One-pot solvothermal synthesis of In-doped amino-functionalized UiO-66 Zr-MOFs with enhanced ligand-to-metal charge transfer for efficient visible-light-driven CO2 reduction.

Metal organic frameworks (MOFs) with high porosity and highly tunable physical/chemical properties can serve as heterogeneous catalysts for CO2 photoreduction, but the application is hindered by the large band gap (Eg) and insufficient ligand-to-metal charge transfer (LMCT). In this study, a simple one-pot solvothermal strategy is proposed to prepare an amino-functionalized MOF (aU(Zr/In)) featuring an amino-functionalizing ligand linker and In-doped Zr-oxo clusters, which enables efficient CO2 reduction driven with visible light. The amino functionalization leads to a significant reduction of Eg as well as a charge redistribution of the framework, allowing the absorption of visible light and the efficient separation of photogenerated carriers. Furthermore, the incorporation of In not only promotes the LMCT process by creating oxygen vacancies in Zr-oxo clusters, but also greatly lowers the energy barrier of the intermediates for CO2-to-CO conversion. With the synergistic effects of the amino groups and the In dopants, the optimized aU(Zr/In) exhibits a CO production rate of 37.58 ± 1.06 µmol g-1 h-1, outperforming the isostructural University of Oslo-66- and Material of Institute Lavoisier-125-based photocatalysts. Our work demonstrates the potential of modifying MOFs with ligands and heteroatom dopants in metal-oxo clusters for solar energy conversion.

One-pot solvothermal synthesis of flower-like Fe-doped In2S3/Fe3S4 S-scheme hetero-microspheres with enhanced interfacial electric field and boosted visible-light-driven CO2 reduction.

S-scheme heterojunctions hold great potential for CO2 photoreduction into solar fuels, but their activities are severely limited by the low efficiency of interfacial charge transfer. In this work, a facile one-pot solvothermal reaction has been developed to dope Fe into flower-like In2S3/Fe3S4 hetero-microspheres (Fe-In2S3/Fe3S4 HMSs), which are demonstrated as an efficient S-scheme photocatalyst for visible-light-driven CO2 photoreduction. The doping of Fe not only reduces the bandgap of In2S3 and thus extends the optical response to the visible-light region, but also increases the densities of donors and sulfur vacancies, which leads to an elevated Fermi level (Ef). The difference of Ef between In2S3 and Fe3S4 is enlarged and their band bending at the interface is therefore enhanced, which results in promoted carriers transfer in the S-scheme pathway due to the reinforced interfacial electric field. Moreover, Fe-doped In2S3 reduces the formation energy of the *CO intermediate, which thermodynamically favors the CO evolution at the surface. As a result, the Fe-In2S3/Fe3S4 HMSs exhibit a significantly boosted CO2 photoreduction activity in comparison with bare In2S3 and Fe-In2S3 samples. This work demonstrates the great potential of heteroatom-engineered S-scheme photocatalysts for CO2 photoreduction.

Sensing Mechanisms: Calcium Signaling Mediated Abiotic Stress in Plants.

Plants are exposed to various environmental stresses. The sensing of environmental cues and the transduction of stress signals into intracellular signaling are initial events in the cellular signaling network. As a second messenger, Ca2+ links environmental stimuli to different biological processes, such as growth, physiology, and sensing of and response to stress. An increase in intracellular calcium concentrations ([Ca2+]i) is a common event in most stress-induced signal transduction pathways. In recent years, significant progress has been made in research related to the early events of stress signaling in plants, particularly in the identification of primary stress sensors. This review highlights current advances that are beginning to elucidate the mechanisms by which abiotic environmental cues are sensed via Ca2+ signals. Additionally, this review discusses important questions about the integration of the sensing of multiple stress conditions and subsequent signaling responses that need to be addressed in the future.

Design of MXene Composites with Biomimetic Rapid and Self-Oscillating Actuation under Ambient Circumstances.

