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A novel melilite IR-NLO oxychalcogenide, Sr2FeGe2OS6, has been prepared for the first time, which represents the first Fe-based example capable of achieving phase-matching features in the IR-NLO chalcogenide system.

A dual-channel superstructured Ni single-atom catalyst with a unique axial oxygen coordination configuration was controllably constructed and affords a preeminent performance for convergent paired electrosynthesis of dimethyl carbonate from CO2.

A novel 2D quaternary thioarsenate, CsZnAsSe3, was obtained by a stereochemically active lone pair (SCALP) induction strategy, which exhibits a 28-fold increase in birefringence compared to the known 3D framework CsZn4Ga5Se12.

Zero-dimensional (0D) organic-inorganic metal halides (OIMHs) hold promise in photoluminescence properties and related applications. Thus far, the photoluminescence quantum yields (PLQYs) of the reported 0D hybrid antimony(III) bromides (HABs) are not as high as those of the chloride analogs; therefore, the improvement of PLQY is an important issue for luminescent HABs. Herein, a supramolecular interaction adjustment strategy to improve the PLQYs of HABs is proposed. Two isostructural 0D HABs that crystallize with different lattice solvent molecules, namely [EtPPh

Two novel quaternary thioarsenates Cs2ZnAs4S8 and [(NH4)Cs]CdAs4S8 with intriguing dimensional transition have been discovered for the first time, which display variable photocurrent response and optical anisotropy.

A new promising IR-NLO material SrCdSiS4 with a 2D layered structure has been designed via a dual-site isovalent substitution strategy. Remarkably, it is the first report on an alkaline-earth metal-based IR-NLO material that breaks through the wall of Eg > 3.5 eV and deff > 1 × AgGaS2.

By introducing Cs into known Cu3SbS4, we successfully obtained a novel thioantimonate, quaternary CsCu3SbS4 with an unprecedented 2D layered structure, which exhibits a giant birefringence (0.232 at 549 nm).

Tailored structural regulation to obtain a new non-centrosymmetric (NCS) compound with excellent optical properties is highly desirable but remains a challenge for nonlinear optical (NLO) material design. In this work, centrosymmetric celsian-type BaGa

Metal-rich chalcogenides with unique network architectures are rare but are of considerable interest because of their intriguing physical properties. In this work, a novel quaternary thioantimonate, Rb2CuSb7S12, has been discovered by a facile surfactant-thermal reaction. It crystallizes monoclinic space group P1 (No. 2) and exhibits a unique Sb-rich three-dimensional (3D) [CuSb7S12]2- framework surrounded by charge-compensating Rb+ cations. It is interesting to note that the Cu/Sb ratio of Rb2CuSb7S12 represents the lowest limit in the quaternary A/Cu/Sb/Q (A = alkali metals; Q = chalcogen) system. Moreover, Rb2CuSb7S12 shows rapid response and good reproducibility based on the photoelectrochemical tests. This study opens up opportunities for discovering the desirable physical properties in metal-rich chalcogenides.

Despite the fact that nonlinear optical (NLO) crystals such as AgGaS2 and AgGaSe2 have been widely used in the infrared (IR) range due to their large second harmonic generation (SHG) coefficients and wide range of IR transparency windows, the small laser-induced damage threshold (LIDT) remains a great issue hindering their high-power applications. Herein, three noncentrosymmetric (NCS) chalcogenides AZn4Ga5Se12 (A = K, Rb, or Cs) are successfully obtained through an appropriate flux method after the extensive design and synthesis of the A/Zn/Ga/Q system. Single-crystal X-ray diffraction data demonstrate that they adopt trigonal space group R3 (No. 146) with three-dimensional diamond-like frameworks composed of [M9Se24] layers (M = Zn or Ga) stacking in the same direction and filled by charge-balancing A+ cations. Noticeably, they all exhibit strong powder SHG responses (2.8-3.7 × AgGaS2) and amazing LIDTs (19.2-23.4 × AgGaS2). In addition, theoretical calculations are performed to further determine the relationship between NCS structures and NLO properties. This work provides effective solutions for overcoming the trade-off between strong SHG and high LIDT in IR-NLO materials.

