Desymmetrization-Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis.

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging the synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated the synthesis of a series of chiral functionalized cyclopropanes with high yield, enantioselectivity, and diastereoselectivity (44 examples, up to 93% yield and >99% ee). A possible reaction mechanism involving cyclopropene desymmetrization by Co-H species and imine addition by Co-alkyl species was proposed. This study provides a novel route to important chiral cyclopropanes and extends the frontier of asymmetric metallaphotoredox catalysis.

Mandibular Osteomyelitis as the Earliest Clinical Manifestation of Maxillary Sinus Lymphoma.

Extranodal natural killer/T-cell lymphoma is a distinct subtype of non-Hodgkin lymphoma that originates from natural killer cells or cytotoxic T cells. Its diagnosis is challenging due to the rarity and lack of awareness, especially in cases where osteomyelitis of the jawbone is the initial symptom. This paper reports a case of extranodal natural killer/T-cell lymphoma presenting primarily with oral ulcers. Through analyzing the clinical and pathological characteristics, differential diagnosis, treatment and prognosis, and reasons for misdiagnosis of the disease, this study aims to provide references for clinical diagnosis and treatment.

Control of Kinetic Pathways toward Supramolecular Chiral Polymorphs for Tunable Circularly Polarized Luminescence.

An amphiphilic aza-BODIPY dye (S)-1 bearing two chiral hydrophilic side chains with S-stereogenic centers was synthesized. This dye exhibited kinetic-controlled self-assembly pathways and supramolecular chiral polymorphism properties in MeOH/H2O (9/1, v/v) mixed solvent. The (S)-1 monomers first aggregated into a kinetic controlled, off-pathway species Agg. A, which was spontaneously transformed into an on-pathway metastable aggregate (Agg. B) and subsequently into the thermodynamic Agg. C. The three aggregate polymorphs of dye (S)-1 displayed distinct optical properties and nanomorphologies. In particular, chiral J-aggregation characteristics were observed for both Agg. B and Agg. C, such as Davydov-split absorption bands (Agg. B), extremely sharp and intense J-band with large bathochromic shift (Agg. C), non-diminished fluorescence upon aggregation, as well as strong bisignated Cotton effects. Moreover, the AFM and TEM studies revealed that Agg. A had the morphology of nanoparticle while fibril or rod-like helical nanostructures with left-handedness were observed respectively for Agg. B and Agg. C. By controlling the kinetic transformation process from Agg. B to Agg. C, thin films consisting of Agg. B and Agg. C with different ratios were prepared, which displayed tunable CPL with emission maxima at 788-805 nm and g-factors between -4.2×10-2 and -5.1×10-2.

Robotics Perception and Control: Key Technologies and Applications.

The integration of advanced sensor technologies has significantly propelled the dynamic development of robotics, thus inaugurating a new era in automation and artificial intelligence. Given the rapid advancements in robotics technology, its core area-robot control technology-has attracted increasing attention. Notably, sensors and sensor fusion technologies, which are considered essential for enhancing robot control technologies, have been widely and successfully applied in the field of robotics. Therefore, the integration of sensors and sensor fusion techniques with robot control technologies, which enables adaptation to various tasks in new situations, is emerging as a promising approach. This review seeks to delineate how sensors and sensor fusion technologies are combined with robot control technologies. It presents nine types of sensors used in robot control, discusses representative control methods, and summarizes their applications across various domains. Finally, this survey discusses existing challenges and potential future directions.

A portable fluorescence detection device based on a smartphone employing carbon nanodots for Mn2+ sensing.

