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Sodium-ion batteries (SIBs) as a promising technology for large-scale energy storage have received unprecedented attention. However, the cathodes in SIBs generally suffer from detrimental cathode-electrolyte interfacial side reactions and structural degradation during cycling, which leads to severe capacity fade and voltage decay. Here, we have developed an ultra-stable Na0.72Ni0.20Co0.21Mn0.55Mg0.036O2 (NCM-CS-GMg) cathode material in which a Mg-free core is encapsulated by a shell with gradient distribution of Mg using coprecipitation method with Mg-hysteretic cascade feedstock followed by calcination. From the interior to outer surface of the shell, as the content of electrochemically inactive Mg gradually increases, the Na+ deintercalation amount gradually decreases after charged. Benefiting from this surface gradient desodiation, the surface transition metal (TM) ion migration from TM layers to Na layers is effectively inhibited, thus suppressing the layered-to-rock-salt phase transition and the resultant microcracks. Besides, the less formation of high-valence TM ions on the surface contributes to a stable cathode-electrolyte interface. The as-prepared NCM-CS-GMg exhibits remarkable cycling life over 3000 cycles with a negligible voltage drop (0.127 mV per cycle). Our findings highlight an effective way to developing sustainable cathode materials without compromising on the initial specific capacity for SIBs., (© 2024 Wiley‐VCH GmbH.)

The treatment of hepatocellular carcinoma (HCC) is particularly challenging due to the inherent tumoral heterogeneity and easy resistance towards chemotherapy and immunotherapy. Arsenic trioxide (ATO) has emerged as a cytotoxic agent effective for treating solid tumors, including advanced HCC. However, its effectiveness in HCC treatment remains limited, and the underlying mechanisms are still uncertain. Therefore, this study aimed to characterize the effects and mechanisms of ATO in HCC. By evaluating the susceptibilities of human and murine HCC cell lines to ATO treatment, we discovered that HCC cells exhibited a range of sensitivity to ATO treatment, highlighting their inherent heterogeneity. A gene signature comprising 265 genes was identified to distinguish ATO-sensitive from ATO-insensitive cells. According to this signature, HCC patients have also been classified and exhibited differential features of ATO response. Our results showed that ATO treatment induced reactive oxygen species (ROS) accumulation and the activation of multiple cell death modalities, including necroptosis and ferroptosis, in ATO-sensitive HCC cells. Meanwhile, elevated tumoral immunogenicity was also observed in ATO-sensitive HCC cells. Similar effects were not observed in ATO-insensitive cells. We reported that ATO treatment induced mitochondrial injury and mtDNA release into the cytoplasm in ATO-sensitive HCC tumors. This subsequently activated the cGAS-STING-IFN axis, facilitating CD8 + T cell infiltration and activation. However, we found that the IFN pathway also induced tumoral PD-L1 expression, potentially antagonizing ATO-mediated immune attack. Additional anti-PD1 therapy promoted the anti-tumor response of ATO in ATO-sensitive HCC tumors. In summary, our data indicate that heterogeneous ATO responses exist in HCC tumors, and ATO treatment significantly induces immunogenic cell death (ICD) and activates the tumor-derived mtDNA-STING-IFN axis. These findings may offer a new perspective on the clinical treatment of HCC and warrant further study., (© 2024. The Author(s).)

Alcoholic liver disease (ALD) poses a substantial global health challenge, with its pathogenesis deeply rooted in mitochondrial dysfunction. Our study explores the pivotal roles of Phosphoglycerate mutase family member 5 (Pgam5) and Voltage-Dependent Anion Channel 1 (VDAC1) in the progression of ALD, providing novel insights into their interplay and impact on mitochondrial integrity. We demonstrate that Pgam5 silencing preserves hepatocyte viability and attenuates ethanol-induced apoptosis, underscoring its detrimental role in exacerbating hepatocyte dysfunction. Pgam5's influence extends to the regulation of VDAC1 oligomerization, a key process in mitochondrial permeability transition pore (mPTP) opening, mitochondrial swelling, and apoptosis initiation. Notably, the inhibition of VDAC1 oligomerization through Pgam5 silencing or pharmacological intervention (VBIT-12) significantly preserves mitochondrial function, evident in the maintenance of mitochondrial membrane potential and reduced reactive oxygen species (ROS) production. In vivo experiments using hepatocyte-specific Pgam5 knockout ( Pgam5 hKO ) and control mice reveal that Pgam5 deficiency mitigates ethanol-induced liver histopathology, inflammation, lipid peroxidation, and metabolic disorder, further supporting its role in ALD progression. Our findings highlight the critical involvement of Pgam5 and VDAC1 in mitochondrial dysfunction in ALD, suggesting potential therapeutic targets. While promising, these findings necessitate further research, including human studies, to validate their clinical applicability and explore broader implications in liver diseases. Overall, our study provides a significant advancement in understanding ALD pathophysiology, paving the way for novel therapeutic strategies targeting mitochondrial pathways in ALD., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

The discovery of magnetism in van der Waals (vdW) materials has established unique building blocks for the research of emergent spintronic phenomena. In particular, owing to their intrinsically clean surface without dangling bonds, the vdW magnets hold the potential to construct a superior interface that allows for efficient electrical manipulation of magnetism. Despite several attempts in this direction, it usually requires a cryogenic condition and the assistance of external magnetic fields, which is detrimental to the real application. Here, we fabricate heterostructures based on Fe 3 GaTe 2 flakes that have room-temperature ferromagnetism with excellent perpendicular magnetic anisotropy. The current-driven nonreciprocal modulation of coercive fields reveals a high spin-torque efficiency in the Fe 3 GaTe 2 /Pt heterostructures, which further leads to a full magnetization switching by current. Moreover, we demonstrate the field-free magnetization switching resulting from out-of-plane polarized spin currents by asymmetric geometry design. Our work could expedite the development of efficient vdW spintronic logic, memory, and neuromorphic computing devices.

Piezoelectric sensors are excellent damage detectors that can be applied to structural health monitoring (SHM). SHM for complex structures of aerospace vehicles working in harsh conditions is frequently required, posing challenging requirements for a sensor's flexibility, radiation hardness, and high-temperature tolerance. Here, we fabricate a flexible and lightweight Pb(Zr 0.53 Ti 0.47 )O 3 piezoelectric film on flexible KMg 3 (AlSi 3 O 10 )F 2 substrate via van der Waals (vdW) heteroepitaxy, endowing it with robust ferroelectric and piezoelectric properties under low energy-high flux protons (LE-HFPs) radiation (10 15 p/cm 2 ). More importantly, the Pb(Zr 0.53 Ti 0.47 )O 3 film sensor maintains highly stable damage monitoring sensitivity on an aluminum plate under harsh conditions of LE-HFPs radiation (10 15 p/cm 2 , flat structure), high temperature (175 °C, flat structure), and mechanical fatigue (bending 10 5 cycles under a radius of 5 mm, curved structure). All these superior qualities are suggested to result from the outstanding film crystal quality due to vdW epitaxy. The flexible and lightweight Pb(Zr 0.53 Ti 0.47 )O 3 film sensor demonstrated in this work provides an ideal candidate for real - time SHM of aerospace vehicles with flat and complex curve-like structures working in harsh aerospace environments.

This study investigated the impact of ultrasonic extraction (UE) on the structure and in vitro antibacterial activity of polysaccharides from sugarcane leaves (SLW). Native sugarcane leaf polysaccharides were treated with ultrasound (480 W) for 3 h to yield sugarcane leaf polysaccharides (SLU). Compared to SLW (33.59 kDa), the molecular weight of SLU (13.08 kDa) was significantly decreased, while the monosaccharide composition of SLU was unchanged. The results of SEM and XRD indicated that UE significantly changed the surface morphology of SLW and destroyed its inner crystalline structure. In vitro experiments showed that SLU had stronger antibacterial activity. These findings revealed that UE treatment could alter the tertiary structure of SLW but had no impact on its primary structure. Furthermore, the antibacterial activity of SLW could be greatly enhanced after UE treatment. As a bioactive additive, SLU has great application potential in functional foods, cosmetics, and pharmaceuticals., (© 2023 Wiley-VHCA AG, Zurich, Switzerland.)