The acquisition of a non-centrosymmetric (NCS) structure and achieving a nice trade-off between a large energy gap (

An electrocatalytic carbon dioxide reduction reaction (CO2RR) is an appealing route to obtain the value-added feedstocks and alleviate the energy crisis. However, how to achieve high-performance electrocatalysts for CO2 reduction to formate is challenging owing to the poor intrinsic activity, insufficient conductivity, and low surface density of active sites. Herein, we fabricated an extremely active and selective hydrangea-like superstructured micro/nanoreactor of ultrathin bismuth nanosheets through an in situ electrochemical topotactic transformation of hierarchical bismuth oxide formate (BiOCOOH). The resulted bismuth nanosheet superstructure is in the form of three-dimensional intercrossed networks of ultrathin nanosheets, forming an ordered open porous structure through self-assembly, which can be used as a micro/nanoreactor to enable a large electrochemically active surface area as well as high atomic utilization. Such a distinctive nanostructure endows the material with high electrocatalytic performances for CO2 reduction to formate with near-unity Faradaic selectivity (>95%) in a wide potential window from -0.78 to -1.18 V. Furthermore, this micro/nanoreactor can give the high current densities over 300 mA cm-2 at low applied potentials without compromising selectivity in a flow cell reactor. Density functional theory (DFT) and in situ attenuated total reflection-infrared spectroscopy (in situ ATR-IR) were further conducted to interpret the CO2RR mechanisms.

Inorganic chalcohalides are attracting a tremendous amount of attention because of their remarkable structural variety and desirable physical properties. Although great advances have been made in recent years, functional inorganic chalcohalides with two-dimensional neutral layers are still rare. Herein, two novel chalcohalides CdSnSX2 (X = Cl or Br) with high yields were obtained by reacting CdX2 with SnS using a traditional solid-state method at 823 K. Both of these chalcohalides adopt orthorhombic space group Cmcm (No. 63) with the following structural values: a = 4.014(4)-4.064(2) A, b = 12.996(2)-13.746(3) A, c = 9.471(2)-9.621(2) A, V = 494.1(8)-537.5(2) A3, and Z = 4. The prominent architectural feature is the unique two-dimensional [CdSnSX2] neutral layer consisting of composite [CdX2] and [SnS] sublattices that are connected alternately through the Cd-S-Sn bonds along the ac plane. The [CdX2] sublattice consists of a single octahedral chain of Cd-centered [CdX4S2] groups sharing cis-X edges, while the [SnS] sublattice consists of a bend-shaped chain of unusual [SnS2X2] units sharing vertices of S atoms. Significantly, each CdSnSX2 form (X = Cl or Br) shows high visible-light-induced photocatalytic activity for rhodamine B degradation, which is ∼7.0 times higher than that of nitrogen-doped TiO2 (TiO2-xNx) under the same experimental conditions. This discovery enriches the categories of inorganic chalcohalides and provides more choices of candidate materials for photocatalytic applications.

The electrochemical CO2 reduction reaction (CO2RR) to value-added and readily collectable liquid products is promising but remains a great challenge due to the lack of efficient and robust electrocatalysts. Herein, a self-supported large-size three-dimensional porous conductive network of bismuthene (Bi-ene-NW) as an efficient superstructured electrocatalytic membrane (ECM) has been pioneeringly assembled, in which the atomically thin Bi-ene with rich edge-site-involved defects is interconnected, highly exposing the active sites. Such ECM can be utilized as an ascendant catalytic cathode, displaying an unprecedented CO2RR performance with near-unity selectivity in a wide potential window and large current density for formate production. Remarkably, when integrated into a gas diffusion electrode (GDE) in a flow cell, Bi-ene-NW was capable of delivering industry-compatible current densities up to 560 mA cm−2 for formate production. Moreover, it was ultrastable to continuously operate for over 500 h at a high current density without significant activity decay. Such outstanding performance should be inseparable from its abundant accessible sites with high intrinsic activity, multiple interconnected channels and superior conductivity for mass/charge transport. The operando ATR-IR and theoretical calculations further deciphered that the rich defects in the roughened plane edges and in-plane pore edges of Bi-ene are conducive to the *OCHO intermediate stabilization.

