Boosting Hydrogen Production via Selective Two-electron Mild Electrochemical Oxidation of Tetrahydroisoquinolines Completely to Dihydroisoquinolines.

Different from the previous study that biomass derivatives replace water oxidation for enhancing hydrogen production, we found that mild oxidation was more conductive to cathodic hydrogen production. In this study, maximum Faradaic efficiency (>99 %) and lower energy consumption for hydrogen production was achieved by precisely controlling the two-electron mild electrochemical oxidation of tetrahydroisoquinolines (THIQs) to dihydroisoquinolines (DHIQs) in place of the four-electron deep oxidation to isoquinolines (IQs). Moreover, the high value-added DHIQs were prepared from THIQs with high selectivity (>99 %) at the low potential of 1.36 V. Operando electrochemical Raman and density functional theory proved that the high selectivity was attributed to the regulable active species of NiOOH induced by the interaction of Co and Fe for preferentially breaking C-H bond rather than N-H of THIQs. This novel method provides important insight into efficient biomass-assisted hydrogen production.

Fast Generation of Hydroxyl Radicals by Rerouting the Electron Transfer Pathway via Constructed Chemical Channels during the Photo-Electro-Reduction of Oxygen.

A strategy for the fast generation of hydroxyl radicals (HO·) via photo-electro-reduction of oxygen by rerouting the electron transfer pathway was proposed. The rate-determining step of HO· production is the formation of H2O2 and the simultaneous reduction of H2O2. Engineering of F-TiO2 with single atom Pd bonded with four F and two O atoms favored the electrocatalytic 2-electron oxygen reduction to H2O2 with as high as 99% selectivity, while the additional channel bond HO-O···Pd-F-TiO2 facilitates the photogenerated electron transfer from the conduction band to single atom Pd to reduce Pd···O-OH to HO·. The optimized HO· production rate is 9.18 µ mol L-1 min-1, which is 2.6-52.5 times higher than that in traditional advanced oxidation processes. In the application of wastewater treatment, this proposed photoelectrocatalytic oxygen reduction method, respectively, shows fast kinetics of 0.324 and 0.175 min-1 for removing bisphenol A and acetaminophen. Around 93.2% total organic carbon and 99.3% acute toxicity removal were achieved. Additionally, the degradation efficiency was less affected by the water source and pH value because of the evitable usage of metallic active sites. This work represents a fundamental investigation on the generation rate of HO·, which would pave the way for the future development of photoelectrocatalytic technologies for water purification.

pH-Induced Symmetry Conversion of DNA Origami Lattices.

DNA nanotechnology has provided credible approaches for assembly of three-dimensional (3D) lattices with complex patterns. However, the symmetries are strictly dependent on their initial configurations and difficult to alter via non-thermal treatments. While switchable nucleic acid structures have been employed to construct deformable DNA motifs, it remains challenging to arrange them anisotropically in 3D lattices to trigger directed collective shape transition and dynamic symmetry conversion. In this work, we used octahedral DNA origami frames to synthesize four DNA origami lattices by placing the pH-reactive i-motif sequences in the desired dimensions. Thereinto, lattices with an anisotropic design can switch between simple cubic (SC) and simple tetragonal (ST) upon pH change. Small angle X-ray scattering (SAXS) results reveal the feasibility of obtaining 3D lattices with sensitive responses to external stimuli, expanding the way to obtain low-symmetry lattices.

Direct Oxygen Transfer from H2 O to Cyclooctene over Electron-Rich RuO2 Nanocrystals for Epoxidation and Hydrogen Evolution.

Production of more than 20 million tons of epoxides per year from olefins suffers from low atom economy due to the use of oxidants and complex catalysts with unsatisfactory selectivity, leading to huge environmental and economic costs. We present a proof-of-concept application of electron-rich RuO2 nanocrystals to boost the highly selective epoxidation of cyclooctene via direct oxygen transfer from water as the sole oxygen source under mild conditions. The enhanced electron enrichment of RuO2 nanocrystals via the Schottky effect with nitrogen-doped carbons largely promotes the capture and activation of cyclooctene to give a high turnover frequency (260 h-1 ) of cyclooctene oxide, far surpassing the reported values (<20 h-1 ) of benchmarked catalysts at room temperature with oxidants. Our electron-rich RuO2 electrocatalysts enable efficient and durable hydrogen production (Faradaic efficiency >90 %) on the cathode without impacting on the selectivity to epoxide (>99 %) on the anode.