Objectives: This study aimed to investigate the efficacy of ultrasound-guided Percutaneous Transhepatic Biliary Drainage (PTCD) for the treatment of Acute Obstructive Suppurative Cholangitis (AOSC) combined with septic shock due to choledocholithiasis, and its effect on inflammatory factors., Methods: Clinical data of 86 patients with AOSC and septic shock admitted to our hospital between January 2019 and May 2021 were retrospectively analyzed and grouped according to different treatment methods. Among them, 43 patients who underwent Endoscopic Retrograde Cholangiopancreatography (ERCP) and Endoscopic Nasobiliary Drainage (ENBD) were included in the Control Group (CNG), and 43 patients who underwent ultrasound-guided PTCD were included in the Study Group (SG)., Results: The total effective rate in the SG (88.37%) was higher than that in the CNG (69.77%) (p < 0.05); after surgery, the serum inflammatory factors PCT, IL-6, TNF-α, CRP levels, liver function indicators such as TBIL, DBIL, AST, ALT levels, and stress response indicators including NPY, PGE2, 5-HT levels were reduced, and were lower in the SG than in the CNG (p < 0.05); postoperatively, CD3+, CD4+, and CD4+/CD8+ levels in the CNG were significantly lower than those before surgery (p < 0.05); Postoperatively, CD3+, CD4+, and CD4+/CD8+ levels in the SG were significantly higher than those in the CNG (p < 0.05); and the complication rate in the SG (6.98%) was lower than that in the CNG (25.58%) (p < 0.05)., Conclusions: Ultrasound-guided PTCD for AOSC combined with septic shock can facilitate the recovery of liver and immune functions with a low complication rate., Competing Interests: Conflicts of interest The authors declare no conflicts of interest., (Copyright © 2023 HCFMUSP. Published by Elsevier España, S.L.U. All rights reserved.)

Fe-based superconductors are one of the current research focuses. FeTe is unique in the series of FeSe 1- x Te x , since it is nonsuperconducting near the FeTe side in the phase diagram in contrast to the presence of superconductivity in other region. However, FeTe thin films become superconducting after oxygen annealing and the mechanism remains elusive. Here, we report the temperature dependences of resistivity, Hall effect and magnetoresistance (MR) of a series of FeTe thin films with different amounts of excess Fe and oxygen. These properties show dramatic changes with excess Fe and oxygen incorporation. We found the Hall coefficients are positive for the oxygen-annealed samples, in contrast to the transition from positive to negative below 50 K for the vacuum-annealed samples. For all samples, both the resistivity and Hall coefficient show a dramatic drop, respectively, at around 50 K-75 K, implying coexistence of superconductivity and antiferromagnetic order for the oxygen-annealed samples. The vacuum-annealed samples show both positive and negative values of MR depending on temperature, while negative MR dominates for the oxygen-annealed samples. We also found that oxygen annealing reduces the excess Fe in FeTe, which has been neglected before. The results are discussed in terms of several contributions, and a comparison is made between the oxygen-annealed FeTe thin films and FeSe 1- x Te x . This work is helpful for shedding light on the understanding of oxygen-annealed FeTe thin films., (© 2023 IOP Publishing Ltd.)

Characterization of covalency of intermolecular interactions in the van der Waals distance limit remains challenging because the interactions between molecules are weak, dynamic, and not measurable. Herein, we approach this issue in a series of supramolecular mixed-valence (MV) donor(D)-bridge(B)-acceptor(A) systems consisting of two bridged Mo 2 units with a C 6 H 6 molecule encapsulated, as characterized by the X-ray crystal structures. Comparative analysis of the intervalence charge transfer spectra in benzene and dichloromethane substantiates the strong electronic decoupling effect of the solvating C 6 H 6 molecule that breaks down the dielectric solvation theory. Ab initio and DFT calculations unravel that the intermolecular orbital overlaps between the complex bridge and the C 6 H 6 molecule alter the electronic states of the D-B-A molecule through intermolecular nuclear dynamics. This work exemplifies that site-specific intermolecular interaction can be exploited to control the chemical property of supramolecular systems and to elucidate the functionalities of side-chains in biological systems., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

Background: Malignant obstructive jaundice (MOJ) is a common pathologic manifestation of malignant biliary obstruction. Recently, several clinical trials have explored the clinical effectiveness of intraluminal 125 I seed-based brachytherapy for MOJ patients, and various outcomes have been reported., Aim: To assess the efficacy and safety of percutaneous biliary stents with 125 I seeds compared to conventional metal stents in patients with unresectable MOJ., Methods: A systematic search of English-language databases (PubMed, Embase, Cochrane Library, and Web of Science) was performed to identify studies published prior to June 2020 that compared stents with or without 125 I seeds in the treatment of unresectable MOJ. The outcomes analyzed included primary outcomes (stent patency and overall survival) and secondary outcomes (complications and liver function parameters)., Results: Six randomized controlled trials and four retrospective studies involving 875 patients were eligible for the analysis. Of the 875 included patients, 404 were treated with 125 I seed stents, while 471 were treated with conventional stents. Unadjusted pooled analysis demonstrated that compared to conventional stents, 125 I seed stents extended the stent patency time [hazard ratio (HR) = 0.36, 95% confidence interval (CI) = 0.28-0.45, P < 0.0001] and overall survival period (HR = 0.52, 95%CI = 0.42-0.64, P < 0.00001). Subgroup analyses based on the type of 125 I seed stent and type of study design showed consistent results. However, there were no significant differences in the occurrence of total complications [odds ratio (OR) = 1.12, 95%CI = 0.75-1.67, P = 0.57], hemobilia (OR = 1.02, 95%CI = 0.45-2.3, P = 0.96), pancreatitis (OR = 1.79, 95%CI = 0.42-7.53, P = 0.43), cholangitis (OR = 1.13, 95%CI = 0.60-2.13, P = 0.71), or pain (OR = 0.67, 95%CI = 0.22-2, P = 0.47). In addition, there were no reductions in the levels of serum indices, including total bilirubin [mean difference (MD) = 10.96, 95%CI = -3.56-25.49, P = 0.14], direct bilirubin (MD = 7.37, 95%CI = -9.76-24.5, P = 0.4), alanine aminotransferase (MD = 7.52, 95%CI = -0.71-15.74, P = 0.07), and aspartate aminotransferase (MD = -4.77, 95%CI = -19.98-10.44, P = 0.54), after treatment. Publication bias was detected regarding the outcome overall survival; however, the conclusions were not changed after the adjustment., Conclusion: Placement of stents combined with brachytherapy using 125 I seeds contributes to a longer stent patency and higher overall survival than placement of conventional stents without extra complications or severe liver damage. Thus, it can be considered an effective and safe treatment for unresectable MOJ., Competing Interests: Conflict-of-interest statement: The authors deny any conflict of interest related to this manuscript., (©The Author(s) 2021. Published by Baishideng Publishing Group Inc. All rights reserved.)

The semiclassical models of nonadiabatic transition were proposed first by Landau and Zener in 1932, and have been widely used in the study of electron transfer (ET); however, experimental demonstration of the Landau-Zener formula remains challenging to observe. Herein, employing the Hush-Marcus theory, thermal ET in mixed-valence complexes {[Mo 2 ]-(ph) n -[Mo 2 ]} + (n = 1-3) has been investigated, spanning the nonadiabatic throughout the adiabatic limit, by analysis of the intervalence transition absorbances. Evidently, the Landau-Zener formula is valid in the adiabatic regime in a broader range of conditions than the theoretical limitation known as the narrow avoided-crossing. The intermediate system is identified with an overall transition probability (κ el ) of ∼0.5, which is contributed by the single and the first multiple passage. This study shows that in the intermediate regime, the ET kinetic results derived from the adiabatic and nonadiabatic formalisms are nearly identical, in accordance with the Landau-Zener model. The obtained insights help to understand and control the ET processes in biological and chemical systems.

