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Titanium-based metal–organic framework as visible-light activated chemiresistive sensor.

This paper adopts the random matrix optimization fusion of Bell’s translation model to conduct in-depth research and analysis on the teaching model of English translation in colleges and universities. Bell’s translation model theory explicates the mental model of the translation process to a certain extent based on psycholinguistic research results. Using the results of random matrix theory on the eigenvalues of the sample covariance matrix, the energy of each subspace is estimated, and the estimated energy is then used to construct the subspace-weighting matrix. The statistical properties of the sample covariance matrix eigenvectors were analyzed using the first-order perturbation approximation, and then asymptotic results from random matrix theory on the projection of the sample covariance matrix signal subspaces to the real signal parametrization were used to obtain the weighting matrix based on the random matrix eigenvectors. The analysis shows that the teacher can help students understand the teaching content and master the knowledge points by using guided meta-discoursal to indicate the logical relationships inherent in linguistic expressions and make the discourse transitions natural, coherent, and organized. The use of interactive meta-discoursal attracts students’ attention and treats them as participants in the discourse, making them feel a sense of belonging and satisfying their need for psychological belonging, which is beneficial to the students’ main position in the classroom. In teaching methods, there is a principle of comprehensible input, which is to provide students with a lot of interesting and understandable listening and reading input. In the translation classroom, the translation teachers code-switched infrequently and mainly used three types of code-switching: inter-sentence code-switching, intra-sentence code-switching, and additional code-switching to carry out translation teaching. Among them, intra-sentence code-switching accounts for 57.46%, inter-sentence code-switching accounts for 41.53%, and the least frequent is additional code-switching, accounting for 1.01%.

Confined metal clusters as sub-nanometer reactors for electrocatalytic N2 reduction reaction (eNRR) have received increasing attention due to the unique metal-metal interaction and higher activity than single-atom catalysts. Herein, the inspiration of the superior capacitance and unique microenvironment with regular surface cavities of the porous boron nitride (p-BN) nanosheets, we systematically studied the catalytic activity for NRR of transition-metal single-clusters in the triplet form (V3, Fe3, Mo3 and W3) confined in the surface cavities of the p-BN sheets by spin-polarized density functional theory (DFT) calculations. After a two-step screening strategy, Mo3@p-BN was found to have high catalytic activity and selectivity with a rather low limiting potential (–0.34 V) for the NRR. The anchored Mo3 single-cluster can be stably embedded on the surface cavities of the substrate preventing the diffusion of the active Mo atoms. More importantly, the Mo atoms in the Mo3 single-cluster would act as “cache” to accelerate electron transfer between active metal centers and nitrogen-containing intermediates via the intimate Mo-Mo interactions. The cooperation of Mo atoms can also provide a large number of occupied and unoccupied d orbitals to make the "donation–backdonation" mechanism more effective. This work not only provides a quite promising electrocatalyst for NRR, but also brings new insights into the rational design of triple-atom NRR catalysts.

Stellera chamaejasme has become a problematic weed in northern and south-western grasslands of China. To evaluate a possible role of endophytes in its strong competitive capacity, the endophytic bacterial community of S. chamaejasme was investigated by culture-dependent and independent methods, and the growth-promoting traits of some culturable isolates as well as the benefit of endophyte ST3CS3 (Brevundimonas sp.) on host plants growth were studied. The results showed that 823 OTUs were generated with a 97% similarity level in the culture-independent study. They were classified into 29 phyla, 61 classes, 147 orders, 237 families and 440 genera. Among them, Pseudomonas and Ralstonia were the most dominant genera in belowground parts (G) (64.25%) and aboveground parts (S) (26.54%) respectively. The diversity and species richness of endophytes in S were significantly higher than that of G (P 0.001, t-test). Contrary to this, the number of culturable bacteria in S was a little lower than that of G (P 0.05, t-test). Totally, 176 isolates belonging to 30 morphotypes were obtained in the culture-dependent study. Among them, Acinetobacter was the most dominant genus in G (51.30%), then followed by Pseudomonas (6.09%) and Brevundimonas (6.09%), while Lysinibacillus (21.31%) was the most dominant genus in S, followed by Pseudomonas (11.48%). Growth-promoting trait tests indicated that 93.65% of the tested isolates (63) exhibited nitrogen-fixing, IAA-synthesizing, phosphorus or potassium solubilizing capacity, in which 77.97% belonged to Proteobacteria, a phylum found to contain more active isolates. Pot experiments demonstrated that endophyte ST3CS3 can significantly improve host plants growth and increase its nitrogen and chlorophyll content (P 0.01, t-test). Therefore, we suggest that strong competitiveness of S. chamaejasme may in part be due to possession of high ratios of plant growth-promoting proteobacterial endophytes such as Pseudomonas, Acinetobacter and Brevundimonas.

