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The photocatalytic hydrogenation of CO2 by Cu-deposited ZnO (Cu/ZnO) polar surfaces is investigated through density functional theory (DFT) calculations combined with experimental work.

Molecular aggregation affects the electronic interactions between molecules and has emerged as a powerful tool in material science. Molecular aggregation finds wide applications in the research of new physical effects; however, its value for chemical reaction development has been far less explored. Herein, we report the development of aggregation-enabled alkene insertion into carbon–halogen bonds. The spontaneous cleavage of C–X (X = Cl, Br, or I) bonds generates an intimate ion pair, which can be quickly captured by alkenes in the aggregated state. Additional catalysts or promoters are not necessary under such circumstances, and solvent quenching experiments indicate that the aggregated state is critical for initiating such sequences. The ionic insertion mode and the intimate ion pair mechanism are supported by mechanistic studies, density functional theory calculations, and symmetry-adapted perturbation theory analysis. Results show that the non-aggregated state may quench the transition state and terminate the insertion process.

Background Breast cancer is the most common malignant tumor that threatens women's health. The study of long-chain non-coding RNA (lncRNA) in breast cancer has been paid more and more attention, which is related to the progression of breast cancer, but the specific mechanism is not clear. Methods In this study, we explored the role of lncRNA BC069792 in breast cancer. In vitro and in vivo functional experiments were carried out in cell culture and mouse models. High-throughput next-generation sequencing technology and real-time fluorescence quantitative PCR technology were used to evaluate differentially expressed genes and mRNA expression, Western blot and immunohistochemical staining were used to detect protein expression. RNA immunoprecipitation assay and dual-luciferase activity assay were used to evaluate the competing endogenous RNAs (ceRNA), and rescue and mutation experiments were used for verification. Results We found that lncRNA BC069792 was expressed at low level in breast cancer tissues, and significantly decreased in breast cancer with high pathological grade, lymph node metastasis and high Ki-67 index groups. Moreover, BC069792 inhibited the proliferation, invasion and metastasis of breast cancer cells in vitro and in vivo. Mechanically, BC069792 acts as a molecular sponge to adsorb hsa-miR-658 and hsa-miR-4739, to up-regulate the protein expression of Potassium Voltage-Gated Channel Q4 (KCNQ4), inhibit the activities of JAK2 and p-AKT, and play a role in inhibiting breast cancer growth. Conclusions LncRNA BC069792 plays the role of tumor suppressor gene in breast cancer and is a new diagnostic index and therapeutic target in breast cancer.

The combination of gene therapy and chemotherapy provides a We developed a simple and versatile approach to prepare a series of two-in-one nanodrugs through direct self-assembly of cyanine-labeled single-stranded DNA (Cys-DNA) and different types of drug molecules. Molecular dynamics simulation showed that the Cys introduced into the DNA could enhance the noncovalent interaction between Cys-DNA and drug molecules. More drug molecules were incorporated into Cys-DNA, tending to spontaneously form hybrid Cys-DNA/drug nanosphere. Such nanospheres serve as both carriers and cargoes, excluding the extra use of nontherapeutic excipients and showing ultrahigh drug loading capacity. Following this approach, an antisense oligonucleotides/doxorubicin nanodrug model was constructed, demonstrating the significant synergistic anti-tumor therapeutic effect. As a proof of the concept, our study establishes a simple and reproducible two-in-one nucleic acid-based drug formulation.

Rhodium(I)-catalyzed cycloisomerization reactions of 1,6-allenynes with a tethered alkene (homoallylallene–alkyne substrate) or alkyne (homopropargylallene–alkyne substrate) have recently shown gre...