Knockdown of YKL-40 inhibits angiogenesis through regulation of VEGF/VEGFR2 and ERK1/2 signaling in endometrial cancer.

Studies have demonstrated that small interfering RNA (siRNA) targeting YKL-40 (siYKL-40) inhibits the proliferation, migration, invasion, and induces antiapoptotic abilities of endometrial cancer (EC) HEC-1A cells. However, its effect on angiogenesis is unclear. The present study aimed to investigate the role of YKL-40 in endometrial cancer and the related molecular mechanisms. YKL-40 was knocked down by transfection with siYKL-40 and the effects on angiogenesis, cell viability, and signaling pathways were investigated. The results showed that siYKL-40 inhibited VEGFA levels and tube formation in endothelial cells. Additionally, inhibition of YKL-40 decreased the expression levels of vascular endothelial growth factor (VEGF), phosphorylated vascular endothelial growth factor receptor 2 (pVEGFR2), and phosphorylated extracellular signal-regulated kinases 1 and 2 (pERK1/2). Furthermore, a nude mice xenograft model of EC showed that siYKL-40 inhibited tumor growth. Inhibition of YKL-40 led to suppression of angiogenesis and reduction of microvessel density through VEGF/VEGFR2 and ERK1/2 signaling in endometrial cancer cells. Taken together, this study demonstrated novel molecular mechanisms for role of YKL-40 in EC.

DNA Origami-Enabled Biosensors.

Biosensors are small but smart devices responding to the external stimulus, widely used in many fields including clinical diagnosis, healthcare and environment monitoring, etc. Moreover, there is still a pressing need to fabricate sensitive, stable, reliable sensors at present. DNA origami technology is able to not only construct arbitrary shapes in two/three dimension but also control the arrangement of molecules with different functionalities precisely. The functionalization of DNA origami nanostructure endows the sensing system potential of filling in weak spots in traditional DNA-based biosensor. Herein, we mainly review the construction and sensing mechanisms of sensing platforms based on DNA origami nanostructure according to different signal output strategies. It will offer guidance for the application of DNA origami structures functionalized by other materials. We also point out some promising directions for improving performance of biosensors.

Observations and analysis with the spline-based Rydberg-Klein-Rees approach for the 3(1)Σg(+) state of Rb2.

Ro-vibrational term values of the 3(1)Σg (+) state of (85,85)Rb2 and (85,87)Rb2 and resolved fluorescence spectra to the A(1)Σu (+) state are recorded following optical-optical double resonance excitation. The experimental data are heavily perturbed, and as a result, the standard analysis based on Dunham series representation of the energy levels fails. The analysis is done via modeling the adiabatic potential function with the Rydberg-Klein-Rees potential constructed from the generalized smoothing spline interpolation of the vibrational energies Gv and rotational constants Bv.

Solution-Induced Degradation of the Silicon Nanobelt Field-Effect Transistor Biosensors.

Field-effect transistor (FET)-based biosensors are powerful analytical tools for detecting trace-specific biomolecules in diverse sample matrices, especially in the realms of pandemics and infectious diseases. The primary concern in applying these biosensors is their stability, a factor directly impacting the accuracy and reliability of sensing over extended durations. The risk of biosensor degradation is substantial, potentially jeopardizing the sensitivity and selectivity and leading to inaccurate readings, including the possibility of false positives or negatives. This paper delves into the documented degradation of silicon nanobelt FET (NBFET) biosensors induced by buffer solutions. The results highlight a positive correlation between immersion time and the threshold voltage of NBFET devices. Secondary ion mass spectrometry analysis demonstrates a gradual increase in sodium and potassium ion concentrations within the silicon as immersion days progress. This outcome is ascribed to the nanobelt's exposure to the buffer solution during the biosensing period, enabling ion penetration from the buffer into the silicon. This study emphasizes the critical need to address buffer-solution-induced degradation to ensure the long-term stability and performance of FET-based biosensors in practical applications.

Cisplatin-induced ototoxicity: From signaling network to therapeutic targets.