Rosa roxburghii Tratt, the most popular fruit that blooms in the southwest of China, has high antioxidant properties and is rich in different flavonoids. However, the regulatory network and critical genes that regulate the flavonoid biosynthesis of R. roxburghii are still unknown. In this study, HPLC analysis revealed that total flavonoids, anthocyanins, and catechin were enriched in mature fruits, flowers, and leaves, respectively. Differentially expressed genes (DEGs) between five organs of R. roxburghii involved in flavonoid metabolism were obtained by transcriptome sequencing. A total of 1130 DEGs were identified, including 166 flavonoid pathway biosynthesis genes, 622 transcription factors (TFs), 301 transporters, and 221 cytochrome P450 proteins. A weighted gene co-expression network analysis (WGCNA) of the DEGs was conducted to construct co-expression networks. Regarding enzymes in the biosynthesis of flavonoids, cytochrome P450 CYP749A22 and CYP72A219 were highlighted in the regulation of total flavonoids of mature fruits. Anthocyanin 3-O-glucosyltransferase and F3′H were the top two critical enzymes for anthocyanin accumulation in flowers. By contrast, caffeic acid 3-O-methyltransferase, 4-coumarate-CoA ligase, and shikimate O-hydroxycinnamoyltransferase were essential for catechin accumulation in leaves. Additionally, we analyzed the eigengene network of the “black” module, which had high correlations with total flavonoids (r = 0.9, p = 5 × 10−6). There were 26 eigengenes in the “black” module, consisting of 6 flavonoid biosynthesis, 14 TFs, and 6 transporters. Among them, the transcription factors RrWRKY45 (DN142829_c1_g5), RrTCP20 (DN146443_c1_g1), and RrERF118 (DN141507_c3_g2) were screened as the hub genes, which significantly correlated with total flavonoids in R. roxburghii. The present biochemical and transcriptomic data provide insights into functional genomics for breeding R. roxburghii with flavonoid accumulation.

A semiconducting metal–organic crystalline nanotube array (MO-CNA) was constructed by the induction of Pb⋯S secondary interactions, exhibiting highly selective and sensitive NO2 sensing with a low limit of detection.

The kiwifruit (Actinidia arguta var. purpurea) produces oval shaped fruits containing a slightly green or mauve outer exocarp and a purple-flesh endocarp with rows of tiny black seeds. The flesh color of the fruit results from a range of anthocyanin compounds, and is an important trait for kiwifruit consumers. To elucidate the molecular mechanisms involved in anthocyanin biosynthesis of the sarcocarp during A. arguta fruit development, de novo assembly and transcriptomic profile analyses were performed. Based on significant Gene Ontology (GO) biological terms, differentially expressed genes were identified in flavonoid biosynthetic and metabolic processes, pigment biosynthesis, carbohydrate metabolic processes, and amino acid metabolic processes. The genes closely related to anthocyanin biosynthesis, such as phenylalanine ammonia-lyase (PAL), chalcone synthase (CHS), and anthocyanidin synthase (ANS), displayed significant up-regulation during fruit development according to the transcriptomic data, which was further confirmed by qRT-PCR. Meanwhile, a series of transcription factor genes were identified among the DEGs. Through a correlation analysis. AaMYB1 was found to be significantly correlated with key genes of anthocyanin biosynthesis, especially with CHS. Through a transient expression assay, AaMYB1 induced anthocyanin accumulation in tobacco leaves. These data provide an important basis for exploring the related mechanisms of sarcocarp anthocyanin biosynthesis in A. arguta. This study will provide a strong foundation for functional studies on A. arguta and will facilitate improved breeding of A. arguta fruit.

Electrocatalytic nitrogen reduction reaction (eNRR) is a promising method for the sustainable production of ammonia as an alternative to the traditional energy-intensive Haber-Bosch process. In this work, an efficient strategy by atomic spin regulation to promote NRR through Fe-transition metal (TM) hybrid heteronuclear dual-atom catalysts has been studied. By means of DFT computations, the stability, activity, and selectivity of 30 kinds of Fe-based dual-atoms anchored on N-doped porous graphene are systematically investigated to evaluate their catalytic performance. Fe/MoNC is screened as an excellent NRR catalyst with the limiting potentials of 0.63 V, and also suppresses HER. In the Fe/MoNC, the neighboring Fe atom regulates the spin state of the Mo center in MoN

It is well known that charge separation is crucial for efficient photocatalytic solar conversion. Although some covalent-organic frameworks (COFs) exhibit visible-light harvest, the large exciton binding energies reduce their photocatalytic efficiencies. Herein, we developed a novel method to post-treat the olefin-linked COFs with end-capping polycyclic aromatic hydrocarbons (PAHs) for spontaneous charge separation. Interestingly, a type-II heterostructure is constructed in our perylene-modified COFs which displays drastically enhanced performance for photocatalytic CO

