Crystalline Phase Engineering to Modulate the Interfacial Interaction of the Ruthenium/Molybdenum Carbide for Acidic Hydrogen Evolution.

Ruthenium (Ru) is an ideal substitute to commercial Pt/C for the acidic hydrogen evolution reaction (HER), but it still suffers from undesirable activity due to the strong adsorption free energy of H* (ΔGH*). Herein, we propose crystalline phase engineering by loading Ru clusters on precisely prepared cubic and hexagonal molybdenum carbide (α-MoC/ß-Mo2C) supports to modulate the interfacial interactions and achieve high HER activity. Advanced spectroscopies demonstrate that Ru on ß-Mo2C shows a lower valence state and withdraws more electrons from the support than that of Ru on α-MoC, indicative of a strong interfacial interaction. Density functional theory reveals that the ΔGH* of Ru/ß-Mo2C approaches 0 eV, illuminating an enhancement mechanism at the Ru/ß-Mo2C interface. The resultant Ru/ß-Mo2C exhibits an encouraging performance in a proton exchange membrane water electrolyzer with a low cell voltage (1.58 V@ 1.0 A cm-2) and long stability (500 h@ 1.0 A cm-2).

Chiral Au-Pd Alloy Nanorods with Tunable Optical Chirality and Catalytically Active Surfaces.

Integrating the plasmonic chirality with excellent catalytic activities in plasmonic hybrid nanostructures provides a promising strategy to realize the chiral nanocatalysis toward many chemical reactions. However, the controllable synthesis of catalytically active chiral plasmonic nanoparticles with tailored geometries and compositions remains a significant challenge. Here it is demonstrated that chiral Au-Pd alloy nanorods with tunable optical chirality and catalytically active surfaces can be achieved by a seed-mediated coreduction growth method. Through manipulating the chiral inducers, Au nanorods selectively transform into two different intrinsically chiral Au-Pd alloy nanorods with distinct geometric chirality and tunable optical chirality. By further adjusting several key synthetic parameters, the optical chirality, composition, and geometry of the chiral Au-Pd nanorods are fine-tailored. More importantly, the chiral Au-Pd alloy nanorods exhibit appealing chiral catalytic activities as well as polarization-dependent plasmon-enhanced nanozyme catalytic activity, which has great potential for chiral nanocatalysis and plasmon-induced chiral photochemistry.

Tuning the Plexcitonic Optical Chirality Using Discrete Structurally Chiral Plasmonic Nanoparticles.

Constructing chiral plexcitonic systems with tunable plasmon-exciton coupling may advance the scientific exploitation of strong light-matter interactions. Because of their intriguing chiroptical properties, chiral plasmonic materials have shown promising applications in photonics, sensing, and biomedicine. However, the strong coupling of chiral plasmonic nanoparticles with excitons remains largely unexplored. Here we demonstrate the construction of a chiral plasmon-exciton system using chiral AuAg nanorods and J aggregates for tuning the plexcitonic optical chirality. Circular dichroism spectroscopy was employed to characterize chiral plasmon-exciton coupling, in which Rabi splitting and anticrossing behaviors were observed, whereas the extinction spectra exhibited less prominent phenomena. By controlling the number of molecular excitons and the energy detuning between plasmons and excitons, we have been able to fine-tune the plexcitonic optical chirality. The ability to fine-tune the plexcitonic optical chirality opens up unique opportunities for exploring chiral light-matter interactions and boosting the development of emerging chiroptical devices.

Oxygen Functional Groups Regulate Cobalt-Porphyrin Molecular Electrocatalyst for Acidic H2O2 Electrosynthesis at Industrial-Level Current.

