Gold/Chiral Amine Relay Catalysis Enables Asymmetric Synthesis of C2-Quaternary Indolin-3-ones.

A mild and effective strategy for the asymmetric synthesis of C2-quaternary indolin-3-ones from 2-alkynyl arylazides and ketones by gold/chiral amine relay catalysis is described. In this reaction, 2-alkynyl arylazides undergo gold-catalyzed cyclization, nucleophilic attack, and oxidation to form intermediate 2-phenyl-3H-indol-3-ones, followed by an l-proline-catalyzed asymmetric Mannich reaction with ketones, to afford corresponding products in satisfactory yields with excellent enantio- and diastereoselectivities.

Schiff Base Complex Cocatalyst with Coordinatively Unsaturated Cobalt Sites for Photoelectrochemical Water Oxidation.

Integrating inorganic oxygen evolution cocatalysts (OECs) with photoanodes is regarded as an available strategy to increase the photogenerated charge utilization for accelerated water oxidation kinetics. Nevertheless, most widely used transition metal (oxyhydr)oxides OECs suffer from inevitable charge recombination at photoanode/OECs interfaces and underabundant catalytic active sites. Herein, a cobalt-organic complex with microflower-like features (denoted as MF) was constructed by coordination of Schiff base ligands and Co2+ metal ions and then decorated on porous BiVO4 employed as photoanodes for photoelectrochemical (PEC) water oxidation. The as-synthesized BiVO4/MF photoanode achieves a photocurrent density of 4.38 mA cm-2 and at 1.23 VRHE in 0.5 M Na2SO4 electrolyte under simulated 1 sun illumination, over approximately 5.48 times larger than that of BiVO4 counterpart, and exhibits a 120 mV cathodic shift of onset potential with outstanding photostability. Systematic characterizations reveal that the improved PEC efficiency is mainly attributed to the well-designed coordinatively unsaturated Co2+ sites, which not only serve as powerful photohole extraction engines along reversed interfacial Co-O-Bi bonds to promote charge transfer across the BiVO4/complex interface but also act as reaction active centers by accelerating surface water oxidation kinetics. This work provides new insights for designing highly effective OECs for PEC water oxidation.

A Dynamic Task Allocation Framework in Mobile Crowd Sensing with D3QN.

With the coverage of sensor-rich smart devices (smartphones, iPads, etc.), combined with the need to collect large amounts of data, mobile crowd sensing (MCS) has gradually attracted the attention of academics in recent years. MCS is a new and promising model for mass perception and computational data collection. The main function is to recruit a large group of participants with mobile devices to perform sensing tasks in a given area. Task assignment is an important research topic in MCS systems, which aims to efficiently assign sensing tasks to recruited workers. Previous studies have focused on greedy or heuristic approaches, whereas the MCS task allocation problem is usually an NP-hard optimisation problem due to various resource and quality constraints, and traditional greedy or heuristic approaches usually suffer from performance loss to some extent. In addition, the platform-centric task allocation model usually considers the interests of the platform and ignores the feelings of other participants, to the detriment of the platform's development. Therefore, in this paper, deep reinforcement learning methods are used to find more efficient task assignment solutions, and a weighted approach is adopted to optimise multiple objectives. Specifically, we use a double deep Q network (D3QN) based on the dueling architecture to solve the task allocation problem. Since the maximum travel distance of the workers, the reward value, and the random arrival and time sensitivity of the sensing tasks are considered, this is a dynamic task allocation problem under multiple constraints. For dynamic problems, traditional heuristics (eg, pso, genetics) are often difficult to solve from a modeling and practical perspective. Reinforcement learning can obtain sub-optimal or optimal solutions in a limited time by means of sequential decision-making. Finally, we compare the proposed D3QN-based solution with the standard baseline solution, and experiments show that it outperforms the baseline solution in terms of platform profit, task completion rate, etc., the utility and attractiveness of the platform are enhanced.

Asymmetric Double Oxidative [3 + 2] Cycloaddition for the Synthesis of CF3-Containing Spiro[pyrrolidin-3,2'-oxindole].

An asymmetric double oxidative [3 + 2] cycloaddition is reported. Oxidation of 3-((2,2,2-trifluoroethyl)amino)indolin-2-ones and ß-aryl-substituted aldehydes simultaneously and subsequent asymmetric cycloaddition in the presence of the chiral amino catalyst generated highly functionalized chiral CF3-containing spiro[pyrrolidin-3,2'-oxindole] with four contiguous stereocenters stereoselectively, which is characterized by directly constructing two C-C bonds from four C(sp3)-H bonds. This new method features mild conditions, broad substrate scope, and excellent functional group compatibility.