Vehicle taillight detection is essential to analyze and predict driver intention in collision avoidance systems. In this article, we propose an end-to-end framework that locates the rear brake and turn signals from video stream in real-time. The system adopts the fast YOLOv3-tiny as the backbone model and three improvements have been made to increase the detection accuracy on taillight semantics, i.e., additional output layer for multi-scale detection, spatial pyramid pooling (SPP) module for richer deep features, and focal loss for alleviation of class imbalance and hard sample classification. Experimental results demonstrate that the integration of multi-scale features as well as hard examples mining greatly contributes to the turn light detection. The detection accuracy is significantly increased by 7.36%, 32.04% and 21.65% (absolute gain) for brake, left-turn and right-turn signals, respectively. In addition, we construct the taillight detection dataset, with brake and turn signals are specified with bounding boxes, which may help nourishing the development of this realm. Ministry of Education (MOE) National Research Foundation (NRF) This work was supported in part by the National Natural Science Foundation of China under Grant 61803104; in part by the Ministry of Education (MOE) Academic Research Fund of Singapore under Grant R266000096133, Grant R266000096731, and Grant MOE2017-T2-2153; in part by the Singapore National Research Foundation under Grant NRF-RSS2016004; and in part by the Deanship of Scientific Research at King Saud University, Riyadh, Saudi Arabia, for funding this work through the Vice Deanship of Scientific Research Chairs: Chair of Smart Technologies.

The Gram-negative bacterial species Pectobacterium actinidiae causes summer canker in kiwifruit plants. However, little is known about its virulence factors and mechanisms of genetic adaptation. We aimed to identify the key determinants that control the virulence of P. actinidiae in kiwifruit by genomic and functional analyses. Analysis of four P. actinidiae isolates indicated low genetic variability with an average of 98.7% genome-level sequence similarity and 82% shared protein-coding gene content. Phylogenetic analysis, based on both bulk single nucleotide polymorphisms (SNPs) and single-copy genes, revealed that P. actinidiae strains cluster into a single clade, which is closely related to the clades of P. odoriferum (species with a completely different host range). Through comparison between these two clades of strains, 746 unique core orthologs/genes were clustered in the clades of P. actinidiae, especially key virulence determinants involved in the biosynthesis of secretion systems (type III, IV, and VI), iron, flagellar structure, and the quorum-sensing system. Our results provide insights into the pathogenomics underlying the genetic diversification and evolution of pathogenicity in P. actinidiae species.

The construction of hydrophobic nanochannel with hydrophilic sites for bionic devices to proximally mimick real bio-system is still challenging. Taking the advantages of MOF chemistry, a highly oriented CuTCPP thin film has been successfully reconstructed with ultra-thin nanosheets to produce abundant two-dimensional interstitial hydrophobic nanochannels with hydrophilic sites. Different from the classical active-layer material with proton transport in bulk, CuTCPP thin film represents a new type of active-layer with proton transport in nanochannel for bionic proton field-effect transistor (H+ -FETs). The resultant device can reversibly modulate the proton transport by varying the voltage on its gate electrode. Meanwhile, it shows the highest proton mobility of ≈9.5×10-3 cm2 V-1 s-1 and highest on-off ratio of 4.1 among all of the reported H+ -FETs. Our result demonstrates a powerful material design strategy for proximally mimicking the structure and properties of bio-systems and constructing bionic electrical devices.

Considerable efforts have been made to enhance the hydrogen evolution reaction (HER) catalytic performance of Janus MoSSe monolayer, which have been considered to be a promising candidate due to the unique asymmetry structure. However, the activation effect remains non-optimal for the inert Janus MoSSe basal plane at present. Herein, a train of transition metal (TM) atoms were anchored on the S-/Se-/Mo-defective MoSSe basal plane to screen effective TM single-atom catalysts for HER through density functional theory (DFT) computations. Interestingly, the single Co atom anchored on Mo-defective MoSSe and the single Zn or Cd atom anchored on S-defective MoSSe were judged to possess excellent HER performance yielding a near-zero ΔGH (ΔGH = −0.050, −0.095, −0.098 eV, respectively), which is comparable to the optimized Pt-SACs. The enhanced HER activity is attributed to the doping of TM atoms (Co, Zn and Cd) which improves the conductivity of the original MoSSe and offers unoccupied states near the Fermi level decreasing the energy barrier of electrons transfer between H and TMs@MoSSe surface. In addition, the change of unoccupied antibonding states of active atoms leads to appropriate interaction between the active sites and H. The hybridization between H-s orbital and the TMs@MoSSe systems around the Fermi level also suggests the formation of stable bonding-antibonding hydrogen adsorption states. This work reveals an effective way of activating MoSSe basal plane for HER.