Administration of cisplatin, a common chemotherapeutic drug, has an inevitable side effect of sensorineural hearing loss. The main etiologies are stria vascularis injury, spiral ganglion degeneration, and hair cell death. Over several decades, the research scope of cisplatin-induced ototoxicity has expanded with the discovery of the molecular mechanism mediating inner ear cell death, highlighting the roles of reactive oxygen species and transport channels for cisplatin uptake into inner ear cells. Upon entering hair cells, cisplatin disrupts organelle metabolism, induces oxidative stress, and targets DNA to cause intracellular damage. Recent studies have also reported the role of inflammation in cisplatin-induced ototoxicity. In this article, we preform a narrative review of the latest reported molecular mechanisms of cisplatin-induced ototoxicity, from extracellular to intracellular. We build up a signaling network starting with cisplatin entering into the inner ear through the blood labyrinth barrier, disrupting cochlear endolymph homeostasis, and activating inflammatory responses of the outer hair cells. After entering the hair cells, cisplatin causes hair cell death via DNA damage, redox system imbalance, and mitochondrial and endoplasmic reticulum dysfunction, culminating in programmed cell death including apoptosis, necroptosis, autophagic death, pyroptosis, and ferroptosis. Based on the mentioned mechanisms, prominent therapeutic targets, such as channel-blocking drugs of cisplatin transporter, construction of cisplatin structural analogues, anti-inflammatory drugs, antioxidants, cell death inhibitors, and others, were collated. Considering the recent research efforts, we have analyzed the feasibility of the aforementioned therapeutic strategies and proposed our otoprotective approaches to overcome cisplatin-induced ototoxicity.

When, Where and How Does it Fail? A Spatial-Temporal Visual Analytics Approach for Interpretable Object Detection in Autonomous Driving.

Arguably the most representative application of artificial intelligence, autonomous driving systems usually rely on computer vision techniques to detect the situations of the external environment. Object detection underpins the ability of scene understanding in such systems. However, existing object detection algorithms often behave as a black box, so when a model fails, no information is available on When, Where and How the failure happened. In this paper, we propose a visual analytics approach to help model developers interpret the model failures. The system includes the micro- and macro-interpreting modules to address the interpretability problem of object detection in autonomous driving. The micro-interpreting module extracts and visualizes the features of a convolutional neural network (CNN) algorithm with density maps, while the macro-interpreting module provides spatial-temporal information of an autonomous driving vehicle and its environment. With the situation awareness of the spatial, temporal and neural network information, our system facilitates the understanding of the results of object detection algorithms, and helps the model developers better understand, tune and develop the models. We use real-world autonomous driving data to perform case studies by involving domain experts in computer vision and autonomous driving to evaluate our system. The results from our interviews with them show the effectiveness of our approach.

A universal way to enrich the nanoparticle lattices with polychrome DNA origami "homologs".

DNA origami technology has rapidly developed into an ideal means to programmably crystallize nanoparticles. However, most existing DNA origami three-dimensional platforms normally used a single type of DNA origami unit, which greatly limits the types of nanoparticle superlattices that can be synthesized. Here, we report a universal strategy to vastly enrich the library of nanoparticle superlattices, based on multiple-unit (≥4 units) DNA origami platforms, which were constructed by programmably cocrystallizing three different DNA origami octahedral "homologs." Through selectively inserting nanoparticles into DNA origami monomers, numerous nanoparticle superlattices can be synthesized on the basis of the same platform. In this work, we obtained 85 types of DOF/AuNP (DNA origami frame/gold nanoparticle) superlattices using three different DNA origami platforms as examples. We believe that our strategy can provide possible access to fabricate virtually endless types of nanoparticle superlattices and promote the construction of functional materials with special properties.

A compact gain-enhanced microwave helical antenna for 87Rb atomic experiments.

We present a compact and gain-enhanced microwave helical antenna for manipulating ultracold 87Rb atoms coherently. By replacing the reflecting plate with an enhancing cup, the voltage standing wave ratio is reduced by 0.5 in the frequency range of 6.73-6.93 GHz, which covers the resonant frequency between the ground-state hyperfine levels of the 87Rb atom. The gain of the helical antenna is increased by 1.25-1.63 dBi, whose length is 89 mm. Applying the antenna to ultracold 87Rb atomic experiments, we achieve a Rabi frequency of 60(1) ×2π kHz of the oscillation between the hyperfine levels.