Combined QM/MM calculations and MD simulations are utilized to investigate the detailed mechanisms of reactions catalyzed by wild-type nickel-dependent quercetin 2,4-dioxygenase (Ni-QueD) and its Glu76Asp and Glu76Gln mutants. The conserved nickel-ligating Glu76 residue in the deprotonated form is found to be essential for initiating the catalytic reaction by proton coupled electron transfer process. The generated protonated Glu76 promotes the subsequent reaction by regulating hydrogen-bonding (H-bonding) interaction with the carbonyl groups of quercetin. Investigations of Glu76Gln and Glu76Asp mutants show that mutation of Glu76 suppresses such H-bonding interaction and results in the lower catalytic activity observed experimentally. Thus, our results reveal the critical role of Glu76 residue in steering the reactivity of Ni-QueD. This work is not only useful for better understanding the mechanisms of reactions catalyzed by other metal ion-dependent QueDs, but also provides insights into how enzymes achieve specific reactions by utilizing H-bonding interaction from the metal center-ligating residues.

Isolated intracranial myeloid sarcoma (MS) is an unusual variant tumor with few cases reported so far in the medical literature. A 29-year-old woman was admitted to our hospital presenting progressive visual loss in the right eye and weight loss (20 kg) without a previous history of hematological disease (HD). Radiologic evaluation showed the evidence of intracranial mass. Histologically, the resected tumor was composed of a uniform population of primitive cells and primarily misdiagnosed as a T-cell non-Hodgkin's lymphoma (NHL). Chemotherapy with cyclophosphamide, doxorubicin, vinblastine, and prednisone (CHOP) was ineffective. A biopsy and histopathological evaluation were repeated, and immunohistochemical staining revealed the positivity of immature cells to an extensive panel of myeloid markers. These findings were consistent with a diagnosis of MS and bone marrow infiltration. Literature reviews of previous cases were also undertaken.

The species diversity of silicon (including traditional tetrahedral coordinated silicon and hypervalent penta- and hexa-coordinate silicon) gives rise to the structural richness and diverse properties of silicates. Among these silicon species, hypervalent silicon is very rare, not to mention almost unexplored mixed-anion hypervalent fluoroxosilicate species. In this work, we successfully obtained a mixed-anion fluorooxosilicophosphate Na4Si2PO4F9 consisting of two uncommon hypervalent fluoroxosilicate species, namely, trans-SiO2F4 species and SiOF5 species. To the best of our knowledge, such hypervalent silicon species are reported for the first time in inorganic compounds. Remarkably, the coexistence of two distinct hypervalent fluoroxosilicate species in one compound is somewhat conflicted with Pauling's parsimony rule, but it indeed achieves an unlikely connection by PO4 and our phonon dispersion calculation confirms the structure stability of Na4 Si2 PO4 F9 . Temperature-dependent conductivity measurements show that Na4 Si2 PO4 F9 is a promising solid ionic conductor with a high conductivity of 4.0×10-5 S⋅cm-1 at 700 K and a low active energy of about 53.1 KJ⋅mol-1 . This work will enrich the structure chemistry of silicates and may provide a new platform for solid ionic batteries.

Autophagy and apoptosis are dynamic processes that determine the fate of cells, and regulating these processes can treat cancer. GEFT is highly expressed in rhabdomyosarcoma (RMS), which accelerates the tumorigenicity and metastasis of RMS by activating Rac1/Cdc42 signaling, but the regulatory mechanisms of autophagy and apoptosis are unclear. In our study, we found that the RMS tissues had high Rac1, Cdc42, mTOR, and Bcl-2 expression levels and low Beclin1, LC3, and Bax expression levels compared with the normal striated muscle tissues (P < 0.05). In addition, multivariate analysis has proven that Rac1 is an independent prognostic factor (P < 0.05), and the high expression level of the Beclin1 protein was closely associated with the tumor diameter of the RMS patients (P = 0.044), whereas the high expression level of the LC3 protein was associated with the clinical stage of the RMS patients (P = 0.027). Furthermore, GEFT overexpression could inhibit autophagy and apoptosis in RMS. A Rac1/Cdc42 inhibitor was added, and the inhibition of autophagy and apoptosis decreased. Rac1 and Cdc42 could regulate mTOR to inhibit autophagy and apoptosis in RMS. Overall, these studies demonstrated that the GEFT–Rac1/Cdc42–mTOR pathway can inhibit autophagy and apoptosis in RMS and provide evidence for innovative treatments.