Effects of robot-assisted minimally invasive surgery on osteoporotic vertebral compression fracture: a systematic review, meta-analysis, and meta-regression of retrospective study.

OBJECTIVE: To conduct a systematic review on the effect of robot-assisted minimally invasive surgery (R-MIS) on the clinical outcomes and complications of patients with osteoporotic vertebral compression fractures (OVCFs). METHODS: The researchers searched the papers published on PubMed, The Cochrane Library, Web of Science, Embase, Scopus, Ovid MEDLINE, Wiley Online Library, China National Knowledge Infrastructure (CNKI), Chinese biomedical literature service system (SinoMed), and China Medical Association Data. The standardized mean difference (SMD) or mean difference (MD), relative risk (RR), and 95% confidence interval (CI) were calculated. Besides, the data was merged through the random-effect model or common-effect model. A meta-regression mixed-effects single-factor model was utilized to analyze the sources of heterogeneity. RESULTS: Twelve studies were included, involving 1042 OVCFs cases. The prognosis of patients treated with R-MIS was significantly improved, such as Oswestry disability index (ODI) score (MD = -0.65, P = 0.0171), Cobb's angles (MD = -1.03, P = 0.0027), X-ray fluoroscopy frequency (SMD = -2.41, P < 0.0001), Length of hospital stay (MD = -0.33, P = 0.0002), and Cement leakage (RR = 0.37, P < 0.0001). However, no obvious improvement was found in the results of Visual analog scale (VAS) score (MD = -0.16, P = 0.1555), Volume of bone cement (MD = 0.22, P = 0.8339), and Operation time (MD = -3.20, P = 0.3411) after being treated by R-MIS. The meta-regression analysis demonstrated that R-MIS presented no significant impact on the covariates of VAS and Operation time. CONCLUSION: R-MIS can significantly reduce the patients' ODI, Cobb's angles, X-ray fluoroscopy frequency, and Cement leakage ratio, and shorten the Length of hospital stay. Therefore, R-MIS may be an effective method to promote the patients' functional recovery, correct spinal deformity, reduce the X-ray fluoroscopy frequency, shorten the Length of hospital stay, and reduce the complications of OVCFs bone Cement leakage.

Gold-Catalyzed Cascade Reaction of 2-Alkynyl Aryl Azides with Enecarbamates for Direct Synthesis of α-(3-Indolyl)ketones.

α-(3-Indolyl)ketones are essential building blocks for the generation of biologically active molecules. We described a new method for the direct assembly of α-(3-indolyl)ketones through the cascade reaction of 2-alkynyl aryl azides with enecarbamates, in which the in situ generated α-imino gold carbene intermediate was trapped by enecarbamate to achieve umpolung reactivity of indole at the 3-position.

Synergy of Ultrathin CoOx Overlayer and Nickel Single Atoms on Hematite Nanorods for Efficient Photo-Electrochemical Water Splitting.

To solve surface carrier recombination and sluggish water oxidation kinetics of hematite (α-Fe2 O3 ) photoanodes, herein, an attractive surface modification strategy is developed to successively deposit ultrathin CoOx overlayer and Ni single atoms on titanium (Ti)-doped α-Fe2 O3 (Ti:Fe2 O3 ) nanorods through a two-step atomic layer deposition (ALD) and photodeposition process. The collaborative decoration of ultrathin CoOx overlayer and Ni single atoms can trigger a big boost in photo-electrochemical (PEC) performance for water splitting over the obtained Ti:Fe2 O3 /CoOx /Ni photoanode, with the photocurrent density reaching 1.05 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (RHE), more than three times that of Ti:Fe2 O3 (0.326 mA cm-2 ). Electrochemical and electronic investigations reveal that the surface passivation effect of ultrathin CoOx overlayer can reduce surface carrier recombination, while the catalysis effect of Ni single atoms can accelerate water oxidation kinetics. Moreover, theoretical calculations evidence that the synergy of ultrathin CoOx overlayer and Ni single atoms can lower the adsorption free energy of OH* intermediates and relieve the potential-determining step (PDS) for oxygen evolution reaction (OER). This work provides an exemplary modification through rational engineering of surface electrochemical and electronic properties for the improved PEC performances, which can be applied in other metal oxide semiconductors as well.

Enantioseparation in Hierarchically Porous Assemblies of Homochiral Cages.