Fruit prickles are widely distributed on the pericarp and exhibit polymorphic traits at different developmental stages. Although they are multicellular appendages that are well-known for helping plants defend against biotic and abiotic stresses, their origination and molecular mechanism are still less known. Here, we studied the origination and molecular mechanism of fruit prickles in Rosa roxburghii. Using morphological and histological observations, we found that the fruit prickle primordium of R. roxburghii originated from the ground meristem that underwent cell division to form flagelliform prickles, continued to enlarge, and finally lignified to form mature fruit prickles. We amplified a homolog of candidate gene TRANSPARENT TESTA GLABRA1 (TTG1) from R. roxburghii, named RrTTG1. RrTTG1 harbored four conserved WD-repeat domains and was exclusively nuclear-localized. Using qRT-PCR and in situ hybridization, we found that RrTTG1 was constitutively expressed and highly expressed during the initiation and cell expansion phases of fruit prickles. Ectopic expression analysis in Arabidopsis proved that RrTTG1 substantially enhanced the number of trichome and pigmentation production and inhibited root hair formation. Besides, RrTTG1 complemented the phenotypes of the ttg1 mutant in Arabidopsis, thus indicating that RrTTG1 played pleiotropic roles akin to AtTTG1. We demonstrated that the RrTTG1 only interacted with RrEGL3, a homolog of ENHANCER OF GLABRA3 (EGL3), via yeast two-hybrid (Y2H) and bimolecular fluorescence complementation (BiFC) assays. Briefly, RrTTG1 might positively regulate the initiation of fruit prickle primordium and cell enlargement by forming the RrTTG1-RrEGL3-RrGL1 complex in R. roxburghii. Therefore, our results help characterize the RrTTG1 in R. roxburghii and also elucidate the establishment of the prickles regulatory system in the Rosaceae plants.

The kiwifruit (

The hydrolysis of earth-abundant AlIII has implications in mineral mimicry, geochemistry and environmental chemistry. Third-order nonlinear optical (NLO) materials are important in modern chemistry due to their extensive optical applications. The assembly of AlIII ions with π-conjugated carboxylate ligands is carried out and the hydrolysis and NLO properties of the resultant material are studied. A series of Al32 -oxo clusters with hydrotalcite-like cores and π-conjugated shells are isolated. X-ray diffraction revealed boundary hydrolysis occurs at the equatorially unsaturated coordination sites of AlIII ions. Charge distribution analysis and DFT calculations support the proposed boundary substitution. The Al32 -oxo clusters possess a significant reverse saturable absorption (RSA) response with a minimal normalized transmittance up to 29 %, indicating they are suitable candidates for optical limiting (OL) materials. This work elucidates the hydrolysis of AlIII and provides insight into layered materials that also have strong boundary activity at the edges or corners.

A new conductive coordination polymer (CCP), Ag(SPh–NO2)·AgNO3, with a three-dimensional (3D) non-porous structure composed of a unique 2D inorganic layered structure linked by an organic linker, was reported. The 3D CCP Ag(SPh–NO2)·AgNO3 exhibits semiconductor behavior, with electronic conductivity as high as 2.7 × 10−6 S cm−1 at 295 K, which is comparable to the vast majority of highly conductive 3D coordination polymers. The chemiresistive humidity sensing ability of Ag(SPh–NO2)·AgNO3 was studied over a wide relative humidity (RH) range (10–90% RH) at room temperature. The sensor showed exceptionally high moisture responsiveness, with a 106-fold increase in response at 90% RH and excellent sensitivity to humidity in the range of 10–80% RH. The sensing mechanism was further studied using alternating current (AC) impedance spectroscopy and direct current (DC) instantaneous reverse polarity experiments. The exceptionally high response of the Ag(SPh–NO2)·AgNO3-based sensor at high RH is attributed to the periodic arrangement of the ion species via reversible coordination bonds in the structure. H3O+ and Ag+ are easily formed on its hydrophilic surface, through which the free transport of ionic carriers dominates the conductivity change. Using density functional theory (DFT) calculations, it is further demonstrated that the reversibly coordinated AgNO3 in the structure can be easily occupied by water molecules, which is thermodynamically spontaneous in the presence of humidity. Furthermore, the functional AgNO3 groups and their reversible coordination bonds enabled Ag(SPh–NO2)·AgNO3 to show exceptionally high moisture responsiveness.

A bilayer hexagonal wheel Sn18-oxo cluster, as the largest tin-oxo wheel to date, was successfully constructed by structural directing of organic ligands. Moreover, the ligands show important effects on the electronic structure and third-order nonlinear optical properties of the Sn18-oxo wheel, which is demonstrated by detailed theoretical calculations.