BackgroundPrimitive myxoid mesenchymal tumor of infancy (PMMTI) is a rare tumor and its molecular mechanism and prognosis remain unclear. We here report a case of PMMTI, and review the reported literature of PMMTI.Case presentationA one-year-old boy found a lump in his right groin. The size of the mass was 1 cm×1 cm. Computed tomography showed a round, slightly dense shadow of 38 mm×32 mm in the right groin. The tumor was removed for pathological examination, and the size of the tumor was 6.0 cm×5.0 cm×3.0 cm. Tumor cells are diffusely distributed, mainly spindle cells. The blood vessels were abundant, many adipocytes can be observed in some areas, and focal lymphocyte infiltration can be seen in a few areas. Immunophenotype was as follows: histone H3 at lysine 27 (H3K27me3), B-cell lymphoma 6 corepressor (BCOR) and Bcl-2 were positive, cluster of differentiation 99 (CD99) showed diffuse reactivity, BCL6 was scattered positive, Ki-67 proliferation index was 20%. Dual-color fluorescence in situ hybridization (FISH) showed red and green signal nuclei caused by the deletion of ETV6 gene rearrangement. The patient underwent extensive surgical resection during the recurrence period and was in good condition 7 months later.ConclusionsPMMTI is at least a low-grade malignancy. BCOR, BCL2, BCL6, and CD99 can be used as special IHC markers, and most PMMTI cases exhibit BCOR ITD change. H3K27me3 may be used as a new IHC marker for PMMTI.

One-dimensional (1D) semiconductor nanorods are important for numerous applications ranging from optics and electronics to biology, yet the direct synthesis of high-quality metal halide perovskite nanorods remains a challenge. Here, we develop an intermediate monomer reservoir synthetic strategy to realize the controllable growth of uniform and low-defect CsPbBr3 perovskite nanorods. Intermediates composed of CsPb2Br5 and Cs3In2Br9 are obtained through the substitution of Pb2+ with In3+ cations in the template of CsPbBr3 nanocubes and act as a precursor reservoir to gradually release monomers, ensuring both the slow growth rate and low defects of nanorods. We have used branched tris(diethylamino)phosphine as a ligand, which not only has unequal binding energies with different crystal faces to promote the orientation growth but also provides strong steric hindrance to shield the nanorods in solution. Because of minor amount of defects and an effective ligand passivation, in addition to significantly enhanced stability, the perovskite nanorods show a high photoluminescence quantum yield of up to 90% and exhibit a net mode gain of 980 cm-1, the latter being a record value among all the perovskite materials. An extremely low amplified spontaneous emission threshold of 7.5 μJ cm-2 is obtained under excitation by a nanosecond laser, which is comparable to that obtained using femtosecond lasers in other recent studies.

There is a long-standing mechanistic consensus that alcohol oxidation by cytochrome P450 enzymes is triggered by hydrogen abstraction from the α-C–H bond of the alcohol. Through combined molecular ...

Background: Soft tissue sarcomas include multiple histological subtypes and are highly aggressive. Moreover, SR-B1 is associated with malignant behavior and poor prognosis in a variety of cancers. However, there have been no attempts to assess whether SR-B1 expression in soft tissue sarcoma. We aimed to detect the expression levels of the SR-B1 protein in soft tissue sarcoma. Methods: We assessed SR-B1 expression via immunohistochemistry and tissue microarrays in 107 soft tissue sarcomas with 4 phenotypes: 26 liposarcomas, 18 Ewing's sarcomas, 20 rhabdomyosarcomas and 43 leiomyosarcomas. Results: Tumor cell SR-B1 expression was seen in 18/26 (69.2%) liposarcomas, 1/18 (5.55%) Ewing's sarcomas, 1/20 (5.00%) rhabdomyosarcomas, 2/43 (4.70%) leiomyosarcomas and was stained in the cell membrane. We found that SR-B1 expression in liposarcomas (18/26) was significantly higher than that in non-lipomatous sarcomas (4/77) (χ2 = 49.811, p = 0.000) and in well-differentiated liposarcoma (13/15) was significantly higher than that in dedifferentiated liposarcoma (5/11) (p = 0.038). No significant correlation was found between SR-B1 and gender, nationality, size and tumor location (p > 0.05), but it was significantly associated with ages (χ2 = 11.426, p = 0.001) and sarcoma phenotypes (χ2 = 49.817, p = 0.000). Conclusion: Our findings highlight the highly expression of SR-B1 in liposarcomas. SR-B1 may be a potential biomarker for the diagnosis of liposarcoma and may indicate the degree of differentiation of liposarcomas.