Electrosynthesis of hydrogen peroxide (H2O2) based on proton exchange membrane (PEM) reactor represents a promising approach to industrial-level H2O2 production, while it is hampered by the lack of high-efficiency electrocatalysts in acidic medium. Herein, we present a strategy for the specific oxygen functional group (OFG) regulation to promote the H2O2 selectivity up to 92% in acid on cobalt-porphyrin molecular assembled with reduced graphene oxide. In-situ X-ray adsorption spectroscopy, in-situ Raman spectroscopy and Kelvin probe force microscopy combined with theoretical calculation unravel that different OFGs exert distinctive regulation effects on the electronic structure of Co center through either remote (carboxyl and epoxy) or vicinal (hydroxyl) interaction manners, thus leading to the opposite influences on the promotion in 2e- ORR selectivity. As a consequence, the PEM electrolyzer integrated with the optimized catalyst can continuously and stably produce the high-concentration of ca. 7 wt% pure H2O2 aqueous solution at 400 mA cm-2 over 200 h with a cell voltage as low as ca. 2.1 V, suggesting the application potential in industrial-scale H2O2 electrosynthesis.

On-chip non-uniform geometric metasurface for multi-channel wavefront manipulations.

Metasurfaces integrated with waveguides have been recently explored as a means to control the conversion between guided modes and radiation modes for versatile functionalities. However, most efforts have been limited to constructing a single free-space wavefront using guided waves, which hinders the functional diversity and requires a complex configuration. Here, a new, to the best of our knowledge, type of non-uniformly arranged geometric metasurface enabling independent multi-channel wavefront engineering of guided wave radiation is ingeniously proposed. By endowing three structural degrees of freedom into a meta-atom, two mechanisms (the Pancharatnam-Berry phase and the detour phase) of the metasurface are perfectly joined together, giving rise to three phase degrees of freedom to manipulate. Therefore, an on-chip polarization demultiplexed metalens, a wavelength-multiplexed metalens, and RGB-colored holography with an improved information capacity are successively demonstrated. Our results enrich the functionalities of an on-chip metasurface and imply the prospect of advancements in multiplexing optical imaging, augmented reality (AR) holographic displays, and information encryption.

Optical vortex coronagraphy for high-contrast imaging of femtosecond laser filaments.

A high-contrast imaging technique for phase objects based on the optical vortex coronagraph (OVC) is proposed. This method offers the unique advantage of background-free imaging due to the introduction of azimuthal phase in the Fourier plane. We employed the OVC method to detect femtosecond laser-induced air plasma and compared it with the classic diffractometry and fluorescent imaging methods. We achieved a phase sensitivity of ∼0.035 waves that surpassed the capabilities of the other two methods. The combination of this highly sensitive imaging technique with the pump-probe method holds promise for applications in ultrafast imaging of laser-material interactions.

Quantitative evaluation of therapy options for relapsed/refractory diffuse large B-cell lymphoma: A model-based meta-analysis.

New therapies for relapsed/refractory diffuse large B-cell lymphoma (r/rDLBCL) have emerged in recent years, but there have been no comprehensive quantitative comparisons of the efficacy of these therapies. In this study, the efficacy characteristics of 11 types of treatment strategy and 63 treatment regimens were compared by model based meta-analysis. We found that compared with monotherapy, association therapy had significant benefits in terms of overall survival (OS), progression-free survival (PFS), and objective response rate (ORR). However, whereas treatment regimens involving chemotherapy contributed to significant improvements in ORR and PFS, OS was not improved. In terms of treatment strategy, we identified chemotherapy in association with immunotherapy sequential autologous stem cell transplantation (ASCT), the association of two different types of immunotherapies, chemotherapy sequential ASCT, chemotherapy in association with immunotherapy, and chemotherapy in association with two types of immunotherapies as showing better efficacy. With respect to specific treatment regimens, we found that the following had better efficacy: rituximab in association with inotuzumab ozogamicin; rituximab in association with carmustine, etoposide, cytarabine, and melphalan sequential ASCT (R-BEAM+ASCT); lenalidomide in association with rituximab, etoposide, cisplatin, cytarabine, and methylprednisolone; iodine-131 tositumomab in association with BEAM sequential ASCT; and chemotherapy sequential chimeric antigen receptor T-cell immunotherapy, with median OS of 48.2, 34.2, 27.8, 25.8, and 25 months, respectively. Moreover, with respect to association therapy, there was a strong correlation between the 6-month PFS and 2-year OS. The findings of this study provide the necessary quantitative information for clinical practice and clinical trial design for the treatment of r/rDLBCL.