The vital role of the spin polarization in the electrocatalytic N2 reduction reaction (eNRR) stimulates us to explore the potential of the newly discovered two-dimensional (2D) vdW ferromagnetic materials as NRR electrocatalysts. Here, using density functional theory (DFT) computations, we report the first theoretical prediction that the single-layer defective Fe3GeTe2 acts as a 2D ferromagnetic material toward the NRR with outstanding electrocatalytic activity and high selectivity. Notably, all six hydrogenation steps are exothermic and spontaneous. The highly centralized spin-polarization on the exposed Fe4 center in defective Fe3GeTe2 leads to strong backdonation and substantial activation of the NN triple bond. Moreover, the metallic character of the defective Fe3GeTe2 ensures high-speed transport of carriers. This work not only provides a quite promising electrocatalyst for the NRR but also promotes the application of emerging 2D ferromagnets in the field of energy conversion.

Present herein is the first example of aluminium nanoring assembly by fatty acids. And the auxiliary alcohol sites can be modified either by monohydric alcohols (AlOC-33 to AlOC-35) or diols (AlOC-36 to AlOC-38). The monohydric alcohol modified ten-membered aluminium (Al10) rings are coplanar, while the diol modified ones possess a saddle-shaped configuration. Interestingly, the diol modified Al10 ring (AlOC-36) can convert into a coplanar ring (AlOC-33-B). AlOC-33-B possesses a similar molecular structure but a different supramolecular structure with AlOC-33. The structural transformation is confirmed to be a thermodynamically spontaneous process through density-functional theory (DFT) calculations.

Many metal-organic cages (MOCs) and a few hydrogen-bonded organic cages (HOCs) have been investigated, but little is reported about cooperative self-assembly of MOCs and HOCs. Herein, we describe an unprecedented MOC&HOC co-crystal composed of tetrahedral Ti4 L6 (L=embonate) cages and in-situ-generated [(NH3 )4 (TIPA)4 ] (TIPA=tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine) cages. Chiral transfer is observed from the enantiopure Ti4 L6 cage to enantiopure [(NH3 )4 (TIPA)4 ] cage. Two homochiral supramolecular frameworks with opposite handedness (PTC-235(Δ) and PTC-235(Λ)) are formed. Such MOC&HOC co-crystal features high stability in water and other solvents, affording single-crystal-to-single-crystal transformation to trap CH3 CN molecules and identify disordered NH4 + cations. A tablet pressing method is developed to test the third-order nonlinear optical property of KBr-based PTC-235 thin film. Such a thin film exhibits an excellent optical limiting effect.

We report the first example of carbon nanotube (CNT)-like assembly of the titanium (Ti) framework, Ti oxo inorganic cluster (Ti6O6) hexagonal rings into a titanium oxide (Ti–O) nanotube, prepared b...

Fruit prickles are widely distributed on the pericarp and exhibit polymorphic traits at different developmental stages. Although they are multicellular appendages that are well-known for helping plants defend against biotic and abiotic stresses, their origination and molecular mechanism are still less known. Here, we studied the origination and molecular mechanism of fruit prickles in

Subtilisin QK is a nattokinase-like serine protease which demonstrates high efficiency for direct cross-linked fibrin degradation, without activation of plasminogen. It was resistant capacity against the digestion of mimics pancreatic enzyme and could be absorbed throughout ex vivo intestine with fibrinolytic activity in a time-dependent manner. The result of bioluminescence image using nude mice also proved that rSubtilisin QK could infiltrate into all organs from intestinal mucosa. Since rSubtilisin QK could also elevated the levels of plasma levels of fibrin/fibrinogen degradation products and D-dimer (they are sensitive indicators of in vivo fibrinolytic activity) in rats, its prevention effect was investigated in κ-carrageenan-induced rat model. Thrombosis rats were oral treated with rSubtilisin QK for 7 days, and the length of tail-thrombosis was then measured. Compared to control group, the average length of tail-thrombosiswere reduced and the vessel cross section of ears and tails occupied by thrombosis was relieved among the thrombosis rats treated with rSubtilisin QK. Furthermore, the levels of tissue plasminogen activator were increased in cultured HUVECs stimulated with rSubtilisin QK, while plasminogen activator inhibitor-1 showed the opposite trend simultaneously, suggesting the activation of plasminogen. In conclusion, rSubtilisin QK exerted thrombolytic effects in vivo and may be a potential oral thrombolytic agent.