The Late Oligocene-Early Miocene epoch represents a critical stage in the collisional history of the India-Eurasia dominant collision zone. Within this timeframe, a set of tectonic events occurred simultaneously or progressively. However, the key responsible for triggering these nearly coeval events remains unclear. This study used an integrated analysis of both geological and geophysical data to document the tectonic interactions throughout the Himalayan Orogenic Belt from west to east. Deep seismic reflection profiles outline crustal geometry of a decoupled Indian subduction front, and the overlying sheets over the Main Himalayan Thrust (MHT) is evidenced with a sequence of detachment-associated ramp-anticlines. Meanwhile, regional magnetotelluric (MT) profiles document rheologic connections in the form of a high-conductivity anomaly running top-to-the south between the southernmost Tibet and the areas beyond the Yarlung-Zangbo Suture Zone to the south. The overall architecture provides a complete picture of the complex deformation pattern beneath the tectonic convergence system. Together with previous studies in surface geological investigations, we propose that the enhanced duplex stacking of the underthrusting Indian crust increased crustal shortening of the convergence system. The consequent sudden exposure of the northern Himalayan domes released the accumulated stress to trigger the onset of a south-dipping passive roof thrusting through the convergence system to the southernmost Tibetan Plateau. Recognition of this exchange pattern from crustal duplex stacking to passive roof thrusting replenished an understanding of the tectonic interactions of the ongoing India-Eurasia collision.

Atomically thin colloidal quasi-two-dimensional (2D) semiconductor nanoplatelets (NPLs) have attracted tremendous attention due to their excellent properties and stimulating applications. Although some advances have been achieved in Cd- and Pb-based semiconductor NPLs, research into heavy-metal-free NPLs has been reported less due to the difficulties in the synthesis and the knowledge gap in the understanding of the growth mechanism. Herein wurtzite ZnTe NPLs with an atomic thickness of about 1.5 nm have been successfully synthesized by using Superhydride (LiEt3BH) reduced tributylphosphine–Te (TBP-Te) as the tellurium precursor. Mechanistic studies, both experimentally and theoretically, elucidate the transformation from metastable ZnTe MSC-323 magic-size nanoclusters (MSCs) to metastable ZnTe MSC-398, which then forms wurtzite ZnTe NPLs via an oriented attachment mechanism along the [100] and [002] directions of the wurtzite structure. This work not only provides insightful views into the growth mechanism of 2D NPLs but also opens an avenue for their applications in optoelectronics.

Synergetic optical resolution and chiral amplification of tetrahedral Ti4L6 cages by enantiopure coordination cations have been realized in this work. Anionic ΔΔΔΔ-[Ti4L6] and ΛΛΛΛ-[Ti4L6] cages (L...

Multiscale simulations have been performed to address the longstanding issue of "dioxygen activation" by the binuclear copper monooxygenases (PHM and DβM), which have been traditionally classified as "noncoupled" binuclear copper enzymes. Our QM/MM calculations rule out that Cu