Integrating tunable characteristics and multiple functions into a single metasurface has become a new scientific and technological undertaking that needs to deal with huge challenges, especially in the terahertz frequency region. The multifunctional design combining the broadband absorption and broadband polarization conversion using a single switchable metasurface is proposed in this paper. The switchable performance can be realized by treating the insulation to metal phase transition properties of vanadium dioxide (VO 2 ). At high temperature (74 °C), the proposed metasurface can be used as a broadband absorber which consists of a VO 2 square ring, polyimide (PI) spacer, and VO 2 film. Simulated results show that the terahertz wave absorption can reach above 90% with the bandwidth ratio of 75% in the frequency range of 0.74 THz-1.62 THz. This absorber is insensitive to polarization resulted from the symmetry structure and also shows a good performance at large incident angles. Once the temperature is lower than the cooling phase transition temperature (about 62 °C) and VO 2 is in insulation state, the metasurface can be transformed into a broadband linear-to-circular polarization converter. Numerical simulation depicts that the ellipticity reaches to -1 and the axis ratio is lower than 3 dB from 1.47 THz to 2.27 THz. The designed switchable metasurface provides the potential to be used in the fields of advanced research and intelligent applications in the terahertz frequency region.

A trans-dimolybdenum nicotinate (m-Mo2) complex and its isonicotinate isomer (p-Mo2) were synthesized and characterized crystallographically, and their single-molecule charge transport properties were investigated using the STM break junction (STM-BJ) technique. With a quadruply bonded Mo2 complex unit integrated into molecular backbones, the single-molecule conductance for complex molecules was increased by more than one order of magnitude compared with that of the organic π-conjugated analogues 1,4-bis(4-pyridyl)benzene (p-Ph) and 1,4-bis(3-pyridyl)benzene (m-Ph). More interestingly, unlike m-Ph, m-Mo2 with meta connected pyridyl anchors presents larger conductance than that of p-Mo2 with two para connected pyridyl groups. DFT-based transmission calculations revealed that the significant conductance enhancement of Mo2 molecules originates from the largely reduced HOMO-LUMO gap, and the unique d(δ)-p(π) conjugation between the Mo2 unit and the pyridine rings gives rise to a delocalized electronic structure that endows the Mo2 molecules with an unexpected high conductance.

Heterostructures composed of superconductor and ferroelectrics (SC/FE) are very important for manipulating the superconducting property and applications. However, growth of high-quality superconducting iron chalcogenide films is challenging because of their volatility and FE substrate with rough surface and large lattice mismatch. Here, we report a two-step growth approach to get high-quality FeSe 0.5 Te 0.5 (FST) films on FE Pb(Mg 1/3 Nb 2/3 ) 0.7 Ti 0.3 O 3 with large lattice mismatch, which show superconductivity at only around 10 nm. Through a systematic study of structural and electric transport properties of samples with different thicknesses, a mechanism to grow high-quality FST is discovered. Moreover, electric-field-induced remarkable change of T c (superconducting transition temperature) is demonstrated in a 20 nm FST film. This work paves the way to grow high-quality films which contain volatile element and have large lattice mismatch with the substrate. It is also helpful for manipulating the superconducting property in SC/FE heterostructures.

Studies of intermolecular interactions enhance our knowledge of chemistry across molecular and supramolecular levels. Here, we show that host-guest quadrupolar interaction has a profound influence on the molecular system. With covalently bonded dimolybdenum complex units as the electron donor (D) and acceptor (A) and a thienylene group (C 4 H 2 S) as the bridge (B), the mixed-valence D-B-A complexes are shaped with clefts in the middle of the molecule. Interestingly, in aromatic solvents, the D-A electronic coupling constants (H ab ) and electron transfer rates (k et ) are dramatically reduced. Theoretical computations indicate that an aromatic molecule is encapsulated in the cleft of the D-B-A array; quadrupole-quadrupole interaction between the guest molecule and the C 4 H 2 S bridge evokes a charge redistribution, which increases the HOMO-LUMO energy gap, intervening in the through-bond electron transfer. These results demonstrate that a supramolecular system is unified underlying the characteristics of the assembled molecules through constitutional, electronic, and energetic complementarities., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

This paper presents an autonomous multi-input (multi-beam) reconfigurable power-management chip for optimal energy harvesting from weak multi-axial human motion using a multi-beam piezoelectric energy harvester (PEH). The proposed chip adaptively operates in either voltage-mode or synchronous-electrical-charge-extraction-mode (VM-SECE) to improve overall efficiency, extract maximum energy regardless of the PEH beams' impedance/voltage/frequency variations, and protect the chip against large inputs, eliminating the need for high-voltage processes. It can simultaneously harvest energy from up to 6 beams using only one shared off-chip inductor. It uses an active negative voltage converter to extend the input-voltage range to as low as 35 mV. In addition, an active voltage doubler with a small footprint is implemented for faster cold start. A prototype VM-SECE chip was fabricated in a 0.35-μm 2P4M standard CMOS process occupying 1.9 mm 2 active area. To fully characterize the chip performance, it was tested with both a commercial single-beam PEH and a custom-made PEH with five mechanically plucked thin-film beams. With the commercial PEH, compared to an on-chip full-wave active rectifier (FAR) with 95.6% efficiency, the VM-SECE chip harvested 3.28x more power for shock inputs at 1 Hz frequency and 4.39 g acceleration. With the custom 5-beam PEH for a pseudo-walking condition, compared to the on-chip FAR, the VM-SECE chip harvested 1.59x and 2.38x more power for 1-and 5-beam operations, respectively.

The aim of this study was to analyze the expressions and significance of B7-H3 and CTLA-4 in the clinical stages of non-small-cell lung cancer (NSCLC). Seventy patients with NSCLC who underwent surgical resection or biopsy between January 2016 and February 2018 were enrolled. Among them, 30 were cases of paracancerous tissues and were assigned to the control group (CON). These cases were analyzed using immunochemical methods. Of the 70 cases, 48 were of adenocarcinoma, 19 were of squamous cell carcinoma, and 3 were of adenosquamous carcinoma. The expression rates of B7-H3 and CTLA-4 in the observation group (OBS) were 64.2% and 57.1% respectively, and those in the CON group were 6.7% and 0%, respectively (χ 2 =27.988, 28.571, P <0.001). The expression levels of B7-H3 and CTLA-4 in patients with poor differentiation, in stages III-IV, or with lymph node metastasis were significantly higher than those in patients with good-to-moderate differentiation, in stages I-II, and without lymph node metastasis ( P <0.05). There was a positive correlation between the expressions of B7-H3 and CTLA-4 in the OBS group (r=0.74, P <0.05). B7-H3 and CTLA-4 are highly expressed and positively correlated with each other in NSCLC patients and are also closely related to clinical stages., Competing Interests: None., (IJCEP Copyright © 2019.)

Quadruply bonded dimolybdenum complexes with a σ 2 π 4 δ 2 electronic configuration for the ground state have rich metal-centered photochemistry. An earlier study showed that stoichiometric or less amount of molecular hydrogen was produced upon irradiation by ultraviolet light (λ = 254 nm) of K 4 Mo 2 (SO 4 ) 4 in sulfuric acid solution, which was attributed to the reductive capability of the ππ* excited state. To make use of the δ electrons for visible-light-induced photocatalytic hydrogen evolution, a multicomponent heterogeneous photocatalytic system containing K 4 Mo 2 (SO 4 ) 4 photosensitizer, TiO 2 electron relay, and MoS 2 cocatalyst is designed and tested. With ascorbic acid added as a sacrificial reagent, irradiation by artificial sunlight (AM 1.5) on the reaction in 5 M H 2 SO 4 has produced 13 400 μmol g -1 of molecular hydrogen (based on the Mo 2 complex), which is 30 times higher than the hydrogen yield obtained from the reaction of bare K 4 Mo 2 (SO 4 ) 4 with H 2 SO 4 under ultraviolet light irradiation. Further improvement of hydrogen evolution is achieved by addition of oxalic acid, along with an electron donor, which gives an additional 50% increase in H 2 yield. Spectroscopic analyses indicate that, in this case, a junction between the Mo 2 complex and TiO 2 is built by the oxalate bridging ligand, which facilitates charge injection and separation from the Mo 2 core. This Mo 2 -TiO 2 -MoS 2 system has achieved a high hydrogen evolution rate up to 4570 μmol g -1 h -1 . The efficiency of K 4 Mo 2 (SO 4 ) 4 as a metal-centered photosensitizer is also proved by parallel experiments with a dye chromophore, fluorescein, which presents comparable H 2 yields and hydrogen evolution rates. Most importantly, in this study, detailed analyses illustrate that the photocatalytic cycle with hydrogen gas as an outcome of the reaction is established by involvement of the δδ* excited state generated by visible light irradiation. Therefore, this work shows the potential of quadruply bonded Mo 2 complexes as photosensitizers for photocatalytic hydrogen evolution.