The measurement of fluorescence emission for quantitative analysis is typically based on a traditional spectrofluorometer, which limits an onsite detection approach. Thus, an alternative device should be developed for fulfilling this analysis outside of the laboratory. Therefore, a low-cost, portable, and low-energy consumption fluorescence reader-based smartphone device was developed. An ultraviolet light-emitting diodes (UV-LED) was used to construct the fluorescence device-based smartphone as a low-power excitation light source. The smartphone camera was used as a detector for detecting photons from the fluorescence emission process of the fluorescence probe and was connected to a digital image platform. Transparent acrylic with orange and yellow colors was employed as a filter for reducing the interference from light source intensity. The obtained digital image was converted to red, green and blue (RGB) intensity using a custom-designed smartphone application. N,S-doped carbon nanodots (N,S-CDs) were demonstrated to be a good fluorescence indicator for determining trace quantities of Mn2+ in cosmetics. The approach exhibited high selectivity and sensitivity, detecting and quantifying analytes at 1-5 µM concentrations. Furthermore, the method's detection limit of 0.5 µM reflects its capacity to detect trace amounts of a target analyte. Mn2+ in cosmetic products was successfully analyzed using this device with high accuracy comparable with the results from inductively coupled plasma-optical emission spectroscopy (ICP-OES).

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron-Enriched Lattice Oxygen Species.

Direct synthesis of dimethyl carbonate (DMC) from CO2 plays an important role in carbon neutrality, but its efficiency is still far from the practical application, due to the limited understanding of the reaction mechanism and rational design of efficient catalyst. Herein, abundant electron-enriched lattice oxygen species were introduced into CeO2 catalyst by constructing the point defects and crystal-terminated phases in the crystal reconstruction process. Benefitting from the acid-base properties modulated by the electron-enriched lattice oxygen, the optimized CeO2 catalyst exhibited a much higher DMC yield of 22.2 mmol g-1 than the reported metal-oxide-based catalysts at the similar conditions. Mechanistic investigations illustrated that the electron-enriched lattice oxygen can provide abundant sites for CO2 adsorption and activation, and was advantageous of the formation of the weakly adsorbed active methoxy species. These were facilitating to the coupling of methoxy and CO2 for the key *CH3OCOO intermediate formation. More importantly, the weakened adsorption of *CH3OCOO on the electron-enriched lattice oxygen can switch the rate-determining-step (RDS) of DMC synthesis from *CH3OCOO formation to *CH3OCOO dissociation, and lower the corresponding activation barriers, thus giving rise to a high performance. This work provides insights into the underlying reaction mechanism for DMC synthesis from CO2 and methanol and the design of highly efficient catalysts.

Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides.

Olefin-linked covalent organic frameworks (COFs) have exhibited great potential in visible-light photocatalysis. In principle, expanding fully conjugated COFs can facilitate light absorption and charge transfer, leading to improved photocatalysis. Herein, three olefin-linked COFs with the same topology are synthesized by combining 2,4,6-trimethyl-1,3,5-triazine (TMT) with 1,3,5-triformylbenzene (TFB), 1,3,5-tris(4-formylphenyl)benzene (TFPB), and 1,3,5-tris(4-formylphenylethynyl)benzene (TFPEB), namely, TMT-TFB-COF, TMT-TFPB-COF, and TMT-TFPEB-COF, respectively. From TMT-TFB-COF to TMT-TFPB-COF, expanding phenyl rings provides only limited expansion for π-conjugation due to the steric effect of structural twisting. However, from TMT-TFPB-COF to TMT-TFPEB-COF, the insertion of acetylenes eliminates the steric effect and provides more delocalized π-electrons. As such, TMT-TFPEB-COF exhibits the best optoelectronic properties among these three olefin-linked COFs. Consequently, the photocatalytic performance of TMT-TFPEB-COF is much better than those of TMT-TFB-COF and TMT-TFPB-COF on the oxidation of organic sulfides into sulfoxides with oxygen. The desirable reusability and substrate compatibility of the TMT-TFPEB-COF photocatalyst are further confirmed. The selective formation of organic sulfoxides over TMT-TFPEB-COF under blue light irradiation proceeds via both electron- and energy-transfer pathways. This work highlights a rational design of expanding the π-conjugation of fully conjugated COFs toward selective visible-light photocatalysis.

Spin polarized Fe1-Ti pairs for highly efficient electroreduction nitrate to ammonia.