Objective. To investigate the changes in vertebral function after minimally invasive surgery in patients with thoracolumbar spinal fractures and investigate the impact of percutaneous minimally invasive surgery on patients’ quality of life by following up the patients in the long term. Methods. A retrospective analysis was performed to select 80 patients with thoracolumbar spinal fractures treated in our hospital from April 2013 to October 2018, and the patients were divided into a study group and a control group according to the difference in their choice of procedure. The two groups were compared in terms of perioperative wound pain, serum creatine kinase (CK) activity, and C-reactive protein (CRP) levels, and the two groups were followed up for 2 years to compare the changes in anterior vertebral body height and Cobb’s angle during the follow-up period and to compare the differences in quality of life between the two groups. Results. (1) The pain level of patients in the study group was significantly lower than that of the control group at the 1st and 3rd postoperative days ( p < 0.05 ). (2) The CK activity and CPR level of patients in the study group were significantly lower than that of the control group at the 1st and 3rd postoperative days ( p < 0.05 ). (3) Compared with the preoperative period, the height of the anterior border of the vertebral body and the Cobb’s angle in both groups showed significant changes at 7 d, 6 months, one year, and two years after surgery ( p < 0.05 ), suggesting that both procedures can significantly restore the height of the injured vertebra and improve the function of the vertebral body. (4) The somatic, physical, and psychological functions of patients in the study group were significantly greater than those in the control group at 6 months postoperatively ( p > 0.05 ). Conclusion. Compared to traditional open surgery, minimally invasive percutaneous surgery for thoracolumbar fractures can significantly reduce perioperative pain and improve perioperative stress in patients, while achieving better surgical outcomes and a significantly improved quality of life in patients at long-term follow-up.

Electron delocalization in aromatic materials significantly impacts their third-order nonlinear optics (NLO). Despite organometallic complexes with Craig-Mobius aromaticity attracting great attention for their unusual physicochemical properties, their third-order NLO have been little studied to date. Herein, 12 Craig-Mobius aromatic organometallics with a stable structure similar to osmapentalyne, namely, carbolong complexes, are screened by DFT. They exhibit high third-order NLO responses because of the d and p electron delocalization in the organometallic ring. Furthermore, electron-hole distribution analyses draw a conclusion that extending the conjugated plane will increase the π-conjugation system to enhance the local excitation in the plane, and the introduction of typical aromatic ligands can result in the organometallic ring-to-ligand charge transfer (RLCT), which are effective methods to improve the third-order NLO response. This study opens a new window in the application of Craig-Mobius aromatic complexes and provides a new approach for third-order NLO materials design.

The development of metal-organic frameworks (MOFs) with nonlinear optical (NLO) properties is of pronounced significance for optical devices. Herein, a series of 2D MOFs ZnTPyP(M) (TPyP = 5,10,15,20-tetrakis(4-pyridyl)porphyrin, M = Cu, Ni, Mn, H2) films with [010]-orientation growth composed of ultrathin nanosheets from a pyridylporphyrinic ligand are first obtained by using a liquid-phase epitaxial (LPE) layer-by-layer (lbl) growth approach. ZnTPyP(M) films show a giant nonlinear optical limiting (OL) response and can be modulated by tuning the type of metalloporphyrinic ligands. As a result, ZnTPyP(Cu) film exhibits the highest nonlinear absorption coefficient of 5.7 × 10-6 m/W compared to other reported NLO materials. Density functional theory calculations were consistent with the experimental results, revealing that the tunable π-π* local excitation and the increased delocalization of the metalloporphyrinic group regulate the NLO performance of ZnTPyP(M) films. These findings provide new insight into the effect of 2D porphyrinic MOFs toward the NLO response and offer new film candidates for nonlinear OL application.

The insufficient oxidation capacity, high carrier recombination rate and limited sunlight absorption seriously suppress the photocatalytic activity of pure g-C3N4. Using state-of-the-art hybrid density functional theory, we report an efficient method to tackle all aforementioned issues of g-C3N4 by metal-nonmetal (S and K) co-doping here. We find the adsorption of K atom on hollow site causes dynamic strain of g-C3N4. The S + K co-doping not only shifts the band edges downwards to achieve a much large overpotential of ca. 0.76 V, but also significantly extends the visible-light absorption threshold of g-C3N4. More importantly, the newly established channel between neighboring heptazine units in the doped structure is highly favorable for the separation of charge carriers. Our results help the design of high-performance visible-light-responsive g–C3N4–based photocatalyst for solar water splitting.

Two heterometal-oxo Ag2Ti10 (PTC-221) and Ag4Ti8 (PTC-222) clusters were successfully synthesized and characterized, with the doped Ag atoms surrounded by the Ti–O core and exposed to the cluster surface, respectively. Density functional theory (DFT) calculations were carried out to study the electronic structures of PTC-221 and PTC-222, including the frontier orbitals and partial density of states (PDOS). The solid-state UV-vis absorption spectra of PTC-221 and PTC-222 were also recorded. Interestingly, PTC-221 shows intense visible light absorption with an absorption edge around 590 nm and exhibits good photocurrent response in the visible region.