This paper summarizes our recent progress towards Gastric Seed which is an ultrasonically interrogated millimeter-sized implant for gastric electrical activity (also known as slow waves, SWs) recording. We present a proof-of-concept wireless system designed to collect, transmit, and store in vivo SW signals by integrating a prototype Gastric Seed chip, fabricated in a 0.35-μm 2P4M CMOS process, with a commercial-off-the-shelf (COTS) amplifier, 10-bit analog-to-digital converter (ADC), and pair of microcontrollers (MCU) as radio-frequency (RF) transceivers. The chip includes ultrasonic self-regulated power management and addressable pulse-based data transfer. Utilizing two pairs of millimeter-sized stacked power/data ultrasonic transducers spaced by 6 cm in a water tank, the chip achieved a regulated voltage of 2.5 V and a data rate of 16 kbps. The amplifier was configured to have a gain of 60 dB with a 3-dB bandwidth of 18 mHz to 500 mHz. The MCU's built-in 10-bit ADC and RF transceiver were used to digitize the SW signal and transmit the data to a computer. In vivo, SW was recorded wirelessly from the stomach of an anesthetized rat. The recorded SWs showed a frequency of 1.5 cycle-per-minute (cpm) and maximum and minimum amplitudes of 1.03 mV and 0.28 mV peak-to-peak, respectively.

This paper introduces the concept of self-image-guided ultrasonic (SIG-US) wireless power transmission (WPT) for robust and efficient WPT to millimeter-sized biomedical implants distributed inside the body. In SIG-US WPT, a sharp pulse is transmitted periodically by the implant to create short ringing with relatively various delays across an array of external (wearable) ultrasonic transducers. These relative delays are used to drive the external array as in phased-array beamforming, generating a highly focused ultrasound intensity at the implant's location due to the reciprocity. Therefore, regardless of implant's misalignment, orientation, and medium (i.e., without any prior knowledge) optimal parameters for beamforming is found by the SIG-US technique without the need for a conventional imaging system, suffering from high power consumption, size, cost, and complexity. In our proof-of-concept simulation setup with a linear transducer array (11 transducers), the SIG-US technique improved delivered power to a 1 mm 3 implant with 6 mm misalignment (powering distance of 30 mm) by 95.7 times compared with conventional beamforming. In addition, for up to 6 mm implant's misalignment, the received power with the SIG-US technique only varied by 1.2 times compared with 156.3 times variation in the received power in conventional beamforming.

This paper presents the concept of Gastric Seed, which is an ultrasonically interrogated millimeter-sized implant for gastric electrical-wave (also known as slow waves, SWs) recording. A network of Gastric Seeds can be endoscopically implanted within the stomach submucosal space for large-scale SW recording. This paper also summarizes our recent effort towards Gastric Seed development including ultrasonic self-regulated power management and addressable ultrasonic pulse-based data transfer. The proposed power management in the form of a voltage doubler only requires a single off-chip capacitor for simultaneous rectification, regulation and over-voltage protection (OVP) by utilizing ultrasonic transducer's internal capacitance and reverse current. For data transfer, sharp ultrasonic pulses are transmitted to reduce the implant's power consumption. A proof-of-concept addressable chip was fabricated in a 0.35-μm standard CMOS process. Utilizing two pairs of millimeter-sized stacked power/data ultrasonic transducers spaced by 3.75 cm in a water tank, the chip achieved measured regulated voltage of 3 V and data rate of 75 kbps with the data transmitter energy consumption of 440 pJ/bit.

Inverse-electron-demand Diels-Alder reactions have attracted intense research focus. However, enolate and enamine are the most employed intermediates to realize such transformation, and the use of dienolate intermediate remains elusive. Reported herein is the asymmetric inverse-electron-demand oxa-Diels-Alder reaction between allyl ketones and alkenyl 1,2-diketones using a bifunctional thiourea catalyst. The reaction afforded various highly functionalized dihydropyrans with good to excellent enantioselectivities under mild conditions, and further novel transformations on the products have also been realized.

Thermal electron transfer through hydrogen bonds remains largely unexplored. Here we report the study of electron transfer through amide-amide hydrogen bonded interfaces in mixed-valence complexes with covalently bonded Mo 2 units as the electron donor and acceptor. The rate constants for electron transfer through the dual hydrogen bonds across a distance of 12.5 Å are on the order of ∼ 10 10  s -1 , as determined by optical analysis based on Marcus-Hush theory and simulation of ν(NH) vibrational band broadening, with the electron transfer efficiencies comparable to that of π conjugated bridges. This work demonstrates that electron transfer across a hydrogen bond may proceed via the known proton-coupled pathway, as well as an overlooked proton-uncoupled pathway that does not involve proton transfer. A mechanistic switch between the two pathways can be achieved by manipulation of the strengths of electronic coupling and hydrogen bonding. The knowledge of the non-proton coupled pathway has shed light on charge and energy transport in biological systems.