Efficient enantioselective separation using porous materials requires tailored and diverse pore environments to interact with chiral substrates; yet, current cage materials usually feature uniform pores. Herein, we report two porous assemblies, PCC-60 and PCC-67, using isostructural octahedral cages with intrinsic microporous cavities of 1.5 nm. The PCC-67 adopts a densely packed mode, while the PCC-60 is a hierarchically porous assembly featuring interconnected 2.4 nm mesopores. Compared with PCC-67, the PCC-60 demonstrates excellent enantioselectivity and recyclability in separating racemic diols and amides. This solid adsorbent PCC-60 is further utilized as a chiral stationary phase for high-performance liquid chromatography (HPLC), enabling the complete separation of six valuable pharmaceutical intermediates. According to quantitative dynamic experiments, the hierarchical pores facilitate the mass transfer within the superstructure, shortening the equilibrium time for adsorbing chiral substrates. Notably, this hierarchically porous material PCC-60 indicates remarkably higher enantiomeric excess (ee) values in separating racemates than PCC-67 with uniform microporous cavities. Control experiments confirm that the presence of mesopores enables the PCC-60 to separate bulky substrates. These results uncover the traditionally underestimated role of hierarchical porosity in porous-superstructure-based enantioseparation.

Construction of a chiral zinc-camphorate framework for enantioselective separation.

A chiral metal-organic framework (CMOF) with open chiral channels and multiple recognition sites is constructed from camphoric acid and a dipyridyl ligand. It can act as an efficient chiral solid adsorbent, capable of separating a variety of racemic alcohols and epoxides with excellent enantioselectivities.

The RapidIO Routing Strategy Based on the Double-Antibody Group Multi-Objective Artificial Immunity Algorithm.

The RapidIO standard is a packet-switching interconnection technology similar to the Internet Protocol (IP) conceptually. It realizes the high-speed transmission of RapidIO packets at the transport layer, but this greatly increases the probability of network blocking. Therefore, it is of great significance to optimize the RapidIO routing strategy. For this problem, this paper proposes a Double-Antibody Group Multi-Objective Artificial Immune Algorithm (DAG-MOAIA), which improves the local search and global search ability of the population by adaptive crossover and adaptive mutation of the double-antibody groups, and uses co-competition of multi-antibody groups to increase the diversity of population. Through DAG-MOAIA, an optimal transmission path from the source node to multiple destination nodes can be selected to solve the Quality Of Service (QoS) problem during data transmission and ensure the QoS of the RapidIO network. Simulation results show that DAG-MOAIA could obtain high-quality solutions to select better routing transmission paths, and exhibit better comprehensive performance in all simulated test networks, which plays a certain role in solving the problem of the RapidIO routing strategy.

Access to 3-Sulfonamidoquinolines by Gold-Catalyzed Cyclization of 1-(2'-Azidoaryl)propargylsulfonamides through 1,2-N Migration.

We describe a gold-catalyzed cyclization of 1-(2'-azidoaryl)propargylsulfonamides for the synthesis of 3-sulfonamidoquinolines, featuring a rare and highly selective 1,2-N migration. The key α-imino gold carbene intermediate is generated through an intramolecular nucleophilic attack of the azide group to the Au-activated triple bonds in a 6-endo-dig manner.

Wave Propagation in Rotating Functionally Graded Microbeams Reinforced by Graphene Nanoplatelets.

This paper presents a study on wave propagation in rotating functionally graded (FG) microbeams reinforced by graphene nanoplatelets (GPLs). The graphene nanoplatelets (GPLs) are considered to distribute in the diameter direction of the micro-beam in a gradient pattern, which leads to the functionally graded structure. By using the Halpin-Tsai micromechanics model and the rule of mixture, the effective material properties of the microbeam are determined. According to the Euler-Bernoulli beam theory and nonlocal elasticity theory, the rotating microbeams are modeled. A comprehensive parametric study is conducted to examine the effects of rotating speed, GPL distribution pattern, GPL length-to-thickness ratio, GPL length-to-width ratio, and nonlocal scale on the wavenumber, phase speed and group speed of the microbeam. The research findings can play an important role on the design of rotating graphene nanoplatelet (GPL) reinforced microbeams for better structural performance.

Study on a Chiral Structure with Tunable Poisson's Ratio.

