Spectroscopic characterization of carbon monoxide activation by neutral chromium carbides.

Spectroscopic characterization of carbon monoxide activation by neutral metal carbides is of essential importance for understanding the structure-reactivity relationships of catalytic sites, but has been proven to be very challenging owing to the difficulty in size selection. Here, we report a size-specific infrared-vacuum ultraviolet spectroscopic study of the reactions between carbon monoxide with neutral chromium carbides. Quantum chemical calculations were carried out to identify the low-lying structures and to interpret the experimental features. The results reveal that the most stable structure of CrC3(CO)2 consists of a CCO ketenylidene unit and that of CrC4(CO)2 has a semi-bridging CO with a very low CO stretching vibrational frequency at 1821 cm-1. The electron structure analyses show that this semi-bridging CO is highly activated through the delocalized Cr-C-C three-center two-electron (3c-2e) interaction between the antibonding orbitals of CO and the metal carbide skeleton. The formation of these metal carbide carbonyls is found to be both thermodynamically exothermic and kinetically facile in the gas phase. The present findings have important implications for the mechanical understanding of the catalytic processes with isolated metal atoms/clusters dispersed on supports.

Spectroscopic Characterization of Highly Excited Neutral Chromium Tricarbonyl.

Spectroscopic characterization of highly excited neutral transition-metal complexes is important for understanding the multifaceted reaction mechanisms between metals and ligands. In this work, the reactions of neutral chromium atoms with carbon monoxide were probed by size-specific infrared spectroscopy. Interestingly, Cr(CO)3 was found to have an unprecedented 7A2″ septet excited state rather than the singlet ground state. A combination of experiment and theory shows that the gas-phase formation of this highly excited Cr(CO)3 is facile both thermodynamically and kinetically. Electronic structure and bonding analyses indicate that the valence electrons of Cr atoms in the septet Cr(CO)3 are in a relatively stable configuration, which facilitate the highly excited structure and the planar geometric shape (D3h symmetry). The observed septet Cr(CO)3 affords a paradigm for exploring the structure, properties, and formation mechanism of a large variety of excited neutral compounds.

Chromatic Plasmonic Polarizer-Based Synapse for All-Optical Convolutional Neural Network.

Emerging memory devices have been demonstrated as artificial synapses for neural networks. However, the process of rewriting these synapses is often inefficient, in terms of hardware and energy usage. Herein, we present a novel surface plasmon resonance polarizer-based all-optical synapse for realizing convolutional filters and optical convolutional neural networks. The synaptic device comprises nanoscale crossed gold arrays with varying vertical and horizontal arms that respond strongly to the incident light's polarization angle. The presented synapse in an optical convolutional neural network achieved excellent performance in four different convolutional results for classifying the Modified National Institute of Standards and Technology (MNIST) handwritten digit data set. After training on 1,000 images, the network achieved a classification accuracy of over 98% when tested on a separate set of 10,000 images. This presents a promising approach for designing artificial neural networks with efficient hardware and energy consumption, low cost, and scalable fabrication.

Research progress on composite material of bismuth vanadate catalyzing the decomposition of Quinolone antibiotics.

Since quinolone is a kind of synthetic broad-spectrum antibacterial drugs, with the widespread use of this class of antibiotics, the risk and harm to human health have been attendant to the sewage containing quinolones which are discharged into the environment. Photocatalysis is considered as a promising technology for antibiotic degradation for its strong redox properties and reaction rate. As a metal oxidizing substance, Bismuth vanadate (BiVO4) is such a popular and hot material for the degradation of organic pollutants recently due to its good photocatalytic activity and chemical stability. Numerous studies have confirmed that BiVO4 composites can overcome the shortcomings of pure BiVO4 and cleave the main structure of quinolone under photocatalytic conditions. This paper mainly outlines the research progress on the preparation of BiVO4 composites and the degradation of quinolone antibiotics from the perspective of improving the catalysis and degrading the efficiency mechanism of BiVO4 composites.