A series of three Mo 2 dimers bridged by a meta-phenylene group has been studied in terms of electronic coupling (EC) and electron transfer (ET) in comparison with the para isomers. Optical analyses on the mixed-valence complexes indicate that by replacing a para-phenylene bridge with a meta one, the EC between the two Mo 2 centers is dramatically weakened; consequently, the ET rates (k et ) are lowered by two to three orders of magnitude. In the para series, the EC parameters (H ab ) and ET rates (k et ) are greatly affected by O/S atomic alternation of the bridging ligand. However, for the meta analogues, similar EC and ET parameters are obtained, that is, H ab =300-400 cm -1 and k et ≈10 9  s -1 . These results suggest that through-σ-bond and/or through-space coupling channels become operative as the π conjugation is disabled. DFT calculations reveal that destructive quantum interference features seen for the meta series arise from the cancellation of two π-conjugated coupling pathways., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Drug resistance in bacteria is becoming a significant threat to global public health, and the development of novel and efficient antibacterial compounds is urgently needed. Recently, rhodium complexes have attracted attention as antimicrobial agents, yet their antibacterial mechanism remains unknown. In this study, we observed that the dirhodium (II) complex Rh 2 Ac 4 inhibited Streptococcus. pneumoniae growth without significant cytotoxic side-effects on host cells in vitro. We subsequently investigated the antibacterial mechanism of Rh 2 Ac 4 using iTRAQ-based proteomics combined with cellular and biochemical assays. Bioinformatics analysis on the proteomic alterations demonstrated that six molecular functional groups, including metal ion binding and twelve metabolic pathways, were significantly affected after treatment with Rh 2 Ac 4 . The interaction network analysis of metal ion binding proteins suggested that Rh 2 Ac 4 decreased the protein expression levels of SPD&#95;1652, SPD&#95;1590 and Gap, which are associated with haem uptake/metabolism. Cellular and biochemical assays further confirmed that Rh 2 Ac 4 could be taken up by bacteria via the PiuABCD haem-uptake system. The structurally similar Rh complex may compete with Fe-haem to decrease Fe-uptake via the PiuABCD system, disrupting iron metabolism to exert its antibacterial activity against S. pneumoniae. These data indicate that Rh 2 Ac 4 is a promising new drug for the treatment of S. pneumoniae infections., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Racemic mixtures of four stereoisomers are easily formed via many fundamental organic transformations, but the direct utilities of these mixtures have been less studied and remain large challenges to date. In this work, we introduce a new method, i.e., divergent dynamic kinetic resolution, to achieve the separation of racemic mixtures of four stereoisomers. The hypothesis was proved by using a N-heterocyclic carbene-catalyzed benzoin reaction, which afforded two separable diastereomeric products bearing three consecutive stereocenters with good to excellent enantioselectivties. We believe that this resolution protocol will find applications in more transformations., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The aim of the present study was investigate the association of the severity of emphysema of patients with chronic obstructive pulmonary disease (COPD) with airway inflammation and the COPD-specific comorbidity test (COTE) index. A total of 94 patients with COPD were divided into four groups according to the severity of their emphysema; in each patient, comorbidities were recorded and inflammatory biomarkers, including MMP-9 and TIMP-1 were determined in circulating blood. The unbalanced proportion of MMP-9 and its inhibitor, TIMP-1, led to the airway inflammation and lung remodeling in the patients with COPD. A total of 80.85% of the patients had emphysema of different degrees. The quantity of male patients and the smoking index in the three emphysema groups were significantly higher than those in the non-emphysema group (F=7.67 and 5.42, P<0.05). The level of the predicted percent offorced expiratory volume in 1 sec in the non-emphysema group were significantly higher than those in the emphysema group (4.33; P<0.05), and the level of D-dimer in the non-emphysema group was significantly lower than that in the mild and moderate emphysema groups (F=9.38, P<0.05). The low-attenuation area score was negatively correlated with inhaled bronchodilators (r=-0.240, P=0.007) but positively correlated with the frequency of acute exacerbations in the previous year (r=0.211, P=0.001). In terms of treatment, the use of systemic hormone therapy in the emphysema group was more frequent than that in the non-emphysema group (F=6.21, 12.92 and 4.08, P<0.05). The level of MMP-9 was significantly higher in COPD patients with >3 comorbidities, a COTE index of ≥4 and cardiovascular disease as well as coronary heart disease (t=6.40, 2.53, 3.65 and 2.90, P<0.05). The level of MMP-9 was positively correlated with the neutrophilic granulocyte percentage, the number of comorbidities and the COTE index (r=0.193, 0.402 and 0.311, P<0.01). The severity of emphysema in patients with COPD was correlated with the persistence of inflammatory factors in the circulating blood and the frequency of acute exacerbations. It was indicated that MMP-9 has a critical role in numerous comorbidities of COPD.

Background: Altered neuronal development is discussed as the underlying pathogenic mechanism of autism spectrum disorders (ASD). Copy number variations of 16p11.2 have recurrently been identified in individuals with ASD. Of the 29 genes within this region, quinolinate phosphoribosyltransferase ( QPRT ) showed the strongest regulation during neuronal differentiation of SH-SY5Y neuroblastoma cells. We hypothesized a causal relation between this tryptophan metabolism-related enzyme and neuronal differentiation. We thus analyzed the effect of QPRT on the differentiation of SH-SY5Y and specifically focused on neuronal morphology, metabolites of the tryptophan pathway, and the neurodevelopmental transcriptome., Methods: The gene dosage-dependent change of QPRT expression following Chr16p11.2 deletion was investigated in a lymphoblastoid cell line (LCL) of a deletion carrier and compared to his non-carrier parents. Expression of QPRT was tested for correlation with neuromorphology in SH-SY5Y cells. QPRT function was inhibited in SH-SY5Y neuroblastoma cells using (i) siRNA knockdown (KD), (ii) chemical mimicking of loss of QPRT, and (iii) complete CRISPR/Cas9-mediated knock out (KO). QPRT - KD cells underwent morphological analysis. Chemically inhibited and QPRT-KO cells were characterized using viability assays. Additionally, QPRT-KO cells underwent metabolite and whole transcriptome analyses. Genes differentially expressed upon KO of QPRT were tested for enrichment in biological processes and co-regulated gene-networks of the human brain., Results: QPRT expression was reduced in the LCL of the deletion carrier and significantly correlated with the neuritic complexity of SH-SY5Y. The reduction of QPRT altered neuronal morphology of differentiated SH-SY5Y cells. Chemical inhibition as well as complete KO of the gene were lethal upon induction of neuronal differentiation, but not proliferation. The QPRT-associated tryptophan pathway was not affected by KO. At the transcriptome level, genes linked to neurodevelopmental processes and synaptic structures were affected. Differentially regulated genes were enriched for ASD candidates, and co-regulated gene networks were implicated in the development of the dorsolateral prefrontal cortex, the hippocampus, and the amygdala., Conclusions: In this study, QPRT was causally related to in vitro neuronal differentiation of SH-SY5Y cells and affected the regulation of genes and gene networks previously implicated in ASD. Thus, our data suggest that QPRT may play an important role in the pathogenesis of ASD in Chr16p11.2 deletion carriers., Competing Interests: All study participants have given written informed consent, and the genetic study has been positively reviewed by the ethic’s committee Frankfurt (No 267/09).All authors agree to publish the presented work.All authors declare that they have no competing interests.Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Background/aim: This study performed typing of chronic obstructive pulmonary disease (COPD) using high-resolution computed tomography (HRCT) to determine the association with smoking, matrix metalloproteinases, and common comorbidities. Materials and methods: The study enrolled 94 hospitalized patients. Participants were divided into a group of 69 current and former smokers (group A) and a group of 25 that had never smoked (group B). Patients were also divided into 3 categories according to the degree of emphysema and bronchial wall thickness using HRCT to determine the association with levels of matrix metalloproteinase 9 (MMP-9) and TIMP-1, as well as associated comorbidities. These three categories were: type A - no or mild emphysema, with or without bronchial wall thickening; type E - emphysema without bronchial wall thickening; and type M - both emphysema and bronchial wall thickening. Results: The low attenuation area (LAA) scores in group A patients were higher than those in group B (t = 2.86, P < 0.01); correlation analysis showed that smoking was associated with a decline of the forced expiratory volume in 1 s and forced vital capacity ratio (FEV1/ FVC%) and higher LAA scores in patients with COPD (F = 4.46, F = 8.20, P < 0.05). The levels of MMP-9 in group A were higher than those in group B (t = 3.65, P < 0.01). Among COPD patients with more than 3 comorbidities, there were statistically significant differences in both the smoking group and the nonsmoking group (chi-square = 12.08, P < 0.01). When compared to type A patients, who had coincident cardiovascular diseases in the smoking group, patients of type M and E showed statistically significant differences (F = 2.42 and 2.12, P < 0.05). Conclusion: Emphysema was more severe in smokers. Metalloproteinase levels in smokers were higher than those in nonsmokers. Moreover, comorbidities were more severe in smokers., (CC-BY 4.0)

The large bridging ligand 9,10-anthracenedicarboxylate and its thiolated derivatives have been employed to assemble two dimolybdenum complex units and develop three Mo 2 dimers, [Mo 2 (DAniF) 3 ] 2 (μ-9,10-O 2 CC 14 H 8 CO 2 ), [Mo 2 (DAniF) 3 ] 2 (μ-9,10-OSCC 14 H 8 COS), and [Mo 2 (DAniF) 3 ] 2 (μ-9,10-S 2 CC 14 H 8 CS 2 ) (DAniF = N, N'-di( p-anisyl)formamidinate), for the study of conformation dependence of the electronic coupling between the two Mo 2 centers. These compounds feature a large deviation of the central anthracene ring from the plane defined by the Mo-Mo bond vectors, with the torsion angles (ϕ = 50-76°) increasing as the chelating atoms of the bridging ligand vary from O to S. Consequently, the corresponding mixed-valence complexes do not exhibit characteristic intervalence charge transfer absorptions in the near-IR spectra, in contrast to the phenylene and naphthalene analogues, from which these systems are assigned to the Class I in Robin-Day's scheme. Together with the phenylene and naphthalene series, the nine total mixed-valence complexes in three series complete a transition from the electronically uncoupled Class I to the strongly coupled Class II-III borderline via moderately coupled Class II and permit a systematic mapping of the bridge conformation effects on electronic coupling. Density functional theory calculations show that the HOMO-LUMO energy gap, corresponding to the metal (δ) to ligand (π*) transition energy, and the magnitude of HOMO-HOMO-1 splitting in energy are linearly related to cos 2 ϕ. Therefore, our experimental and theoretical results concur to indicate that the coupling strength decreases in the order of the bridging units: phenylene > naphthalene > anthracene, which verifies the through-bond superexchange mechanism for electronic coupling and electron transfer.