Herbal medicines in the treatment of tinnitus: An updated review.

Tinnitus is perception of sound in the absence of an apparent external acoustic stimulus. The condition is prevalent in adults, especially the elderly (≥65 years), and may be associated with cognitive function decline and significantly impacts on the quality of life, heralding difficulties in managing this challenging disorder. Interventions for tinnitus have been varied. However, drugs have not yet been approved for the treatment of tinnitus and there is no pharmacotherapy recommended by existing guidelines. Still, herbal medicines are used for the treatment of tinnitus in many countries, especially Gingko (G.) biloba. In the current updated literature review, we evaluated the efficacy of herbal medicines in the treatment of tinnitus by reviewing the evidence of relevant randomized controlled trials. The authors also highlight some of the issues in clinical trials of herbal medicines given that currently available evidence on herbal medicines for tinnitus is overall of insufficient quality and the conclusions from existing trials are conflicting. Nevertheless, there is a clear and urgent need for safe and effective pharmacotherapy of tinnitus.

Thermalization dynamics of a gauge theory on a quantum simulator.

Gauge theories form the foundation of modern physics, with applications ranging from elementary particle physics and early-universe cosmology to condensed matter systems. We perform quantum simulations of the unitary dynamics of a U(1) symmetric gauge field theory and demonstrate emergent irreversible behavior. The highly constrained gauge theory dynamics are encoded in a one-dimensional Bose-Hubbard simulator, which couples fermionic matter fields through dynamical gauge fields. We investigated global quantum quenches and the equilibration to a steady state well approximated by a thermal ensemble. Our work may enable the investigation of elusive phenomena, such as Schwinger pair production and string breaking, and paves the way for simulating more complex, higher-dimensional gauge theories on quantum synthetic matter devices.

Low-noise and high-power second harmonic generation of 532 nm laser for trapping ultracold atoms.

Optical lattices for coherently manipulating ultracold atoms demand high-power, low-noise, narrow-line-width, and continuous-wave lasers. Here, we report the implementation of a 30 W 532 nm low-noise laser by second harmonic generation from a 1064 nm fiber laser, which is capable to generate optical lattices for a quantum gas microscope of Rb87 atoms. The overall conversion efficiency is 59% at an input power of 51 W with a lithium triborate crystal coupled to a ring cavity. The relative intensity noise of the output laser is suppressed to -120 dBc/Hz in the range of 10 Hz-100 kHz with a high dynamic range of over 50 dB, which is suitable for long-term trapping and coherent manipulation of the quantum gases.

Exosomal lncRNA NEAT1 from cancer-associated fibroblasts facilitates endometrial cancer progression via miR-26a/b-5p-mediated STAT3/YKL-40 signaling pathway.

Cancer-associated fibroblasts cells (CAFs) confer a rapid growth and metastasis ability of endometrial cancer (EC) via exosomes-mediated cellular communication. Long non-coding RNA nuclear enriched abundant transcript 1 (lncRNA NEAT1) drives the malignant phenotypes of EC cells. However, the role of exosomal NEAT1 from CAFs in EC progression remains ambiguous, which needs to be investigated. In our study, NEAT1 and YKL-40 were up-regulated, while miR-26a/b-5p was down-regulated in EC tissues. Moreover, NEAT1 expression was increased in CAF-exosomes compared with that in NF-exosomes. In addition, the exosomal NEAT1 derived from CAFs could transfer to EC cells and promote YKL-40 expression. Further exploration showed that exosomal NEAT1 enhanced YKL-40 expression via regulating miR-26a/b-5p-STAT3 axis in EC cells. More importantly, exosomal NEAT1 accelerated in vivo tumor growth via miR-26a/b-5p-STAT3-YKL-40 axis. Taken together, our study reveals that exosomal NEAT1 from CAFs contributes to EC progression via miR-26a/b-5p-mediated STAT3/YKL-40 pathway, which indicates the therapeutic potential of exosomal NEAT1 for treating EC.

A high-power and low-noise 532-nm continuous-wave laser for quantum gas microscopy.