A Flexible and Wearable Photodetector Enabling Ultra-Broadband Imaging from Ultraviolet to Millimeter-Wave Regimes.

Flexible and miniaturized photodetectors, offering a fast response across the ultraviolet (UV) to millimeter (MM) wave spectrum, are crucial for applications like healthcare monitoring and wearable optoelectronics. Despite their potential, developing such photodetectors faces challenges due to the lack of suitable materials and operational mechanisms. Here, the study proposes a flexible photodetector composed of a monolayer graphene connected by two distinct metal electrodes. Through the photothermoelectric effect, these asymmetric electrodes induce electron flow within the graphene channel upon electromagnetic wave illumination, resulting in a compact device with ultra-broadband and rapid photoresponse. The devices, with footprints ranging from 3 × 20 µm2 to 50 × 20 µm2, operate across a spectrum from 325 nm (UV) to 1.19 mm (MM) wave. They demonstrate a responsivity (RV) of up to 396.4 ± 5.1 mV W-1, a noise-equivalent power (NEP) of 8.6 ± 0.1 nW Hz- 0.5, and a response time as small as 0.8 ± 0.1 ms. This device facilitates direct imaging of shielded objects and material differentiation under simulated human body-wearing conditions. The straightforward device architecture, aligned with its ultra-broadband operational frequency range, is anticipated to hold significant implications for the development of miniaturized, wearable, and portable photodetectors.

Infrared spectroscopic study of solvation and size effects on reactions between water molecules and neutral rare-earth metals.

Elucidating the solvation and size effects on the reactions between water and neutral metals is crucial for understanding the microscopic mechanism of the catalytic processes but has been proven to be a challenging experimental target due to the difficulty in size selection. Here, MO4H6 and M2O6H7 (M = Sc, Y, La) complexes were synthesized using a laser-vaporization cluster source and characterized by size-specific infrared-vacuum ultraviolet spectroscopy combined with quantum chemical calculations. The MO4H6 and M2O6H7 complexes were found to have H˙M(OH)3(H2O) and M2(µ2-OH)2(η1-OH)3(η1-OH2) structures, respectively. A combination of experiments and theory revealed that the formation of H˙M(OH)3(H2O) and M2(µ2-OH)2(η1-OH)3(η1-OH2) is both thermodynamically exothermic and kinetically facile in the gas phase. The results indicated that upon the addition of water to H˙M(OH)3, the feature of the hydrogen radical is retained. In the processes from mononuclear H˙M(OH)3 to binuclear M2(µ2-OH)2(η1-OH)3(η1-OH2), the active hydrogen atom undergoes the evolution from hydrogen radical → bridging hydrogen → metal hydride → hydrogen bond, which is indicative of a reduced reactivity. The present system serves as a model for clarifying the solvation and size effects on the reactions between water and neutral rare-earth metals and offers a general paradigm for systematic studies on a broad class of the reactions between small molecules and metals at the nanoscale.

Capturing Hydrogen Radicals by Neutral Metal Hydroxides.

Capturing the hydrogen radical is of central importance in various systems ranging from catalysis to biology to astronomy, but it has been proven to be challenging experimentally because of its high reactivity and short lifetime. Here, neutral MO3H4 (M = Sc, Y, La) complexes were characterized by size-specific infrared-vacuum ultraviolet spectroscopy. All these products were determined to be the hydrogen radical adducts in the form of H•M(OH)3. The results indicate that the addition of the hydrogen radical to the M(OH)3 complex is both thermodynamically exothermic and kinetically facile in the gas phase. Moreover, the soft collisions in the cluster growth channel with the helium expansion were found to be demanded for the formation of H•M(OH)3. This work highlights the pivotal roles played by the soft collisions in the formation of hydrogen radical adducts and also opens new avenues toward the design and chemical control of compounds.

Size-Specific Infrared Spectroscopic Study of the Reactions between Water Molecules and Neutral Vanadium Dimer: Evidence for Water Splitting.