1-Borabicyclo[1.1.0]but-2(3)-ene (1BB) is a singlet biradical with two single electrons that can form an ionic resonance structure through a charge shift. The ionic resonance structure is a B-heterocyclic carbene (BHC), which can act as a carbene, Lewis base, or L- and Z-type ligand, to give adducts and complexes. Through a range of quantum methods, four types of stable compounds (A-D) derived from 1BB have been designed. These compounds retain the unique features of 1BB. As a consequence, the structures, stability, and Wiberg bond indices of the Lewis adducts of A-D with Lewis acids (BePh2 , BH3 , AlH3 , AlCl3 , C5 BH5 , and C13 BH9 ) and CuI , AgI , and AuI complexes have been investigated. Results show that A-D can indeed react as carbenes. Interestingly, compounds A-D, as L-type ligands, can attach to BePh2 , BH3 , AlH3 , AlCl3 , C5 BH5 , C13 BH9 , and CuCl and form compounds with planar tetracoordinate carbon (ptC), whereas Z-type ligands A-D can bind to AgCl and AuCl to provide complexes with planar tetracoordinate boron (ptB). In addition, the binuclear complexes of ClX(1BB)CuCl (X=Ag, Au) have been studied and A-D behave as both L- and Z-type ligands, in which these complexes contain both ptC and ptB. Thus, a novel method for designing compounds with ptC and ptB is presented. These rationally designed compounds involve the elements of carbene, ptC, ptB, and L- and Z-type ligands, and are expected to be unique and useful in experimental chemistry once they are synthesized.

BIF-20, a zeolite-like porous boron imidazolate framework with high density of exposed B–H bonding, is combined with graphitic carbon nitride (g-C3N4) nanosheets via a facile electrostatic self-assembly approach under room temperature, forming an elegant composite BIF-20@g-C3N4 nanosheet. The as-constructed composite preferably captures CO2 and further photoreduces CO2 in high efficiency. The photogenerated excitations from the carbon nitride nanosheet can directionally migrate to B–H bonding, which effectively suppresses electron–hole pair recombination and thus greatly improves the photocatalytic ability. Compared to the g-C3N4 nanosheet, the BIF-20@g-C3N4 nanosheet composite displayed a much-enhanced photocatalytic CO2 reduction activity, which is equal to 9.7-fold enhancements in the CH4 evolution rate (15.524 μmol g–1 h–1) and 9.85-fold improvements in CO generation rate (53.869 μmol g–1 h–1). Density functional theory simulations further prove that the presence of B–H bonding in the composite is fav...

Summary: The Heck reaction, along with other cross-coupling reactions, led to a revolution in organic chemistry. In the last 50 years, metal-catalyzed, photo-induced, or base-mediated Heck and Heck-type reactions have been elegantly developed. Brønsted acid-catalyzed Heck (or Heck-type) reactions are still unknown, however. By introducing alkyl peroxides as the key intermediates, primary, secondary, and tertiary aliphatic carboxylic acids are therefore applied here in a one-pot Brønsted acid-catalyzed Heck-type reaction, to deliver E-alkenes exclusively in most cases. The use of HOTf is vital to the reaction, whose mechanism is supported by both experimental and computational results. This method can be expanded to the direct alkylation of complex natural products. : Organic Synthesis; Organic Chemistry Methods; Natural Product Synthesis Subject Areas: Organic Synthesis, Organic Chemistry Methods, Natural Product Synthesis

For EAST experiments, the plasma control system (PCS) needs a lot of diagnostic data produced by the distributed subsystems of EAST to meet the requirements of steady-state plasma control. But due to the factors of different sampling frequencies of the subsystems and the signal distortion caused by long distance transmission, it’s difficult for the PCS alone to acquire all the diagnostic data in each control cycle. So the real-time data sharing system is designed to solve the problem of real-time data transmission between the PCS and the subsystems so as to realize data sharing among the distributed EAST systems. In consideration of the required transfer speed and data volume, a “multiple networks” structure composed of a reflective memory (RFM) network and a Gigabit Ethernet network is used to build this system. To work with this multi-network structure, Red Hat MRG Realtime (Messaging, RealTime, and Grid) operating system (OS) is adopted, as it can provide deterministic response time. This system is responsible for transferring the diagnostic data collected by the data acquisition (DAQ) systems of the various distributed subsystems to the PCS and data server. The PCS receives the data through the RFM network in each PCS control cycle (defined as 100 microseconds) while the data server receives the data through the Ethernet network in every time-slice (defined in the DAQ program). All the relevant diagnostic data are to be available to the PCS through the data sharing system, though the PCS has the ability to choose some specified data according to its own needs during the plasma control. Likely, the above advantages for the PCS also apply for any EAST subsystems connected to the RFM network. In this paper, the details of the real-time data sharing system are described and the future work is also discussed.