Recently, carbon dioxide capture and conversion, along with hydrogen from renewable resources, provide an alternative approach to synthesis of useful fuels and chemicals. People are increasingly interested in developing innovative carbon dioxide hydrogenation catalysts, and the pace of progress in this area is accelerating. Accordingly, this perspective presents current state of the art and outlook in synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols through two leading hydrogenation mechanisms: methanol reaction and Fischer-Tropsch based carbon dioxide hydrogenation. The future research directions for developing new heterogeneous catalysts with transformational technologies, including 3D printing and artificial intelligence, are provided. Carbon dioxide (CO2) capture and conversion provide an alternative approach to synthesis of useful fuels and chemicals. Here, Ye et al. give a comprehensive perspective on the current state of the art and outlook of CO2 catalytic hydrogenation to the synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols.

In the work reported in this article, di(methylsulfonyl) ethane (DMSE) was examined as a neoteric S-related electrolyte additive to elevate LiCoO2/electrolyte interfacial stability at 3.0-4.5 V (compared to Li/Li+). DMSE, when added to the electrolyte, can significantly enhance the high-voltage performance of LiCoO2/graphite cells. Meanwhile, capacity retention increased from 20.8 to 66.5% after 100 cycles owing to the adjunction of 0.5 wt % DMSE to the electrolyte (carbonate solvents and lithium salt). The density functional theory calculation results indicate that DMSE has a greater highest occupied molecular orbital energy in contrast to ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate. Differential capacity versus voltage analysis and linear sweep voltammetry result indicate that DMSE is decomposed in preference to the electrolyte solvents. DMSE's effects are distinguished by electrochemical impedance spectroscopy, Fourier transform infrared spectroscopy, X-ray-diffraction spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The outcomes indicate that the enhanced cycling performance is attributed to the involvement of DMSE in the generation of a thinner film on LiCoO2, which results in lower interfacial impedance and it protects the electrolyte from decomposition at high voltage.

Recent years have witnessed the explosive growth of multimedia applications over networks and increasingly high requirements of consumers for multimedia signals in terms of quality of experience (QoE). Effective and efficient yet energy-saving saliency detection model and quality prediction method are eagerly desired, since they play critical roles in raising users' QoE and promoting the progress of green multimedia communication. Current studies of saliency detection and quality evaluation are far from ideal yet. In this paper we investigate the influence of complexity on visual saliency and quality. Complexity is an essential concept in human perception to visual stimulus, but it is substantially abstract and hard to be endowed with a clear definition. We suppose that brain systematically combines global and local features during the whole process of human perception. Global features lead a dominant position in seeking salient areas under the condition that image complexity is high, namely without obviously isolated foreground objects, whereas local features play a key role in an opposite situation. With this consideration, this paper establishes a novel framework for detecting visual saliency based on image complexity estimation before complexity-adaptive merging of global and local features. Furthermore, the concept of complexity is deployed for blind photographic image quality assessment (IQA) by means of saliency-based weighting. Features which refer to contrast, artifacts, brightness and natural scene statistics (NSS) are modified and integrated to derive a blind IQA model and predict the quality of photos. Based on the above two technologies, this paper introduces smart phones as mobile terminals, cloud platforms for speed-up and energy-saving, and wireless networks for transmission, and provides a practical mobile multimedia application. Comparative experiments validate that, within this application system, our proposed saliency detection model and blind photographic IQA method implement better than existing relevant competitors in terms of effectiveness and efficiency comparison.

Tributyl borate (TBB) is studied as a protective additive that enhances the interfacial stability of a LiNi0.5Mn1.5O4 cathode/electrolyte at 5 V and 55 °C. Upon addition of 0.5 vol % TBB to the ele...

In recent years, organic–inorganic hybrid halide perovskites have attracted great attention. In view of the toxicity of lead, lead-free perovskites have been developed in order to obtain comparable or better photovoltaic performance than MAPbI3. In this study, the structural, electronic, and optical properties of pure and mixed perovskite systems were investigated by using density functional theory calculations. The results reveal that three Pb–Sn–Ge perovskites are predicted to preserve improved structural stabilities over MAPbI3. The band gaps of hybrid perovskites can be tuned by means of Sn–Ge doping. The band gap of MAPb0.50Sn0.25Ge0.25I3 is in the optimum range of 1.3–1.4 eV. Optical property analysis implies that MAPb0.50Sn0.25Ge0.25I3 possesses a comparable absorption ability in the visible light region compared with the MAPbI3 structure. In addition, the results indicate that MAPb0.50Sn0.25Ge0.25I3 with the highest power conversion efficieny of 23.65% can be chosen as a potential candidate for th...