Overall Design of Anode with Gradient Ordered Structure with Low Iridium Loading for Proton Exchange Membrane Water Electrolysis.

Insufficient catalyst utilization, limited mass transport, and high ohmic resistance of the conventional membrane electrode assembly (MEA) lead to significant performance losses of proton exchange membrane water electrolysis (PEMWE). Herein we propose a novel ordered MEA based on anode with a 3D membrane/catalytic layer (CL) interface and gradient tapered arrays by the nanoimprinting method, confirmed by energy dispersive spectroscopy. Benefiting from the maximized triple-phase interface, rapid mass transport, and gradient CL by overall design, such an ordered structure with Ir loading of 0.2 mg cm-2 not only greatly increases the electrochemical active area by 4.2 times but also decreases the overpotentials of both mass transport and ohmic polarization by 13.9% and 8.7%, respectively, compared with conventional MEA with an Ir loading of 2 mg cm-2, thus ensuring a superior performance (1.801 V at 2 A cm-2) and good stability. This work provides a new strategy of designing MEA for high-performance PEMWE.

[Phenotypic and genetic analysis of a Chinese pedigree affected with Oral-facial-digital syndrome].

OBJECTIVE: To explore the clinical phenotype and genetic basis for a Chinese pedigree affected with Oral-facial-digital syndrome type I (OFD1). METHODS: A pedigree with OFD1 who presented at Hebei General Hospital on March 17, 2021 was selected as the subject. Clinical data of the child was collected. Trio-whole exome sequencing (trio-WES) was carried out for the proband and members of her pedigree, and candidate variant was verified by Sanger sequencing. RESULTS: The proband has featured hypotelorism, broad nasal root, flat nasal tip, lobulated tongue, tongue neoplasia, camptodactyly of left fifth finger, syndactyly of right fourth and fifth fingers, and delayed intellectual and language development. Trio-WES revealed that the proband and her daughter, sister and mother have harbored a heterozygous c.224A>G (p.Asn75Ser) variant of the OFD1 gene. The same variant was not found among healthy members from her pedigree. CONCLUSION: The c.224A>G (p.Asn75Ser) variant probably underlay the OFD1 in this pedigree. Above discovery has enriched the spectrum of OFD1 gene variants.

Terahertz Airy beam generated by Pancharatnam-Berry phases in guided wave-driven metasurfaces.

Metasurface antennas scatter traveling guided waves into spatial waves, which act as extendable subsources to overcome the size limitation on emission sources. With the use of a Pancharatnam-Berry phase metasurface stimulated by a circularly polarized wave in a waveguide, the local phase distributions of scattered spatial waves can be made consistent with those of an Airy beam, thereby allowing the generation of high-quality Airy beams. In a slab waveguide, circularly polarized waves are synthesized through superposition of in-plane transverse electric modes. Simulations demonstrate that a 20 mm × 20 mm footprint all-dielectric guided wave-driven metasurface generates a 2D Airy beam at a frequency of 0.6 THz. Furthermore, we employ a metasurface deposited on a strip waveguide to generate a 1D Airy beam under direct stimulation by the fundamental transverse electric mode. Our work not only provides a large-scale emitter, but it also suggests promising potential applications in on-chip imaging and holography.

Facile synthesis of near-infrared responsive on-demand oxygen releasing nanoplatform for precise MRI-guided theranostics of hypoxia-induced tumor chemoresistance and metastasis in triple negative breast cancer.