A chiral structure with a negative Poisson's ratio containing a hollow circle with varying diameters was designed, and the finite element method was used to investigate the variation in the Poisson's ratio when the hollow circle diameter was varied (d = 0, 1, 2, 3, and 4 mm). The simulation results showed that the Poisson's ratio was sensitive to the hollow circle diameter, and the minimum Poisson's ratio was -0.43. Three specimens with different hollow circle diameters (d' = 0, 1, and 3 mm) were 3D-printed from thermoplastic polyurethane, and the Poisson's ratio and equivalent elastic modulus were measured. In the elastic range, the Poisson's ratio increased and the equivalent elastic modulus decreased as the hollow circle diameter increased. The simulation and experimental results showed good agreement. The proposed structure is expected to be applicable to protective sports gear owing to its high energy absorption and the fact that its properties can be modified as required by adjusting the geometric parameters of the unit cell.

Free Vibration Analysis of a Graphene-Reinforced Porous Composite Plate with Different Boundary Conditions.

Plates are commonly used in many engineering disciplines, including aerospace. With the continuous improvement in the capacity of high value-added airplanes, large transport aircrafts, and fighter planes that have high strength, high toughness, and corrosion resistance have gradually become the development direction of airplane plate structure production and research. The strength and stability of metal plate structures can be improved by adding reinforced materials. This paper studies graphene platelets (GPLs) reinforced with a free vibration porous composite plate. The porous plate is constructed with a multi-layer model in a metal matrix containing uniform or non-uniformly distributed open-cell internal pores. Considering the random and directional arrangement of graphene platelets in the matrix, the elastic modulus of graphene composites was estimated using the Halpin-Tsai micromechanical model, and the vibration frequencies of graphene composite were calculated using the differential quadrature method. The effects of the total number of layers, GPL distribution pattern, porosity coefficient, GPL weight fraction, and boundary conditions on the free vibration frequency of GPLs reinforced porous composite plates are studied, and the accuracy of the conclusions are verified by the finite element software.

Regulating Crystal Structure and Atomic Arrangement in Single-Component Metal Oxides through Electrochemical Conversion for Efficient Overall Water Splitting.

Single-component transition-metal oxide (TMO: FeOx, NiOx, or CoOx) nanosheets grown on nickel foam (NF) were electrochemically optimized with Li ion (Na ion)-induced conversion reaction for bifunctional electrocatalysis. The optimum FeOx/NF-Li electrocatalyst exhibits low overpotentials of 239 mV for hydrogen evolution reaction and 276 mV for oxygen evolution reaction at a current density of 100 mA cm-2. A two-electrode water splitting cell using FeOx/NF-Li as both anode and cathode requires only 1.60 V to achieve a current density of 10 mA cm-2. The impressive water splitting performance of the FeOx/NF-Li electrode is revealed to be attributed to Li-induced electrochemical conversion, which alters the crystal structure, creating more active sites for electrocatalytic reactions, as well as introduces O vacancies increasing the electron density and the intrinsic conductivity. More importantly, the atomic arrangement is regulated from tetrahedral Fe(Td) to octahedral Fe(Oh) coordination, which acts as catalytically active sites with reduced Gibbs free energy for the rate-determining steps. This electrochemical conversion reaction can be extended to other TMOs (i.e., NiOx/NF and CoOx/NF) for promoted electrocatalytic water splitting performances. This study provides an in-depth understanding on the nature of atomic and electronic structure evolution to promote the electrocatalytic activity.

Interface and surface engineering of hematite photoanode for efficient solar water oxidation.

Engineering the interface and surface structures of semiconductor-based photoelectrodes for improved charge transfer dynamics and promoted water redox reaction kinetics is essential to achieve efficient photoelectrochemical (PEC) water splitting. In this work, α-Fe2O3 nanorods, successively coated with TiO2 and CoOx thin layers, were reported as the photoanode for solar-driven water oxidation. The obtained α-Fe2O3/TiO2/CoOx photoanode exhibits superior PEC performance as compared to bare α-Fe2O3, with a 3.3-time improvement in photocurrent density at 1.23 V vs reversible hydrogen electrode. This significant enhancement results from the formed heterojunction between α-Fe2O3 and TiO2 for the accelerated photogenerated charge separation and transfer as well as the passivated surface defects by the TiO2 overlayer for reduced charge recombination. Additionally, the existence of CoOx as the oxygen evolution catalyst significantly facilitates the surface reaction kinetics and thus reduces the overpotential for water oxidation. This study demonstrates a collaborative strategy of interface and surface engineering to design novel structures of α-Fe2O3 based photoanodes for highly efficient solar water oxidation.