This paper presents a comprehensive comparison between inductive coupling and ultrasound for wireless power transmission (WPT) to biomedical implants. Several sets of inductive and ultrasonic links for different powering distances ( d 12 ) and receiver dimensions have been optimized, and their key parameters, including power transmission efficiency (PTE) and power delivered to the load (PDL) within safety constraints, have been compared to find out which method is optimal for any given condition. Two design procedures have been presented for maximizing the PTE of inductive and ultrasonic links by finding the optimal geometry for the transmitter (Tx) and receiver (Rx) coils and ultrasonic transducers as well as the optimal operation frequency ( f p ). Our simulation and measurement results showed that the ultrasonic link transcends the inductive link in PTE and somewhat in PDL for a small Rx of 1.1 mm 3 (diameter of 1.2 mm), particularly when the Rx was deeply implanted inside the tissue ( d 12 ≥ 10 mm). However, for a larger 20 mm 3 Rx (diameter of 5 mm), the inductive link achieved higher PTE and PDL, particularly at shorter distances ( d 12 < 30 mm). The optimal loading condition is shown to be quite different in inductive and ultrasonic links. Despite higher performance for small Rx and large d 12 , the ultrasonic link is more sensitive to Rx misalignments and orientations. This led us to propose a new design procedure based on the worst-case misalignment scenario. The simulation results have been validated by measurements. The inductive and ultrasonic links, operating at 30 MHz and 1.1 MHz, achieved measured PTEs of 0.05% and 0.65% for the 1.1 mm 3 Rx located 30 mm inside tissue and oil environments with optimal load resistances of 295 Ω and 3.8 kΩ, respectively.

The discovery of new reaction modes mediated by easily available substrates is an important research topic in organic synthesis. Allyl ketones and related compounds have been demonstrated to undergo γ- or α-selective additions to different electrophiles. We disclose here the Brønsted base-catalyzed reaction of allyl ketones and alkynyl 1,2-diketones, which undergo a unique α-selective addition/intramolecular aldol-type annulation/C-C bond cleavage process, and a series of 2-acyloxycyclopent-3-enones can be obtained under very mild conditions.

Four asymmetrical self-assembled monolayers (SAMs) consisting of two subunits with different Rh2 building blocks present a pronounced rectifying behavior. The rectification ratio (RR) increases on increasing the redox potential difference between the two Rh2 subunits, and the rectifying direction can be reversed by reordering the subunits in the assembly.

Layer-by-layer assembly of the dirhodium complex [Rh 2 (O 2 CCH 3 ) 4 ] (Rh 2 ) with linear N , N '-bidentate ligands pyrazine (L S ) or 1,2-bis(4-pyridyl)ethene (L L ) on a gold substrate has developed two series of redox active molecular wires, (Rh 2 L S ) n @Au and (Rh 2 L L ) n @Au ( n = 1-6). By controlling the number of assembling cycles, the molecular wires in the two series vary systematically in length, as characterized by UV-vis spectroscopy, cyclic voltammetry and atomic force microscopy. The current-voltage characteristics recorded by conductive probe atomic force microscopy indicate a mechanistic transition for charge transport from voltage-driven to electrical field-driven in wires with n = 4, irrespective of the nature and length of the wires. Whilst weak length dependence of electrical resistance is observed for both series, (Rh 2 L L ) n @Au wires exhibit smaller distance attenuation factors ( β ) in both the tunneling ( β = 0.044 Å -1 ) and hopping ( β = 0.003 Å -1 ) regimes, although in (Rh 2 L S ) n @Au the electronic coupling between the adjacent Rh 2 centers is stronger. DFT calculations reveal that these wires have a π-conjugated molecular backbone established through π(Rh 2 )-π(L) orbital interactions, and (Rh 2 L L ) n @Au has a smaller energy gap between the filled π*(Rh 2 ) and the empty π*(L) orbitals. Thus, for (Rh 2 L L ) n @Au, electron hopping across the bridge is facilitated by the decreased metal to ligand charge transfer gap, while in (Rh 2 L S ) n @Au the hopping pathway is disfavored likely due to the increased Coulomb repulsion. On this basis, we propose that the super-exchange tunneling and the underlying incoherent hopping are the dominant charge transport mechanisms for shorter ( n ≤ 4) and longer ( n > 4) wires, respectively, and the Rh 2 L subunits in mixed-valence states alternately arranged along the wire serve as the hopping sites.

We have synthesized and characterized the mixed-ligand dimolybdenum paddlewheel complex Na[(DAniF) 3 Mo 2 (C 3 S 5 )] (Na[1]; DAniF = N,N'-di-p-anisylformamidinate, dmit = 1,3-dithiole-2-thione-4,5-dithiolate), which has a six-membered chelating [Mo 2 S 2 C 2 ] ring created by equatorial coordination of the dmit (C 3 S 5 ) ligand to the Mo 2 unit. One-electron oxidation of Na[1] using Cp 2 FePF 6 yields the neutral complex [(DAniF) 3 Mo 2 (C 3 S 5 )] ([1]), and removal of two electrons from Na[1] using AgBPh 4 gives [(DAniF) 3 Mo 2 (C 3 S 5 )]BPh 4 ([1]BPh 4 ). In the crystal structures, [1] - and [1] present dihedral angles of 118.9 and 142.3° between the plane defined by the Mo-Mo bond vector and the dmit ligand, respectively, while DFT calculations show that in [1] + the Mo-Mo bond and the dmit ligand are coplanar. Complex [1] is paramagnetic with a g value of 1.961 in the EPR spectrum and has a Mo-Mo bond distance of 2.133(1) Å, increased from 2.0963(9) Å for [1] - . Consistently, a broad absorption band is observed for [1] in the near-IR region, which arises from charge transfer from the dmit ligand to the cationic Mo 2 5+ centers. Interestingly, complex [1] + has an aromatic [Mo 2 S 2 C 2 ] core, as evidenced by a large diamagnetic anisotropy, in addition to the coplanarity of the core structure, which shifts downfield the 1 H NMR signal of the horizontal methine proton (ArN-(CH)-NAr) but upfield those of the vertical protons, relative to the methine proton resonances for the precursor ([1] - ). The magnetic anisotropy (Δχ = χ ⊥ - χ ∥ ) for the [Mo 2 S 2 C 2 ] ring in [1] + is -105.5 ppm cgs, calculated from the McConnell equation, which is about 2-fold larger than that for benzene. The aromaticity of the [Mo 2 S 2 C 2 ] ring is supported by theoretical studies, including single-point calculations and gauge-including atomic orbital (GIAO) NMR spectroscopic calculations at the density functional theory (DFT) level. DFT calculations also show that the [Mo 2 S 2 C 2 ] core in [1] + possesses a set of three highest occupied and three lowest unoccupied molecular orbitals in π character, corresponding to those of benzene in symmetry, and six π electrons that conform to the Hückel 4n + 2 rule for aromaticity. Therefore, this study shows that an aromatic [Mo 2 S 2 C 2 ] core is formed by coupling the δ orbital of the Mo≣Mo bond with the π orbital of the C═C bond through the bridging atoms (S), thus validating the equivalency in bonding functionality between δ and π orbitals.