Electrochemical nitrate reduction to ammonia offers an attractive solution to environmental sustainability and clean energy production but suffers from the sluggish *NO hydrogenation with the spin-state transitions. Herein, we report that the manipulation of oxygen vacancies can contrive spin-polarized Fe1-Ti pairs on monolithic titanium electrode that exhibits an attractive NH3 yield rate of 272,000 µg h-1 mgFe-1 and a high NH3 Faradic efficiency of 95.2% at -0.4 V vs. RHE, far superior to the counterpart with spin-depressed Fe1-Ti pairs (51000 µg h-1 mgFe-1) and the mostly reported electrocatalysts. The unpaired spin electrons of Fe and Ti atoms can effectively interact with the key intermediates, facilitating the *NO hydrogenation. Coupling a flow-through electrolyzer with a membrane-based NH3 recovery unit, the simultaneous nitrate reduction and NH3 recovery was realized. This work offers a pioneering strategy for manipulating spin polarization of electrocatalysts within pair sites for nitrate wastewater treatment.

Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron-Handled Pyrazoles.

Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base-boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron-handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research.

Study on human-SRL synchronized walking based on coupled impedance.

Introduction: Supernumerary robotic limbs (SRL) is a novel category of wearable robotics. Unlike prostheses (compensation for human limbs) and exoskeletons (augmentation of human limbs), SRL focuses on expanding human limbs and enhancing human activities, perception, and operation through the mutual collaboration of mechanical limbs and human limbs. The SRL of lower limbs are attached to the human waist, synchronized with the human walking in the forward direction, and can carry weight independently in the vertical direction. Methods: In order to enhance the synchronization performance of the human-machine system during walking and minimize interference with human gait, it is essential to investigate the coupling dynamics within the human-SRL system. To facilitate our research, this paper focuses on relatively ideal working conditions: level road surfaces, no additional weight-bearing on the SRL, and humans walking in a straight line without any turns. We build upon the passive dynamic walking theory and utilize the human-SRL system model established by MIT to develop a coupling system model. Through numerical simulations, we identify the optimal values for the stiffness and damping coefficients of the human-machine connection. Additionally, we have designed the wheel-legged SRL structure and constructed the SRL control system for experimental validation. Results: It is found that a better synchronization of the human-machine walking process can be achieved by configuring suitable spring and damping units in the human-machine connection part. Discussion: In this study, we explored the concept of SRL and its potential benefits for enhancing human motion, conducting simulations and experiments based on the coupled dynamics of human-SRL systems. The results indicate that by equipping the human-machine connection component with suitable spring and damping units, synchronization during the walking process can be improved.

Insights into the Diffusion Behaviors of Water over Hydrophilic/Hydrophobic Catalysts During the Conversion of Syngas to High-Quality Gasoline.

Although considerable efforts towards directly converting syngas to liquid fuels through Fischer-Tropsch synthesis have been made, developing catalysts with low CO2 selectivity for the synthesis of high-quality gasoline remains a big challenge. Herein, we designed a bifunctional catalyst composed of hydrophobic FeNa@Si-c and HZSM-5 zeolite, which exhibited a low CO2 selectivity of 14.3 % at 49.8 % CO conversion, with a high selectivity of 62.5 % for gasoline in total products. Molecular dynamic simulations and model experiments revealed that the diffusion of water molecules through hydrophilic catalyst was bidirectional, while the diffusion through hydrophobic catalyst was unidirectional, which were crucial to tune the water-gas shift reaction and control CO2 formation. This work provides a new fundamental understanding about the function of hydrophobic modification of catalysts in syngas conversion.

A membership-function-based broad learning system for human-robot interaction force estimation under drawing task.

Estimating interaction force is of great significance in the field of human-robot interaction (HRI) thanks to its guarantee of interaction safety. To this end, this paper proposes a novel estimation method by leveraging broad learning system (BLS) and human surface electromyography (sEMG) signals. Since the previous sEMG may also contain valuable information of human muscle force, it would cause the estimation to be incomplete and abate the estimation accuracy in the case of neglecting the previous sEMG. To remedy this thorn, a new linear membership function is first developed to calculate contributions of sEMG at different sampling times in the proposed method. Subsequently, the contribution values calculated by the membership function are integrated with features of sEMG to be considered as the input layer of BLS. For extensive studies, five different features extracted from sEMG signals and their combination are explored to estimate the interaction force by the proposed method. Lastly, the performance of the proposed method is compared with those of three well-known methods through experimental test regarding the drawing task. The experimental results confirm that combining the time domain (TD) with frequency domain (FD) features of sEMG can enhance the estimation quality. Moreover, the proposed method outperforms its contenders with respect to estimation accuracy.