BACKGROUND: Hypoxia is an important factor that contributes to chemoresistance and metastasis in triple negative breast cancer (TNBC), and alleviating hypoxia microenvironment can enhance the anti-tumor efficacy and also inhibit tumor invasion. METHODS: A near-infrared (NIR) responsive on-demand oxygen releasing nanoplatform (O2-PPSiI) was successfully synthesized by a two-stage self-assembly process to overcome the hypoxia-induced tumor chemoresistance and metastasis. We embedded drug-loaded poly (lactic-co-glycolic acid) cores into an ultrathin silica shell attached with paramagnetic Gd-DTPA to develop a Magnetic Resonance Imaging (MRI)-guided NIR-responsive on-demand drug releasing nanosystem, where indocyanine green was used as a photothermal converter to trigger the oxygen and drug release under NIR irradiation. RESULTS: The near-infrared responsive on-demand oxygen releasing nanoplatform O2-PPSiI was chemically synthesized in this study by a two-stage self-assembly process, which could deliver oxygen and release it under NIR irradiation to relieve hypoxia, improving the therapeutic effect of chemotherapy and suppressed tumor metastasis. This smart design achieves the following advantages: (i) the O2 in this nanosystem can be precisely released by an NIR-responsive silica shell rupture; (ii) the dynamic biodistribution process of O2-PPSiI was monitored in real-time and quantitatively analyzed via sensitive MR imaging of the tumor; (iii) O2-PPSiI could alleviate tumor hypoxia by releasing O2 within the tumor upon NIR laser excitation; (iv) The migration and invasion abilities of the TNBC tumor were weakened by inhibiting the process of EMT as a result of the synergistic therapy of NIR-triggered O2-PPSiI. CONCLUSIONS: Our work proposes a smart tactic guided by MRI and presents a valid approach for the reasonable design of NIR-responsive on-demand drug-releasing nanomedicine systems for precise theranostics in TNBC.

Carbon-Defect-Driven Electroless Deposition of Pt Atomic Clusters for Highly Efficient Hydrogen Evolution.

Pt atomic clusters (Pt-ACs) display outstanding electrocatalytic performance because of their unique electronic structure with a large number of highly exposed surface atoms. However, the small size and large specific surface area intrinsically associated with ACs pose challenges in the synthesis and stabilization of Pt-ACs without agglomeration. Herein, we report a novel one-step carbon-defect-driven electroless deposition method to produce ultrasmall but well-defined and stable Pt-ACs supported by defective graphene (Pt-AC/DG) structures. A theoretical simulation clearly revealed that the defective regions with a lower work function and hence a higher reducing capacity compared to those of normal hexagonal sites triggered the reduction of Pt ions preferentially at the defect sites. Moreover, the strong binding energy between Pt and carbon defects effectively restricted the migration of spontaneously reduced Pt atoms to immobilize/stabilize the resultant Pt-ACs. Electrochemical analyses demonstrated the high performance of Pt-ACs in catalyzing the hydrogen evolution reaction, showing a greatly enhanced mass activity, a high Pt utilization efficiency, and excellent stability compared with commercial Pt/C catalysts. The integration of proton exchange membrane water electrolysis with Pt-AC/DG as a cathode exhibited an excellent hydrogen generation activity and extraordinary stability (during 200 h of electrolysis) with a greatly reduced Pt usage compared with commercial Pt/C catalysts.

Analysis of Time-Course, Dose-Effect, and Influencing Factors of Antidepressants in the Treatment of Acute Adult Patients With Major Depression.

OBJECTIVE: Model-based meta-analysis was used to describe the time-course and dose-effect relationships of antidepressants and also simultaneously investigate the impact of various factors on drug efficacy. METHODS: This study is a reanalysis of a published network meta-analysis. Only placebo-controlled trials were included in this study. The change rate in depression rating scale scores from baseline was used as an efficacy indicator because a continuous variable is more likely to reflect subtle differences in efficacy between drugs. RESULTS: A total 230 studies containing 64 346 patients were included in the analysis. The results showed that the number of study sites (single or multi-center) and the type of setting (inpatient or noninpatient) are important factors affecting the efficacy of antidepressants. After deducting the placebo effect, the maximum pure drug efficacy value of inpatients was 18.4% higher than that of noninpatients, and maximum pure drug efficacy value of single-center trials was 10.2% higher than that of multi-central trials. Amitriptyline showed the highest drug efficacy. The remaining 18 antidepressants were comparable or had little difference. Within the approved dose range, no significant dose-response relationship was observed. However, the time-course relationship is obvious for all antidepressants. In terms of safety, with the exception of amitriptyline, the dropout rate due to adverse events of other drugs was not more than 10% higher than that of the placebo group. CONCLUSION: The number of study sites and the type of setting are significant impact factors for the efficacy of antidepressants. Except for amitriptyline, the other 18 antidepressants have little difference in efficacy and safety.