Three quadruply bonded dimolybdenum complexes equipped with a triarylamine pendant, [(DAniF) 3 Mo 2 (μ-O 2 CC 6 H 4 N(C 6 H 4 CH 3 ) 2 ] (DAniF = N,N'-di(p-anisyl)formamidinate; [OO-ph-N]), [(DAniF) 3 Mo 2 (μ-OSCC 6 H 4 N(C 6 H 4 CH 3 ) 2 ] ([OS-ph-N]), and [(DAniF) 3 Mo 2 (μ-S 2 CC 6 H 4 N(C 6 H 4 CH 3 ) 2 ] ([SS-ph-N]), have been synthesized and characterized by single crystal X-ray diffraction. In electrochemical measurements, the redox couple for the organic amine group becomes irreversible, reflecting the substantially strong electronic interaction between the dimetal center and organic redox site. The potential difference for the two successive redox events, ca. ΔE 1/2 (E 1/2 (2)(N/N •+ ) - E 1/2 (1)(Mo 2 IV/V )), falls in the range of 0.5-0.8 V as estimated from the differential pulse voltammograms. For the monocation radicals [OO-ph-N] + , [OS-ph-N] + , and [SS-ph-N] + , obtained by chemical oxidation of the neutral precursor, a broad ligand (amine) to metal (Mo 2 ) charge transfer (LMCT) absorption band is observed in the near-IR region. Interestingly, analogous to the intervalence charge transfer (IVCT) bands for mixed-valence complexes, the LMCT absorption bands, which are solvent dependent, decrease in energy and bandwidth as the electronic coupling between the two redox sites increases in an order of increasing S content in the chelating group. The electronic coupling matrix elements (H ab ) are determined by optical analyses from the generalized Mulliken-Hush (GMH) theory, falling in the range of 400-800 cm -1 in CH 2 Cl 2 . These results indicate that in these radical cations the charge is localized. Time-dependent DFT calculations show that the frontier molecular orbitals for these asymmetrical donor-acceptor systems have unbalanced distribution of electron density, and the LMCT bands arise from an electronic transition from the pendant ligand-based to metal-based molecular orbitals, corresponding to donor (N)-acceptor (Mo 2 ) charge transfer.

Three novel asymmetrical dimolybdenum dimers, [Mo 2 (DAniF) 3 ] 2 (μ-OOCCOS) (DAniF = N,N'-di(p-anisyl)formamidinate) ([OO-OS]), [Mo 2 (DAniF) 3 ] 2 (μ-S 2 CCO 2 ) ([SS-OO]), and [Mo 2 (DAniF) 3 ] 2 (μ-SSCCOS) ([SS-OS]), have been synthesized and characterized by either single-crystal X-ray crystallography or 1 H NMR spectroscopy. The structural asymmetry for these compounds gives rise to a redox asymmetry, which enlarges the potential separation (ΔE 1/2 ) between the two [Mo 2 ] units. The mixed-valance (MV) species [OO-OS] + , [SS-OO] + and [SS-OS] + , prepared by one-electron chemical oxidation of the neutral precursors, exhibit an intense and symmetrical intervalence charge transfer (IVCT) absorption band in the near-IR region, along with the high energy metal (δ) to ligand (π*) (ML) and ligand (π) to metal (δ) charge transfer (LMCT) absorptions. The LMCT band, which is absent in the neutral precursors, is reflective of the cationic [Mo 2 ] + unit in the MV species; therefore, it is evidenced that in the MV complexes optical electron transfer from the electron donor to acceptor occurs, while the thermal process is energetically unfavorable. The C(1)-C(2) bonds (1.44-1.48 Å) that connect the two [Mo 2 ] units are significantly shorter than a C-C single bond, showing that the two Mo 2 centers are strongly coupled. For the series, TD-DFT calculations show that the molecular orbitals have an unsymmetrical charge density distribution over the two dimolybdenum sites. For each of the complex systems, the calculated orbital energy gaps, SOMO(δ - δ)-LUMO(bridging ligand π*), HOMO-8(bridging ligand π)-SOMO(δ - δ) and SOMO(δ - δ)-HOMO-1(δ + δ), are in good agreement with the observed MLCT, LMCT and IVCT absorption band energies, respectively. The consistency in energy between the IVCT band and the SOMO(δ - δ)-HOMO-1(δ + δ) gap permits assignment of the MV complexes to Class III in the Robin-Day scheme.

Introduction: The past decade has provided striking insights into a newly identified subset of B cells known as regulatory B cells (Bregs). In addition to producing antibody, Bregs also regulate diseases via cytokine production and antigen presentation. This subset of B cells has protective and potentially therapeutic effects. However, the particularity of Bregs has caused some difficulties in conducting research on their roles. Notably, human B10 cells, which are Bregs that produce interleukin 10, share phenotypic characteristics with other previously defined B cell subsets, and currently, there is no known surface phenotype that is unique to B10 cells., Methods: An online search was performed in the PubMed and Web of Science databases for articles published providing evidences on the role of regulatory B cells in digestive system diseases., Results and Conclusions: Abundant evidence has demonstrated that Bregs play a regulatory role in inflammatory, autoimmune, and tumor diseases, and regulatory B cells play different roles in different diseases, but future work needs to determine the mechanisms by which Bregs are activated and how these cells affect their target cells.

Four thienylene (C 4 H 2 S) bridged Mo 2 dimers, [Mo 2 (DAniF) 3 ] 2 (μ-OOCC 4 H 2 SCOO) (DAniF = N,N'-di(p-anisyl)formamidinate), [Mo 2 (DAniF) 3 ] 2 (μ-N(H)SCC 4 H 2 SCN(H)S), [Mo 2 (DAniF) 3 ] 2 (μ-OSCC 4 H 2 SCSO) and [Mo 2 (DAniF) 3 ] 2 (μ-SSCC 4 H 2 SCSS), have been synthesized and studied in terms of electronic coupling. The subtle structural differences between these compounds vary largely the extent of electron delocalization; consequently, a systematic transition from Class II to Class III via Class II-III is achieved, which is probed using spectral parameters of intervalence charge transfer (IVCT) absorption (band energy, intensity and shape) for the mixed-valence complexes. Significantly, the species in Class II-III displays a low energy, half cut-off and solvent-dependent IVCT band, while a high energy, less asymmetrical IVCT band is observed for the complex in Class III. These results give fresh and detailed understanding of the system transition.

Ultrasound has been recently proposed as an alternative modality for efficient wireless power transmission (WPT) to biomedical implants with millimeter (mm) dimensions. This paper presents the theory and design methodology of ultrasonic WPT links that involve mm-sized receivers (Rx). For given load (R L ) and powering distance (d), the optimal geometries of transmitter (Tx) and Rx ultrasonic transducers, including their diameter and thickness, as well as the optimal operation frequency (f c ) are found through a recursive design procedure to maximize the power transmission efficiency (PTE). First, a range of realistic f c s is found based on the Rx thickness constrain. For a chosen f c within the range, the diameter and thickness of the Rx transducer are then swept together to maximize PTE. Then, the diameter and thickness of the Tx transducer are optimized to maximize PTE. Finally, this procedure is repeated for different f c s to find the optimal f c and its corresponding transducer geometries that maximize PTE. A design example of ultrasonic link has been presented and optimized for WPT to a 1 mm 3 implant, including a disk-shaped piezoelectric transducer on a silicon die. In simulations, a PTE of 2.11% at f c of 1.8 MHz was achieved for R L of 2.5 [Formula: see text] at [Formula: see text]. In order to validate our simulations, an ultrasonic link was optimized for a 1 mm 3 piezoelectric transducer mounted on a printed circuit board (PCB), which led to simulated and measured PTEs of 0.65% and 0.66% at f c of 1.1 MHz for R L of 2.5 [Formula: see text] at [Formula: see text], respectively.