Although responsive actuators have been intensively investigated, it remains challenging to enable rapid and self-oscillating actuation under ambient circumstances without human intervention analogous to living organisms. By hybridizing a unique type of two-dimensional nanomaterials (i.e., MXene) with a particular hydrophilic polymer, a smart and flexible conductive composite was produced with rapid actuation and spontaneous oscillation near a moist surface. Due to the presence of layered microstructures and the moisture-sensitivity improved by surface roughness and intercalated polymeric layers, the composites could reversibly bend up to 180° in 2 s or 210° in 10 s on demand when the circumstantial humidity was varied, being superior or comparable to many actuators in the literature. More importantly, the composite was capable not only of flipping upside down repeatedly on the moist surface but also of self-oscillating ceaselessly under ambient gradient humidity without human intervention, e.g., an oscillation between 30 and 100° with an oscillation frequency of 0.08 Hz. This self-oscillation resulted from the occurrence of rapid asymmetrical hydration and dehydration of the composite between the regions of high and low humidity, which could further be modulated both by different hydrophilic polymers and by photoradiation owing to the photothermal effect of MXene nanosheets. Because of the ubiquitous presence of humidity gradient near the moist surface, this type of smart composite may not only offer a strategy for designing artificial materials that are capable of spontaneous actuation under ambient circumstance without human intervention but also promise potential applications in artificial muscles, autonomous robotics, and energy harvesting from environments.

Bisphenol A(BPA), BPS and BPB-induced oxidative stress and apoptosis mediated by mitochondria in human neuroblastoma cell lines.

The analogues of biphenol A (BPA), including bisphenol S (BPS) and bisphenol B (BPB), are commonly used to replace the application of BPA in containers and wrappers of daily life. However, their safeties are questioned due to their similar chemical structure and possible physiological effects as BPA. To investigate the neurotoxic effects of BPA, BPS, and BPB as well as their underlying mechanism, IMR-32 cell line from male and SK-N-SH cell line from female were exposed respectively to BPA, BPS and BPB with concentrations of 1 nM, 10 nM, 100 nM, 1 µM, 10 µM, and 100 µM for 24 h. Additionally, 24 h exposure of BPA combining epigallocatechin gallate (EGCG) (4 µM and 8 µM for IMR-32 and SK-N-SH respectively) were conducted. Results demonstrated that BPs exposure could promote reactive oxygen species production and increase level of malondialdehyde (MDA) while decrease levels of superoxide dismutase (SOD). Intensive study revealed that after exposure to BPA mitochondrial membrane potential (MMP) dropped down and the protein expression levels of Bak-1, Bax, cytochrome c and Caspase-3 were up-regulated but Bcl-2 were down-regulated significantly. Moreover, apoptosis rate was raised and cell activity declined remarkably in the neuroblastoma cells. All the effects induced by BPA could be alleviated by the adding of EGCG, which similar alleviations could be inferred in IMR-32 and SK-N-SH cells induced by BPS and BPB. Furthermore, BPS showed lower neurotoxic effects compared to BPA and BPB. Interestingly, the neurotoxic effects of BPA on IMR-32 cells were significantly higher than those on SK-N-SH cells. In conclusion, the results suggested that BPA, BPS and BPB could induce oxidative stress and apoptosis via mitochondrial pathway in the neuroblastoma cells and male is more susceptible to BPs than female.

Molecular Insight into Water Transport through Heterogeneous GO-based Two-Dimensional Nanocapillary.

Nanofluidics in two-dimensional (2-D) heterogeneous layered materials with hybrid overlapping structures exhibit promising potential in filtration and separation applications. However, molecular transport across the heterogeneous interlayer galleries remains largely unexplored, in particular, there exists disputation in the function and performance of hybrid graphene oxide (GO)-based laminate membrane for the water transport. Herein, heterogeneous 2-D GO-based nanochannels were employed as a typical platform to investigate the water flow by nonequilibrium molecular dynamics (MD) simulation. It is demonstrated that both heterogeneous and homogeneous GO nanochannels exhibit similar reduced water flow behavior, even if one surface of the 2-D channel is the pristine graphene. In particular, the flow rate in the hybrid GO/pristine graphene nanochannels does not lie between those of the oxidized and the pristine regions, and the high-friction GO surface suppresses the water transport and controls the entire flow performance. This result is qualitatively consistent with the recent experimental observation. By comparing with the MD simulation, a hydrodynamic model was developed to describe the flow rate for 2-D heterogeneous nanochannels. The reduced water transport has been revealed as the distinct vertical dragging effect, arising from the synergistic effect between the interfacial affinity from GO surfaces and the interlayer molecular interaction. Our results provide novel physical pictures for the molecular transport inside heterogeneous 2-D nanochannels.