Low-noise, high-power 532-nm lasers are of great interest in many scientific research studies, such as gravitational wave detection and ultracold atom experiments. In particular, in the experiments of quantum gas microscopy, a large power of laser is necessary during the imaging process, while low noise is important for preventing the atoms from being heated up. In this work, we report on the generation of such a 532-nm continuous-wave laser by coherently combining two laser beams produced by single-pass second-harmonic generation. The power of the combined laser is up to 17 W. With the help of intensity stabilization, we are able to suppress the relative intensity noise to below -120 dBc/Hz. The generated laser satisfies the experimental requirements for integrating optical superlattices with a quantum gas microscope.

Two-dimensional TiO2-g-C3N4 with both TiN and CO bridges with excellent conductivity for synergistic photoelectrocatalytic degradation of bisphenol A.

TiO2-mediated photoelectrocatalysis is emerging as a promising way to degrade refractory contaminates. Nevertheless, the concrete application of TiO2 is seriously limited because of its poor conductivity, unexpected recombination of photoinduced charges, and broad bandgap (3.2 eV). In this work, two-dimensional (2D) TiO2-g-C3N4 with both TiN and CO bridges is successfully constructed and assembled with carbon fibers to realize efficient photoelectrochemical (PEC) pollutant degradation. Density functional theory (DFT) calculations suggest that the generated interface heterojunction of 2D TiO2-g-C3N4 can provide quick charge separation and transfer via both TiN and CO bridges, resulting in a prepared catalyst that can facilitate the effective separation and transportation of photoinduced electron-hole pairs. In addition, according to electrochemical impedance spectroscopy, the 2D TiO2-g-C3N4 composition with the generated interface heterojunction reduces internal resistance and becomes more conducive to electrocatalysis compared with pure TiO2 or g-C3N4. Using bisphenol A (BPA) as a typical refractory contaminate, the 2D TiO2-g-C3N4/carbon fiber electrode exhibits a higher PEC activity, with reaction rates 1.7, 2.5, and 3 times faster than that of g-C3N4, TiO2, and commercial P25, respectively. Furthermore, the greatest BPA degradation of the PEC system is much higher than the sum of the photocatalytic (PC) and electrocatalytic (EC) systems. Additionally, the enhanced activities of electrocatalysis and photocatalysis for the degradation of BPA is attributed to the collaboration of the interfacial effect and excellent electrical conductivity derived from the 2D structure of the TiO2-g-C3N4 heterojunction. This study proposes a new tactic for the design and construction of photoelectrocatalysts via a synergistic interfacial effect to improve the photocatalytic and electrocatalytic degradation activities for refractory pollutants.

Laparoscopic versus open surgery for rectal cancer: a systematic review and meta-analysis of randomized controlled trials.

BACKGROUND AND AIM: Laparoscopic and open rectum surgery for rectal cancer remains controversial. This systematic review compared the short-term and long-term efficiency and complications associated with laparoscopic and open resection for rectal cancer. MATERIALS AND METHODS: We searched PubMed, Embase, Cochrane Library, ISI Web of Knowledge and the China Biology Medicine Database to identify potential randomized controlled trials from their inception to March 31, 2014 without language restriction. Additional articles were identified from searching bibliographies of retrieved articles. Two reviewers independently assessed the full-text articles according to the pre-specified inclusion and exclusion criteria as well as the methodological quality of included trials. The meta-analysis was performed using RevMan 5.2. RESULTS: A total of 16 randomized controlled trials involving 3,045 participants (laparoscopic group, 1,804 cases; open group, 1,241 cases) were reviewed. Laparoscopic surgery was associated with significantly lower intraoperative blood loss, earlier return of bowel movement and reduced length of hospital stay as compared to open surgery, although with increased operative time. It also showed an obvious advantage for minimizing late complications of adhesion-related bowel obstruction. Importantly, there were no significant differences in other postoperative complications, oncological clearance, 3-year and 5-year or 10 year recurrence and survival rates between two procedures. CONCLUSIONS: On the basis of this meta-analysis we conclude that laparoscopic surgery has advantages of earlier postoperative recovery, less blood loss and lower rates of adhesion-related bowel obstruction. In addition, oncological outcome is comparable after laparoscopic and open resection for rectal cancer.