The mechanism of the ruthenium carboxylate-catalyzed hydrogenation of carboxylic acids was investigated by using density functional theory (DFT) calculations. The novel mechanism including two hydrogenation cycles was proposed for this reaction. The first cycle is the hydrogenation of the carboxylic acid to an aldehyde, while the second cycle is the hydrogenation of the aldehyde to an alcohol. These two catalytic cycles share similar elementary steps, including H2 heterolysis, hydride migration of the carboxylic acid or aldehyde, and catalyst regeneration. In this hydrogenation mechanism, the carboxylic acid is not only a reactant, but also an important proton source. Furthermore, the noncovalent interaction (e.g. hydrogen bonding interaction) between the ligand and carboxylic acid substrate could promote the hydrogenation of the carboxylic acid through stabilizing the transition state of the most energy-demanding step (i.e., hydride migration in the first catalytic cycle). Besides, the strong electron-donating ability of the dppb ligand could also facilitate the hydride migration.

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.

Two new polar polyselenides Rb4Ge4Se12 (1) and Cs4Ge4Se12 (2) with rarely reported dimeric [Ge2Se4(μ-Se2)]4− units were synthesized. They present large second-harmonic generation (SHG) intensities of 7.5 and 6.5 times that of the benchmark AgGaS2 with type I phase-matching behavior, high laser induced damaged thresholds, wide transmission region and congruently melting behavior, making them excellent candidates for IR nonlinear optical (NLO) applications. The SHG functional motifs of both compounds are determined to be [Ge2Se4(μ-Se2)]4− unit by time-dependent density functional theory calculation, which further reveals that charge transfers from the lone pairs of terminal Se atoms to the five σ* orbitals of five-membered ring Ge2Se3 have a predominant contribution to the total SHG effect.

A rhodium-catalyzed azide–alkyne cycloaddition of internal ynamides is described. The reaction could be performed in a wide range of solvents, including aqueous media, under mild conditions without careful exclusion of air and moisture, giving a variety of 5-amino-triazoles as a single regioisomer. The mechanism of regioselective cycloaddition was rationalized by means of density functional theory calculations.

Planar tetracoordinate carbon (ptC) with intriguing planar bond structure has triggered great attentions. In this work, B/Be-terminated decoration form armchair hybridized boron nitride and graphene nanoribbons with ptC structure (ptC-aBCNNRs) are investigated theoretically for third-order nonlinear optical (NLO) response by employing time-dependent density functional theory combined with sum-over-states method. Our calculations reveal Be and B decorated on ptC-aBCNNRs would result in opposite variation of energy gaps, and strongly enhance the NLO response in different third-order NLO processes. The strong third-order NLO response predicted for ptC-aBCNNRs is originated from the charge redistribution induced by ptC structure and hexagonal-BN ribbon insertion.

The solid oxide CO2 electrolyzer has the potential to provide storage solutions for intermittent renewable energy sources as well as to reduce greenhouse gas emissions. One of the key challenges remains the poor adsorption and activity toward CO2 reduction on the electrolyzer cathode at typical operating conditions. Here, we show a novel approach in tailoring a perovskite titanate (La, Sr)TiO3+δ cathode surface, by the in situ growing of SrO nanoislands from the host material through the control of perovskite nonstoichiometry. These nanoislands provide very enhanced CO2 adsorption and activation, with stability up to 800 °C, which is shown to be in an intermediate form between carbonate ions and molecular CO2. The activation of adsorbed CO2 molecules results from the interaction of exsolved SrO nanoislands and the defected titanate surface as revealed by DFT calculations. These cathode surface modifications result in an exceptionally high direct CO2 electrolysis performance with current efficiencies near 100%.