A New Filtering System for Using a Consumer Depth Camera at Close Range.

Using consumer depth cameras at close range yields a higher surface resolution of the object, but this makes more serious noises. This form of noise tends to be located at or on the edge of the realistic surface over a large area, which is an obstacle for real-time applications that do not rely on point cloud post-processing. In order to fill this gap, by analyzing the noise region based on position and shape, we proposed a composite filtering system for using consumer depth cameras at close range. The system consists of three main modules that are used to eliminate different types of noise areas. Taking the human hand depth image as an example, the proposed filtering system can eliminate most of the noise areas. All algorithms in the system are not based on window smoothing and are accelerated by the GPU. By using Kinect v2 and SR300, a large number of contrast experiments show that the system can get good results and has extremely high real-time performance, which can be used as a pre-step for real-time human-computer interaction, real-time 3D reconstruction, and further filtering.

Surface sulfurization activating hematite nanorods for efficient photoelectrochemical water splitting.

Surface treatment is an effective method to improve the photoelectrochemical (PEC) performance of photoelectrodes. Herein, we introduced a novel strategy of surface sulfurization to modify hematite (α-Fe2O3) nanorods grown in an aqueous solution, which triggered encouraging improvement in PEC performances. In comparison to the solution-grown pristine α-Fe2O3 nanorod photoanode that is PEC inefficient and always needs high temperature (>600 °C) activation, the surface sulfurized α-Fe2O3 nanorods show photocurrent density increased by orders of magnitude, reaching 0.46 mA cm-2 at 1.23 V vs. RHE (reversible hydrogen electrode) under simulated solar illumination. This improvement in PEC performances should be attributed to the synergy of the increased carrier density, the reduced surface charge carrier recombination and the accelerated water oxidation kinetics at the α-Fe2O3/electrolyte interface, as induced by the incorporation of S ions and the formation of multi-state S species (Fe-Sx-Oy) at the surface of α-Fe2O3 nanorods. This study paves a new and facile approach to activate α-Fe2O3 and even other metal oxides as photoelectrodes for improved PEC water splitting performances, by engineering the surface structure to relieve the bottlenecks of charge transfer dynamics and redox reaction kinetics at the electrode/electrolyte interface.

Visible light-induced electronic structure modulation of Nb- and Ta-doped α-Fe2O3 nanorods for effective photoelectrochemical water splitting.

The photoelectrochemical (PEC) water splitting activity of Nb and Ta-doped hematite (α-Fe2O3) nanorods was investigated with reference to electronic structures by in situ synchrotron x-ray absorption spectroscopy (XAS). Current density-potential measurements demonstrate that the PEC activity of α-Fe2O3 nanorods depends strongly on the species and concentrations of dopants. The doping of α-Fe2O3 nanorods with a low level of Nb or Ta can improve their electrical conductivity and thereby facilitate charge transport and reduced electron-hole recombination therein. The photoconversion effects of Nb and Ta-doped α-Fe2O3 by in situ XAS in the dark and under illumination revealed opposite evolutions of the spectral intensities of the Fe L-edge and Nb/Ta L-edge, indicating that charge transfer and a conduction pathway are involved in the photoconversion. Analytic in situ XAS results reveal that the α-Fe2O3 that is doped with a low level of Nb has a greater photoconversion efficiency than that doped with Ta because Nb sites are more active than Ta sites in α-Fe2O3. The correlation between PEC activity and the electronic structure of Nb/Ta-doped α-Fe2O3 is examined in detail using in situ XAS and helps to elucidate the mechanism of PEC water splitting in terms of the electronic structure.

Fabrication of porous TiO2 nanorod array photoelectrodes with enhanced photoelectrochemical water splitting by helium ion implantation.

Porous photoelectrodes show high efficiency in hydrogen production by water splitting. However, fabrication of porous nanorods is usually difficult. Here, we report a simple approach to fabricate a kind of novel porous rutile titanium dioxide nanorod array by an advanced ion implantation method using multiple-energy helium ion implantation and subsequent annealing. The porous nanostructure enhances the photoelectrochemical performance of the titanium dioxide nanorod array photoelectrodes under Uv-visible light illumination, where the highest photocurrent density was relatively about 10 times higher than that of the pristine titanium dioxide nanorod array. The formation of nanocavities mainly contributes to the enhancement of the photocurrent density by trapping holes inside to separate the charge carriers. The study demonstrates that ion implantation could be an effective approach to develop novel porous nanostructural photoelectrodes for the application of hydrogen production.