Seismic and medical ultrasound imaging of velocity and density variations by nonlinear vectorial inverse scattering.

We present an iterative nonlinear inverse scattering algorithm for high-resolution acoustic imaging of density and velocity variations. To solve the multi-parameter nonlinear direct scattering problem, the acoustic wave equation for inhomogeneous media in the frequency domain is transformed into a vectorial integral equation of the Lippmann-Schwinger type for the combined pressure and pressure-gradient field. To solve the multi-parameter nonlinear inverse scattering problem, we use the Newton-Kantorovich method in conjunction with matrix-free representations of the Fréchet derivative operators and their adjoints. The approximate Hessian information that is accounted for in our iterative solution of the (nonlinear) multi-parameter inverse scattering problem is essential for the mitigation of multi-parameter cross talk effects. Numerical examples related to seismic and medical ultrasound breast imaging illustrate the performance of the new algorithm for multi-parameter acoustic imaging.

Field Effect Transistor Gas Sensors Based on Mechanically Exfoliated Van der Waals Materials.

The high surface-to-volume ratio and flatness of mechanically exfoliated van der Waals (vdW) layered materials make them an ideal platform to investigate the Langmuir absorption model. In this work, we fabricated field effect transistor gas sensors, based on a variety of mechanically exfoliated vdW materials, and investigated their electrical field-dependent gas sensing properties. The good agreement between the experimentally extracted intrinsic parameters, such as equilibrium constant and adsorption energy, and theoretically predicted values suggests validity of the Langmuir absorption model for vdW materials. Moreover, we show that the device sensing behavior depends crucially on the availability of carriers, and giant sensitivities and strong selectivity can be achieved at the sensitivity singularity. Finally, we demonstrate that such features provide a fingerprint for different gases to quickly detect and differentiate between low concentrations of mixed hazardous gases using sensor arrays.

Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality.

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal catalysis, has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed to access central chirality, the construction of axial chirality by metallaphotoredox catalysis still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed asymmetric reductive couplings of biaryl dialdehydes to synthesize axially chiral aldehydes (60 examples, up to 98% yield, >19:1 dr, and >99% ee). This protocol shows good functional group tolerance, broad substrate scope, and excellent diastereo- and enantioselectivity.

A Cryostat Applicable to Long-Wavelength Light-Driven Scanning Probe Microscopy.

Recently, there has been growing interest in using lightwave-driven scanning probe microscopy (LD-SPM) to break through the Abbe diffraction limit of focusing, yielding insight into various energy couplings and conversion processes and revealing the internal information of matter. We describe a compact and efficient optical cryostat designed for LD-SPM testing under magnetic fields. The exceptional multilayer radiation shielding insert (MRSI) forms an excellent temperature gradient when filled with heat conducting gas, which removes the requirement to install an optical window in the liquid helium cooling shell. This not only critically avoids the vibration and thermal drift caused by solid heat conduction but also minimizes light transmission loss. The application of gate valves and bellows allows a simpler and more effective replacement of the sample and working cell in the test cavity. ANSYS software is used for steady-state thermal analysis of the MRSI to obtain the temperature distribution and heat transfer rate, and the necessity of the flexible copper shielding strips is illustrated by the simulations. The topography and magnetic domain images of 45 nm-thick La0.67Ca0.33MnO3 thin films on NdGaO3(001) substrates under a magnetic field were obtained by a self-made lightwave-driven magnetic force microscope in this cryostat. The resolution and noise spectra during imaging reveal temperature stability and low vibration throughout the cryostat. The experience acquired during the development of this cryostat will help to establish cryostats of similar types for a variety of optic applications requiring the use of cryogenic temperatures.

Supramolecular Structure and Photo-Thermo-Electric Property of Hydrogen-Bonded Liquid Crystalline Polymer Containing Poly(4-vinylpridine) and Cyanostilbene Side Chains.