A manganese complex with a porphyrin-like ligand that catalyzes the highly chemoselective and enantioselective oxidation of heteroaromatic sulfides, including imidazole, benzimidazole, indole, pyridine, pyrimidine, pyrazine, sym-triazine, thiophene, thiazole, benzothiazole, and benzoxazole, with hydrogen peroxide is described, furnishing the corresponding sulfoxides in good to excellent yields and enantioselectivities (up to 90% yield and up to >99% ee) within a short reaction time (0.5 h). The practical utility of the method has been demonstrated in the gram-scale synthesis of chiral sulfoxide. Mechanistic studies, performed with 18O-labeled water (H218O), hydrogen peroxide (H218O2), and cumyl hydroperoxide, reveal that a high-valent manganese–oxo species is generated as the oxygen atom delivering agent via carboxylic acid assisted heterolysis of O–O bonds. Density functional theory (DFT) calculations were also carried out to give further insight into the mechanism of manganese-catalyzed sulfoxidation. O...

Sustainable future energy scenarios require significant efficiency improvements in both electricity generation and storage. High-temperature solid oxide cells, and in particular carbon dioxide electrolysers, afford chemical storage of available electricity that can both stabilize and extend the utilization of renewables. Here we present a double doping strategy to facilitate CO2 reduction at perovskite titanate cathode surfaces, promoting adsorption/activation by making use of redox active dopants such as Mn linked to oxygen vacancies and dopants such as Ni that afford metal nanoparticle exsolution. Combined experimental characterization and first-principle calculations reveal that the adsorbed and activated CO2 adopts an intermediate chemical state between a carbon dioxide molecule and a carbonate ion. The dual doping strategy provides optimal performance with no degradation being observed after 100 h of high-temperature operation and 10 redox cycles, suggesting a reliable cathode material for CO2 electrolysis., Carbon dioxide electrolysers are promising for chemical storage of renewable electricity; however, achieving effective adsorption/activation of CO2 is still an issue. Here the authors make a perovskite titanate cathode where non-stoichiometry and chemical doping are used to tune the surface structures, facilitating CO2 reduction.

Substituted 2-borabicyclo(1.1.0)but-1(3)-enes (2BB’s) are a kind of novel molecules with inverted carbon–carbon bonds whose orders range between one and two. Considering the significant interest in the Diels–Alder (D–A) reactions of substituted cyclopropenes, here we studied the bonding and D–A reactions of 24 substituted 2BB molecules at the B3LYP-D3/6-311G** theoretical level. Computations showed that the inverted C=C bond lengths fall in the range of 1.46–1.50 A and 2BB is of significant characteristic of a singlet biradical with two σ single electrons and π aromatic conjugation over the three-membered rings. Yet ab initio valence bond computations showed that the inverted bonds are charge-shifted, and the ionic resonance structures arising from charge-shifting are of carbene characteristics as well. Thus, substituted 2BB’s can also be considered as B-heterocyclic carbenes. Since the LUMOs of the 2BB derivatives are similar to those of ethene and cyclopropene, we studied their D–A reactions with butadiene. All cycloaddition reactions kinetically and thermodynamically favor the formation of the derivatives of 7-bora-oct-3-ene[4.1.1]propellane undergoing endo transition states. Notably, there is a good correlation between the reaction barriers and the hyperconjugative aromatic and antiaromatic stabilization enthalpies for all substituted 2BB’s. In other words, the differences in their reactivity result from the difference in their aromatic stability.

Herein we employed a first-principles method based on density functional theory to investigate the surface energy and growth kinetics of wurtzite nanoplatelets to elucidate why nanoplatelets exhibit a uniform thickness of eight monolayers. We synthesized a series of wurtzite nanoplatelets (ZnSe, ZnS, ZnTe, and CdSe) with an atomically uniform thickness of eight monolayers. As a representative example, the growth mechanism of 1.39 nm thick (eight monolayers) wurtzite ZnSe nanoplatelets was studied to substantiate the proposed growth kinetics. The results show that the growth of the seventh and eighth layers along the [112̅0] direction of 0.99 nm (six monolayers) ZnSe magic-size nanoclusters is accessible, whereas the growth of the ninth layer is unlikely to occur because the formation energy is large. This work not only gives insights into the synthesis of atomically uniform thick wurtzite semiconductor nanoplatelets but also opens up new avenues to their applications in light-emitting diodes, catalysis, detectors, and lasers.