Aza-Rubottom Oxidation: Synthetic Access to Primary α-Aminoketones.

An aza analogue of the Rubottom oxidation is reported. This facile transformation takes place at ambient temperature and directly converts silyl enol ethers to the corresponding primary α-aminoketones. The use of hexafluoroisopropanol (HFIP) as the solvent is essential for the success of this reaction. Overall this process is well-suited for the aza-functionalization and derivatization of complex organic molecules.

Monitoring tumour microenvironment changes during anti-angiogenesis therapy using functional MRI.

OBJECTIVE: This study aims to explore the feasibility of dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) and blood oxygen level-dependent magnetic resonance imaging (BOLD-MRI) in assessing vessel function and tumour aggressiveness during anti-angiogenesis treatment. MATERIALS AND METHODS: A colon cancer xenograft model was established in BALB/C nude mice with the HCT116 cell line. Sixteen mice were randomly divided into Group A and Group B, which were treated with saline or bevacizumab by intraperitoneal injection on the 1st, 4th, 7th, 10th and 13th days and underwent DCE-MRI and BOLD-MRI examinations before and on the 3rd, 6th, 9th, 12th and 15th days after treatment. Group C was treated with oxaliplatin monotherapy, and Group D was treated with bevacizumab and oxaliplatin as a point of comparison for therapeutic effects. The pathological examinations included HE, HIF-1α, fibronectin and TUNEL staining, as well as α-SMA and CD31 double staining. One-way analysis of variance and correlation analysis were the main methods used for statistical analysis. RESULTS: Group D manifested the highest tumour inhibition rate and smallest tumour volume on day 15, followed by Group C, Group B and Group A. Ktrans (F = 81.386, P < 0.001), Kep (F = 45.901, P < 0.001), Ve (F = 384.290, P < 0.001) and R2* values (F = 89.323, P < 0.001) showed meaningful trends with time in Group B but not Group A. The Ktrans values and tumour vessel maturity index (VMI) were higher than baseline values 3-12 days after bevacizumab treatment. The CD31 positive staining rate and VMI had the strongest correlations with Ktrans values, followed by AUC180, Ve and Kep values. The R2* value positively correlated with the positive staining rates of HIF-1α and fibronectin. CONCLUSION: Intermittent application of low-dose anti-angiogenic inhibitor treatment may help improve the effect of chemotherapy by reducing hypoxia-related treatment resistance and improving drug delivery. DCE-MRI is useful for evaluating vessel maturity and vascular normalization, while BOLD-MRI may help to predict tumour hypoxia and metastatic potential after anti-vascular treatment.

Observation of Anomalous π Modes in Photonic Floquet Engineering.

Recent progress on Floquet topological phases has shed new light on time-dependant quantum systems, among which one-dimensional (1D) Floquet systems have been under extensive theoretical research. However, an unambiguous experimental observation of these 1D Floquet topological phases is still lacking. Here, by periodically bending an ultrathin metallic array of coupled corrugated waveguides, a photonic Floquet simulator was well designed and successfully fabricated to mimic the periodically driven Su-Schrieffer-Heeger model. Intriguingly, under moderate driven frequencies, we report the first observation of the anomalous Floquet topological π mode, propagating along the array's boundary. The different evolutionary behaviors between static and nonstatic topological end modes have been clearly demonstrated by the microwave near-field experiment. Furthermore, the experiment in the fast-driving regime also reveals the universal high-frequency behavior in driven systems. Our photonic simulator can serve as a versatile testing ground for various phenomena related to time-dependant 1D quantum phases, such as Thouless pumping and dynamical localization.