A series of side-chain liquid crystalline polymers P4VP(CN-DBE)x , where x is the molar ratio of cyanostilbene (CN-DBE) to poly(4-vinylpyridine) (P4VP) repeating unit, was synthesized based on the intermolecular hydrogen bonding between P4VP and CN-DBE. Their luminescent property, liquid crystalline structure and photo-thermo-electric property were elucidated using photoluminescence spectra, X-ray diffraction, thermal imaging and thermoelectric experiments. With the increase of x, the supramolecular system can be changed from lamellar structure to hexagonal columnar structure. Moreover, the P4VP(CN-DBE)x polymer with columnar structure exhibits more efficient photothermal effect. The temperature of P4VP(CN-DBE)0.6 can rise to 130 °C within 10 s under the irradiation of ultraviolet lamp. In addition, the supramolecular system possesses unique photo-thermo-electric conversion ability, and 25 mA current can be detected in the circuit coupled with the thermoelectric module. This work broadens the potential applications of hydrogen-bonded polymer, and provides a simple and facile strategy to prepare liquid crystalline polymers with photo-thermo-electric property.

Association between oxidative balance score and prostate specific antigen among older US adults.

Objective: Oxidative Balance Score (OBS) is an index affecting the oxidative stress of dietary and lifestyle factors. We aimed to explore the association of OBS with prostate specific antigen (PSA) among older males. Methods: A total of 5,136 samples were collected in this study to investigate the relationship between OBS and PSA from the National Health and Nutrition Examination Survey. Logistic regression models and restricted cubic spline were used to assess the associations between OBS and PSA. Results: Compared with the Q1 group, the odds ratios for the association between OBS and PSA were 1.005 (1.003, 1.009), 1.003 (1.001, 1.006), and 1.001 (0.978, 1.022) for Q2, Q3, and Q4, respectively. In the age-specific analyses, the association was significant among individuals aged 65 years old and over: the odds ratios for the association between OBS and PSA were 1.019 (1.005, 1.028), 1.028 (1.018, 1.039), and 1.038 (1.022, 1.049) for Q2, Q3, and Q4, respectively. But it was not significant among individuals aged less than 65 years old: the odds ratios for the association between OBS and PSA were 1.016 (0.995, 1.026), 1.015 (0.985, 1.022), and 0.988 (0.978, 1.016) for Q2, Q3, and Q4, respectively. The restricted cubic splines also indicated a nonlinear relationship between OBS and PSA among individuals aged 65 years old and over (Poverall = 0.006, Pnonlinear = 0.021). Conclusion: Our findings provide evidence that OBS is positively associated with higher levels of PSA among older adults. Further large-scale prospective cohort studies are needed to verify our findings.

A piezoelectric rotatable magnetic force microscope system in a 10 T cryogen-free superconducting magnet.

We constructed a piezoelectric rotatable magnetic force microscope (MFM) that works in a 10 T cryogen-free superconducting magnet. The piezoelectric tube is deformed tangentially and drives a bearing under the inertial drive principle so the MFM head can obtain rotary movement. Due to the novel piezoelectric design, the MFM can be hung underneath the heat sink via a soft spring, and it can be rotated in a cryogen-free superconducting magnet so that the direction of the magnetic field can be changed from 0° to 90° continuously. The system functions in magnetic fields of up to 10 T in any direction relative to the tip-sample geometry. This is the first piezoelectric rotatable MFM ever reported. Using this homemade rotatable MFM, we imaged the structure of magnetic tracks on a commercial videotape. When the magnetic field angle changes from 0° to 90°, the magnetic moments on the tape and probe tip also rotate. A magnetic field strength of 0.8 T parallel to the sample surface is required to fully rotate the magnetic moment of the tip we used, but 0.8 T is not enough to fully rotate the magnetic moment of the sample. The piezoelectric rotatable MFM is expected to be widely used to study the anisotropy of magnetic materials due to its superiority in obtaining the same high field in and out of plane (compared with a vector magnet) as well as in maintaining the same scan area precisely (compared with a mechanical rotatable MFM, especially for atomic-scale scan areas).