Photoinduced electron transfer (ET) in Mo 2 dimers, [Mo 2 (DAniF) 3 ] 2 (μ-E 2 C(ph)CE 2 ) (DAniF = N,N'-di(p-anisyl)formamidinate, E = O or S), has been studied by femtosecond transient spectral techniques. Using a 355 nm laser pulse, the δ electrons on the Mo-Mo quadruple bonds are selectively excited and subsequent charge separation yields diradicals [Mo 2 ]˙ - -ph-[Mo 2 ]˙ + and [Mo 2 ]-ph˙ - -[Mo 2 ]˙ + . The charge separation (CS) and recombination (CR) rates are derived by fitting the decay kinetic data of the excited states. Surprisingly, it is found that the CR rate constants (k CR-1 , ∼10 12 s -1 ) for [Mo 2 ]˙ - -ph-[Mo 2 ]˙ + are larger than the data (k CR-2 ) for [Mo 2 ]-ph˙ - -[Mo 2 ]˙ + by about one order of magnitude, although in the first case, the ET distance is doubled and the electronic coupling between the donor and acceptor is weaker. Optical analyses reveal that the free energy changes (ΔG°) for the two CR processes correspond to the δ → δ* and the metal (δ) to bridging ligand (π*) transition energies, respectively, and thus, the ET kinetics is dominated likely by the driving force (-ΔG°).

FoxA transcription factors play vital roles in regulating the expression of organ-specific genes. BmSGF1, the sole FoxA family member in Bombyx mori, is required for development of the silk gland. However, the function of BmSGF1 in development of the nervous system in the silkworm remains unknown. Here, we show that the amino acids sequence of BmSGF1 is evolutionarily conserved in its middle region from Trichoplax adhaerens to human and diverged from the homologues in most other species in its N-terminal region. BmSGF1 expresses in the nervous system at the embryonic stage. Knockdown of Bmsgf1 by RNA interference (RNAi) results in abnormal development of axons. Therefore, our results demonstrate that BmSGF1 is an indispensable regulator for neurodevelopment., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Using 2,6-naphthalenedicarboxylate and its thiolated derivatives as bridging ligands, three Mo2 dimers of the type [Mo2(DAniF)3](E2CC10H6CE2)[Mo2(DAniF)3] (DAniF = N,N'-di-p-anisylformamidinate; E = O, S) have been synthesized and characterized by X-ray diffraction. These compounds can be generally formulated as [Mo2]-naph-[Mo2], where the complex unit [Mo2] ([Mo2(DAniF)3(μ-E2C)]) functions as an electron donor (acceptor) and the naphthalene (naph) group is the bridge. The mixed-valence (MV) complexes, generated by one-electron oxidation of the neutral precursors, display weak, very broad intervalence charge-transfer absorption bands in the near-to-mid-IR regions. The electronic coupling matrix elements for the MV complexes, Hab = 390-570 cm(-1), are calculated from the Mulliken-Hush equation, which fall between those for the phenyl (ph) and biphenyl (biph) analogues reported previously. The three series consisting of three complexes with the same [Mo2] units exhibit exponential decay of Hab as the bridge changes from ph to biph via naph, with decay factors of 0.21-0.17 Å(-1). Therefore, it is evidenced that while the extent of the bridge conjugacy varies, the electronic coupling between the two [Mo2] units is dominated by the Mo2···Mo2 separation. The absorption band energies for metal-to-ligand charge transfer are in the middle of those for the ph and biph analogues, which is consistent with variation of the HOMO-LUMO energy gaps for the complex series. These results indicate that the interplay of the bridge length and conjugacy is to affect the enegy for charge transfer crossing the intervening moiety, in accordance with a superechange mechanism.

Background: MicroRNAs (miRNAs) are short, noncoding RNAs that inhibit the expression of target genes that play roles in tumorigenesis. MiR-21, miR-31, and miR-184 are oncogenic miRNAs for head and neck squamous cell carcinoma (HNSCC). Factor-inhibiting hypoxia (FIH)-inducible factor is known to inactivate hypoxia-induced downstream effectors and is involved in HNSCC suppression. This study investigates whether miR-21, miR-31, and miR-184 target FIH in HNSCC., Methods: Reporter assays, Western blot analysis, quantitative reverse transcriptase-polymerase chain reaction (PCR) analysis, and phenotypic assays were used to prove that miR-21, miR-31, and miR-184 directly target FIH. Clinicopathological implications of the gene expression were also analyzed., Results: MiR-21, miR-31, and miR-184 directly bind to various sites in the 3' untranslated region (UTR) of FIH transcript, and this binding is associated with decreased FIH protein expression in HNSCC cells. Treatment with the precursors of these miRNAs increases the proliferation and migration of HNSCC cells. Concomitant treatment with precursors repressed FIH and enhanced oncogenicity most profoundly. Upregulation of miR-21, miR-31, and miR-184 expression is found in more than 80% of HNSCC tumors and 72% of tumors have concordant upregulation of these 3 oncogenic miRNAs. The highest expression of these miRNAs is present in T4b and stage IVB tumors. Downregulation of FIH mRNA expression is noted in 69% of HNSCC tumors, and in tumors exhibiting high expression of these miRNAs, the FIH mRNA expression is consistently downregulated., Conclusion: This study provides novel clues indicating that miR-21, miR-31, and miR-184 co-target FIH tumor suppressor during pathogenesis in the vast majority of HNSCC., (© 2015 Wiley Periodicals, Inc.)

Assembling two quadruply bonded dimolybdenum units [Mo2 (DAniF)3 ](+) (DAniF=N,N'-di(p-anisyl)formamidinate) with 1,4-naphthalenedicarboxylate and its thiolated derivatives produced three complexes [{Mo2 (DAniF)3 }2 (μ-1,4-O2 CC10 H6 CO2 )], [{Mo2 (DAniF)3 }2 (μ-1,4-OSCC10 H6 COS)], and [{Mo2 (DAniF)3 }2 (μ-1,4-S2 CC10 H6 CS2 )]. In the X-ray structures, the naphthalene bridge deviates from the plane defined by the two Mo-Mo bond vectors with the torsion angle increasing as the chelating atoms of the bridging ligand vary from O to S. The mixed-valent species exhibit intervalence transition absorption bands with high energy and very low intensity. In comparison with the data for the phenylene analogues, the optically determined electronic coupling matrix elements (Hab =258-345 cm(-1) ) are lowered by a factor of two or more, and the electron-transfer rate constants (ket ≈10(11)  s(-1) ) are reduced by about one order of magnitude. These results show that, when the electron-transporting ability of the bridge and electron-donating (electron-accepting) ability of the donor (acceptor) are both variable, the former plays a dominant role in controlling the intramolecular electron transfer. DFT calculations revealed that increasing the torsion angle enlarges the HOMO-LUMO energy gap by elevating the (bridging) ligand-based LUMO energy. Therefore, our experimental results and theoretical analyses verify the superexchange mechanism for electronic coupling and electron transfer., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In order to evaluate the impact of bridge conformation on electronic coupling in donor-bridge-acceptor triad systems, two Mo2 dimers, [Mo2(DAniF)3]2[μ-1,4-{C(O)NH}2-Naph] (1, DAniF = N,N'-di(p-anisyl)formamidinate and Naph = naphthalenyl) and [Mo2(DAniF)3]2[μ-1,4-(CS2)2-2,5-Me2C6H2] (2), have been synthesized and structurally characterized. These two compounds feature a large dihedral angle (>60°) between the central aromatic ring and the plane defined by the Mo-Mo bond vectors, which is distinct from the previously reported phenylene bridged analogues [Mo2(DAniF)3]2[μ-1,4-{C(O)NH}2-ph] (I) and [Mo2(DAniF)3]2[μ-1,4-(CS2)2-C6H4] (II), respectively. Unusual optical behaviors are observed for the mixed-valence (MV) species (1(+) and 2(+)), generated by single-electron oxidation. While 2(+) exhibits a weak intervalence charge transfer (IVCT) absorption band in the near-IR region, the IVCT band is absent in the spectrum of 1(+), which is quite different from what observed for I(+) and II(+). Optical analyses, based on superexchange formalism and Hush model, indicate that, in terms of Robin-Day classification, mixed-valence species 1(+) belongs to the electronically uncoupled Class I and complex 2(+), with Hab = 220 cm(-1), is assigned to the weakly coupled Class II. Together with I(+) and II(+), the four MV complexes complete a transition from Class I to Class II-III borderline as a result of manipulating the geometric topology of the bridge. Given the structural and electronic features for the molecular systems, the impacts of electrostatic interaction (through-space) and electron resonance (through-bond) on electronic coupling are discussed.