobilization of biomolecules such as PSA antibody in this work, through the formation of covalent amide bonds. The peptide hydrogel possessed excellent antifouling property, and it was able to effectively prevent the adsorption of nonspecific proteins, cells and other biomolecules. The developed antifouling biosensor showed a linear response range from 0.1 ng mL-1 to 100 ng mL-1, with a low limit of detection down to 5.6 pg mL-1. These results encourage the wide use of zwitterionic peptide hydrogels as antifouling materials in various sensing and bio-sensing devices.

Syn-Selective Chlorosulfonylation of Alkynes via a Copper-Powder-Initiated Atom Transfer Radical Addition Reaction and Mechanistic Studies.

Copper-powder-catalyzed syn-selective chlorosulfonylation of readily available alkynes by an atom transfer radical addition (ATAR) process has been developed, providing straightforward access to a broad range of (Z)-ß-chlorovinylsulfones in good yields under mild conditions. In addition, this method is ligand-free and features excellent stereoselectivity and high atom economy. Moreover, the product was obtained without an apparent loss of yield when the reaction was performed on the gram scale at a low catalyst loading. In this reaction, the copper powder not only acts as a sulfone radical initiator but also produces the catalytically active CuCl species. Mechanistic investigations and DFT calculation studies revealed that the stereoselectivity is controlled by the thermodynamic stabilities of the in situ-generated cyclic alkenyl CuII complex intermediate, which can serve as a chlorine atom transfer agent.

Effect of concentration of glycidol on the properties of resorcinol-formaldehyde aerogels and carbon aerogels.

By using glycidol as a catalyst, high porosity, low-density resorcinol (R) and formaldehyde (F) aerogels and carbon aerogels (CAs) were synthesized via a sol-gel method. The effect of glycidol and water on the color, density, morphology, textual characteristics and adsorption properties of the resultant RF aerogels and CAs were investigated in detail. The results revealed that the properties of RF aerogels and CAs can be controlled by adjusting the amount of glycidol and water. The resultant RF aerogels and CAs were porous materials, the minimum densities of RF aerogels and CAs were 96 and 110 mg cm-3 respectively while the maximum specific surface areas of RF aerogels and CAs were 290 and 597 m2 g-1. The maximum adsorption capacity of CAs was about 125 mg g-1 on Rhodamine B, which was higher than that of some reported CAs catalyzed by base and acid catalysts. The sol-gel mechanisms of RF aerogels and CAs can be attributed to the opening of the epoxy group of glycidol in the mixture of R and F.

Tumor-induced erythroid precursor-differentiated myeloid cells mediate immunosuppression and curtail anti-PD-1/PD-L1 treatment efficacy.

Despite the unprecedented success of immune checkpoint inhibitors (ICIs) as anti-cancer therapy, it remains a prevailing clinical need to identify additional mechanisms underlying ICI therapeutic efficacy and potential drug resistance. Here, using lineage tracking in cancer patients and tumor-bearing mice, we demonstrate that erythroid progenitor cells lose their developmental potential and switch to the myeloid lineage. Single-cell transcriptome analyses reveal that, notwithstanding quantitative differences in erythroid gene expression, erythroid differentiated myeloid cells (EDMCs) are transcriptionally indistinguishable from their myeloid-originated counterparts. EDMCs possess multifaceted machinery to curtail T cell-mediated anti-tumor responses. Consequently, EDMC content within tumor tissues is negatively associated with T cell inflammation for the majority of solid cancers; moreover, EDMC enrichment, in accordance with anemia manifestation, is predictive of poor prognosis in various cohorts of patients undergoing ICI therapy. Together, our findings reveal a feedforward mechanism by which tumors exploit anemia-triggered erythropoiesis for myeloid transdifferentiation and immunosuppression.

Access to gem-Dibromoenones Enabled by Carbon-Centered Radical Addition to Terminal Alkynes in Water Solution.

We herein report a novel and more practical approach to prepare gem-dibromoenones from terminal alkynes, tetrabromomethane (CBr4), and water in a single step. Mechanistic studies reveal that the generation of a tribromomethyl radical with the assistance of a persulfate salt (K2S2O8) is essential to this transformation. The reaction features readily available chemicals, a broad substrate scope, a green solvent, and mild reaction conditions, providing an efficient alternative for construction of halogen-substituted enones.

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.

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.

Oxidative dehydrogenation of hydrazines and diarylamines using a polyoxomolybdate-based iron catalyst.

We report an efficient method for the oxidative dehydrogenation of hydrazines and diarylamines in aqueous ethanol using Anderson-type polyoxomolybdate-based iron(iii) as a catalyst and hydrogen peroxide as an oxidant. A series of azo compounds and tetraarylhydrazines were obtained in moderate to excellent yields. The reaction conditions and substrate scopes are complementary or superior to those of more established protocols. In addition, the catalyst shows good stability and reusability in water. The preliminary mechanistic studies suggest that a radical process is involved in the reaction.

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.

Metal-Free Radical Thiocyanatosulfonation of Terminal Alkynes in Aqueous Medium.

Here we report a novel and practical approach for preparing (E)-ß-(thiocyanato)vinyl sulfones through the 1,2-thiocyanatosulfonation of terminal alkynes with NH4SCN and sulfonyl hydrazides. Advantages of this reaction include mild conditions, the absence of metal, readily available reagents, a broad substrate scope, good functional group compatibility, and excellent stereoselectivity. The radical species-induced pathway is also demonstrated by mechanistic studies.

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.

Tumor suppressor role of sFRP­4 in hepatocellular carcinoma via the Wnt/ß­catenin signaling pathway.

Hepatocellular carcinoma (HCC) is a malignant tumor located in the liver. Secreted frizzled­related protein 4 (sFRP­4) is associated with cancer occurrence, but the relationship between sFRP­4 and HCC is not completely understood. The present study aimed to investigate the role and mechanism underlying sFRP­4 in HCC. sFRP­4 mRNA expression levels were determined via reverse transcription­quantitative PCR and immunohistochemistry. The Cell Counting Kit­8 assay was performed to evaluate HCCLM3 and Huh7 cell viability. Moreover, HCCLM3 and Huh7 cell proliferation were assessed using the BrdU ELISA assay kit, and cell apoptosis was measured via flow cytometry. Western blotting was conducted to measure ß­catenin and GSK­3ß protein expression levels. The results demonstrated that sFRP­4 expression was significantly downregulated in HCC tissues and cells compared with adjacent healthy tissues and MIHA cells, respectively. Moreover, the results indicated that compared with the control group, sFRP­4 overexpression inhibited HCC cell viability and proliferation, and accelerated HCC cell apoptosis. Furthermore, the results suggested that sFRP­4 inhibited the Wnt/ß­catenin signaling pathway by upregulating GSK­3ß expression and downregulating ß­catenin expression, thus restraining the malignant behavior of HCC cells. In conclusion, the present study indicated that sFRP­4 served a tumor suppressor role in HCC cells by restraining the Wnt/ß­catenin signaling pathway.