Flexibly designed spoof surface plasmon waveguide array for topological zero-mode realization.

We propose a flexibly designed photonic system based on ultrathin corrugated metallic "H-bar" waveguide that supports spoof surface plasmon polariton (SPP) at microwave frequencies. Five designs were presented, in order to demonstrate flexibility according to varying height, period, core width, rotation, and shifting on the "H-bar" unit of the waveguide. The propagation constant between two hybrid designs of period and height structure was then shown in order to study the coupling effect. Next, we constructed a coupled waveguide array that followed the Su-Schrieffer-Heeger (SSH) model. This model was constructed by a hybrid design with the identical propagation constant of each waveguide, except it had dimerized spacing. The propagation feature of topological zero mode was then observed as theoretically expected in the dimerized array. Our proposed spoof SPP waveguide array has great flexibility to be used as a powerful experiment platform, particularly in photonic simulation of the quantum or topological phenomena described by Schrödinger equation in condensed matters.

Cycloaddition reactions of enoldiazo compounds.

Enoldiazo esters and amides have proven to be versatile reagents for cycloaddition reactions that allow highly efficient construction of various carbocycles and heterocycles. Their versatility is exemplified by (1) [2+n]-cycloadditions (n = 3, 4) by the enol silyl ether units of enoldiazo compounds with retention of the diazo functionality to furnish α-cyclic-α-diazo compounds that are themselves subject to further transformations of the diazo functional group; (2) [3+n]-cycloadditions (n = 1-5) by metallo-enolcarbenes formed by catalytic dinitrogen extrusion from enoldiazo compounds; (3) [2+n]-cycloadditions (n = 3, 4) by donor-acceptor cyclopropenes generated in situ from enoldiazo compounds that produce cyclopropane-fused ring systems. The role of dirhodium(ii) and the emergence of copper(i) catalysts are described, as are the different outcomes of reactions initiated with these catalysts. This comprehensive review on cycloaddition reactions of enoldiazo compounds, with emphasis on methodology development, mechanistic insight, and catalyst-controlled chemodivergence, aims to provide inspiration for future discoveries in the field and to catalyze the application of enoldiazo reagents by the wider synthetic community.

Copper-Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides.

Enoldiazoimides, a new subclass of enoldiazo compounds, generate enol-substituted carbonyl ylides whose reactions with sulfur ylides enable an unprecedented formal [4+2] cycloaddition. The resulting multifunctionalized indolizidinones, which incorporate sulfur, are formed in good yields under mild reaction conditions. The uniqueness of this transformation stems from the role of the silyl-protected enol, since the corresponding acetyldiazoimide failed to provide any cross-products in metal-catalyzed reactions with sulfur ylides. This copper-catalyzed cycloaddition is initiated with the generation of enol-substituted carbonyl ylides and sulfur ylides from enoldiazoimides and sulfonium salts, respectively, and proceeds through stepwise six-membered ring formation, C-O and C-S bond cleavage, and silyl and acetyl group migration.

Divergent Rhodium-Catalyzed Cyclization Reactions of Enoldiazoacetamides with Nitrosoarenes.

The first cyclization reactions of enoldiazo compounds with nitrosoarenes have been developed. Under the catalysis of rhodium(II) octanoate, [3 + 2]-cyclization between enoldiazoacetamides and nitrosoarenes occurred through cleavages of the enol double bond and the amide bond, thus furnishing fully substituted 5-isoxazolone derivatives. Upon changing the catalyst to rhodium(II) caprolactamate, the reaction pathway switched to an unprecedented formal [5 + 1]-cyclization that provided multifunctionalized 1,3-oxazin-4-ones with near exclusivity under otherwise identical conditions. Mechanistic studies uncovered distinct catalytic activities and reaction intermediates, which plausibly rationalized the novel reactivity and catalyst-controlled chemodivergence. Furthermore, a mechanism-inspired enantioselective rhodium-catalyzed reaction of γ-substituted enoldiazoacetamide with nitrosobenzene produced highly enantioenriched heterocycle-linked trialkylamine.