The development of cost-effective, high-efficiency, and non-noble metal based electrocatalysts for oxygen evolution reaction (OER) is considered to be the most pivotal portion for electrochemical water splitting to generate renewable energy. Herein, well-aligned mesoporous CoFe2O4 thin film is first developed from surface epitaxial growth of oriented CoFe-based prussian blue analogue thin film (CoFe-PBA thin film) for efficient electrocatalytic OER. CoFe-PBA thin film with preferred [100] orientation is first prepared on the substrate surface by employing liquid phase epitaxial method without any structure-directing surfactants. After thermal pyrolysis, such CoFe-PBA thin film was transformed into well-aligned mesoporous CoFe2O4 thin film. Interestingly, the self-support CoFe2O4 thin film electrode with the mass loading of 1.6 mg cm−2 delivers an oxygen evolution current density of 10 mA cm−2 at an overpotential of 266 mV and exhibits durable stability in 1 M KOH aqueous solution. The remarkable and stable catalytic performance of the CoFe2O4 thin film can be mainly owing to the mesoporous structure of CoFe2O4, efficient charge/electron transfer, the numerous exposed active sites, and the well-structured configuration of the electrode. Hence, this work provides an effective paradigm for preparing binder-free, self-support, and low-cost spinel oxide electrocatalyst for efficient OER derived from surface epitaxial growth of oriented PBA thin film.

It is quite appealing but challenging to predict and synthesize new nonlinear optical (NLO) materials with exceptional performance. Herein, the different Sn4 cluster core structures and third-order NLO properties are studied through electronic structure, excited hole-electron, bonding character, and aromaticity analysis. As a result, Sn4 clusters with ring core structure (Sn4-R) not only have the smallest Egap, the largest UV-vis response intensity, but also the strongest third-order NLO response in our work. As proved by natural bond orbitals' (NBO) analysis, electron localization function (ELF), and adaptive natural density partitioning (AdNDP), the Sn44+ has two in-plane four center-two electron (4c-2e) Sn-Sn σ-bonds, resulting in a good delocalization. For the first time, delocalization of metal cluster cores in tin clusters that is beneficial to the third-order NLO response is proposed, which provides a new guidance to design and prepare third-order NLO materials.

Background Pain management is currently important in neonatal intensive care unit (NICU). The superiority in pain relief of the combined oral sucrose (OS) and nonnutritive sucking (NNS) to other single intervention has not been well established. The administration of sucrose has been considered to potentially induce adverse events, which has been controversial. This study aims to investigate the combined effects and safety in comparison with other single intervention methods, including NNS, OS alone, breast milk and oral glucose. Methods We searched databases including Medline (via Pubmed), Embase (via Ovid), web of science, and Cochrane Library for randomized controlled trials from Jan 1, 2000 to Mar 31, 2021. The data were analyzed in the meta-analysis using Review manager Version 5.3. Pain score was the primary outcome in this meta-analysis. The adverse events were assessed qualitatively. Results A total of 16 studies were eligible in the meta-analysis. The results demonstrated a significant reduction in pain score in the NNS+OS group compared with NNS alone (SMD = -1.69, 95%CI, -1.69,-0.65) or sucrose alone (SMD = -1.39, 95% CI, -2.21,-0.57) during the painful procedures. When compared NNS+OS with breast milk, no significant difference was detected (SMD = -0.19, 95% CI: -0.5, 0.11). Conclusion The combined effects of NNS and OS might be superior to other single intervention method. However, the effects might be mild for moderate-to-severe pain.

Curative therapies for chronic hepatitis B virus (HBV) infection remain a distant goal, and the persistence of stable covalently closed circular DNA (cccDNA) during HBV replication is a key barrier that is hard to break through using the drugs currently approved for HBV treatment. Due to the accuracy, efficiency, and cost-effectiveness of genome editing, CRISPR/Cas technologies are being widely used for gene therapy and in antiviral strategies. Although CRISPR/Cas could possibly clear cccDNA, ensuring its safety is requirement for application. In our study, we analyzed the liver specificity of several promoters and constructed candidate promoters in the CRISPR/Staphylococcus aureus Cas9 (SaCas9) system combined with hepatotropic AAV8 (whereby AAV refers to adeno-associated virus) to verify the efficacy against HBV. The results revealed that the reconstructed CRISPR/SaCas9 system in which the original promoter replaced with a liver-specific promoter could still inhibit HBV replication both in vitro and in vivo. Three functional guide RNAs (gRNAs), T2, T3, and T6, which target the conserved regions of different HBV genotypes, demonstrated consistently better anti-HBV effects with different liver-specific promoters. Moreover, the three gRNAs inhibited the replication of HBV genotypes A, B, and C to varying degrees. Under the action of the EnhII-Pa1AT promoter and AAV8, the expression of SaCas9 was further decreased in other organs or tissues in comparison to liver. These results are helpful for clinical applications in liver by ensuring the effects of the CRISPR/Cas9 system remain restricted to liver and, thereby, reducing the probability of undesired and harmful effects through nonspecific targeting in other organs.

A bilayer hexagonal wheel Sn