Investigation of the reactions between water molecules and neutral metal clusters is important in water splitting but is very challenging due to the inherent difficulty of size selection. Here, we report a size-specific infrared-vacuum ultraviolet spectroscopic study on the reactions of water with neutral vanadium dimer. The V2O3H4 and V2O4H6 products were characterized to have unexpected V2(µ2-OH)(µ2-H)(η1-OH)2 and V2(µ2-OH)2(η1-H)2(η1-OH)2 structures, indicative of a water decomposition. A combination of theory and experiment reveals that the water splitting by V2 is both thermodynamically exothermic and kinetically facile in the gas phase. The present system serves as a model for clarifying the pivotal roles played by neutral metal clusters in water decomposition and also opens new avenues toward systematic understanding of water splitting by a large variety of single-cluster catalysts.

Development of prognostic predictive model with neutrophil-lymphocyte ratio (NLR) in patients with gastric signet ring carcinoma.

ABSTRACT: The risk factors have not been well-defined for prognosis in gastric signet ring cell carcinoma (GSRC) patients. This study is designed to prognosticate survival in GSRC patients by establishing and verifying a predictive model with neutrophil-lymphocyte ratio (NLR).A total of 147 GSRC patients from Department of Surgical Oncology, Neimenggu Baogang Hospital, Inner Mongolia Medical University were retrospectively reviewed. A predictive model was established using Cox proportional hazards. The performance of the model was evaluated by ROC curves.In present study, we found that overall survival (OS) (P < .001, Fig. 1A) and tumor recurrence rate (P = .036, Fig. 1B) in the NLR ≤ 2.8 group were significantly better than those in the NLR > 2.8 group. These results showed that NLR ≤ 2.8 was significant prognostic factor related with both OS and tumor recurrence in patients with GSRC. After adjusting for competing risk factors, NLR ≤ 2.8 (hazard ratio [HR]: 2.625, 95% confidence interval [CI]: 1.505-5.3166, P = .003), tumor size (HR: 3.024, 95% CI: 1.521-4.186, P = .005), and tumor metastasis (HR: 3.303, 95% CI: 1.25-4.525, P = .012) remained independent predictors of tumor recurrence rate and OS. Our results showed that comparing with the model without NLR (area under ROC curve: 0.798), the model with NLR (area under ROC curve: 0.826) had significant better predictive power than the model without NLR, which further confirmed the value of NLR in predicting prognosis of patients with GSRC.In conclusion, a high NLR value independently predicts poor survival in patients with GSRC after surgery. The NLR may help oncologists evaluate outcomes of patients received surgical resection and chemotherapy in order to choose alternative therapies for patients with high NLR value.

Reversible Transformation between Bipolar Memory Switching and Bidirectional Threshold Switching in 2D Layered K-Birnessite Nanosheets.

Birnessite-related manganese dioxides (MnO2) have recently been studied owing to their diverse low-dimensional layered structures and potential applications in energy devices. The birnessite MnO2 possesses a layered structure with edge-shared MnO6 octahedra layer stacked with interlayer of cations. The unique layered structure may provide some distinct electrical properties for the 2D layered nanosheets. In this work, layered K-birnessite MnO2 samples are synthesized by a hydrothermal method. The resistive switching (RS) devices based on single K-birnessite MnO2 nanosheets are fabricated by transferring the nanosheets onto SiO2/Si substrates through a facile and feasible method of mechanical exfoliation. The device exhibits nonvolatile memory switching (MS) behaviors with high current ON/OFF ratio of ∼2 × 105. And more importantly, reversible transformation between the nonvolatile MS and volatile threshold switching (TS) can be achieved in the single layered nanosheet through tuning the magnitude of compliance current (Icc). To be more specific, a relatively high Icc (1 mA) can trigger the nonvolatile MS behaviors, while a relatively low Icc (≤100 µA) can generate volatile TS characteristics. This work not only demonstrates the memristor based on single birnessite-related MnO2 nanosheet, but also offers an insight into understanding the complex resistive switching types and relevant physical mechanisms of the 2D layered oxide nanosheets.