Non-centrosymmetric (NCS) structure is the precondition and foundation for the development of high-performance nonlinear optical (NLO) crystals. In this research, a quaternary NCS thioantimonate, K2Ag3Sb3S7, is designed through an aliovalent-cation-substitution-induced strategy based on the centrosymmetric (CS) parent compound K2Sb4S7 and successfully obtained through a facile surfactant-thermal technology. The unique crystal structure of K2Ag3Sb3S7 belongs to the orthorhombic space group Cmc21 (no. 36) and is made of charge-balanced K+ cations and two-dimensional (2D) anionic layers [Ag3Sb3S7]2− constructed by the vertex-sharing of ∞[Ag3SbS5]4− and ∞[SbS2]− chains. Remarkably, K2Ag3Sb3S7 not only possesses a phase-matching (PM) ability in the IR region, but also displays a perfect balance between a high second-harmonic-generation (SHG) coefficient (1.5 × commercial AgGaS2) and a large laser-induced damage threshold (3.2 × commercial AgGaS2). Moreover, theoretical studies uncover that the synergistic effects of three types of asymmetric building motifs (i.e., [SbS3], [Sb2S5] and [Ag3S6]) contribute to the large SHG effect and birefringence (Δn). This study not only demonstrates that aliovalent cation substitution can be a robust means of obtaining the NCS thioantimonates but also provides a deeper insight into the structure–property relationship of IR-NLO chalcogenides.

BackgroundInformation regarding the impact of cardiovascular disease (CVD) on disease progression among patients with mild coronavirus disease 2019 (COVID-19) is limited.MethodsThis study evaluated the association of underlying CVD with disease progression in patients with mild COVID-19. The primary outcome was the need to be transferred to intensive care due to disease progression. The patients were divided with and without CVD as well as stable and intensive care groups.ResultsOf 332 patients with mild COVID-19, median age was 51 years (IQR, 40-59 years), and 200 (61.2%) were female. Of 48 (14.5%) patients with CVD, 23 (47.9%) progressed to severe disease status and required intensive care. Compared with patients without CVD, patients with CVD were older, and more likely to have fatigue, chest tightness, and myalgia. The rate of requiring intensive care was significantly higher among patients with CVD than in patients without CVD (47.92% vs. 12.4%; PConclusionsPatients with mild COVID-19 complicating CVD in are susceptible to develop severe disease status and requirement for intensive care.Key PointsQuestionWhat is the impact of coexisting cardiovascular diseases (CVD) on disease progression in patients with mild COVID-19?FindingsAlthough most patients with mild COVID-19 were discharged alive from hospital, approximately 47.9% patients with coexisting CVD developed severe disease status and required intensive care. CVD is an independent risk factor of intensive care among patients with mild COVID-19.MeaningCoexisting CVD is associated with unfavorable outcomes among patients with mild COVID-19. Special monitoring is required for these patients to improve their outcome.

Self-supporting ultrathin FeNi-layered double hydroxide nanosheet arrays with atomically dispersed Cr atoms were firstly fabricated from stainless steel mesh by a facile ligand-assisted capping growth approach. Their unique nanostructure and a strong synergetic effect between the atomically dispersed Cr dopants and the active sites afford an exceptional OER activity.

Background: Previous studies reported the prognostic value of the triglyceride-glucose (TyG) index in the course of cardiovascular (CV) diseases. Still, it remains unclear whether baseline and trajectories of TyG index are prospectively associated with incident CV events among patients with type 2 diabetes mellitus (T2DM).Methods: We performed a secondary analysis in patients with long-lasting T2DM from the Action to Control Cardiovascular Risk in Diabetes (ACCORD) study. The primary outcome was the first occurrence of adverse CV events including nonfatal myocardial infarction, nonfatal stroke, or death from cardiovascular causes, and the TyG index was measured at 11 visits. Cox proportional hazards regression analysis was used to observe the association between baseline and trajectories of TyG index and adverse CV outcomes.Results: During a median follow-up period of 8.8 years, 1,815 (17.8%) developed at least one primary endpoint event. After adjusting for traditional cardiovascular risk factors, each 1-SD increase in the TyG index was associated with a 19.00% higher risk of adverse CV events, similar in individuals categorized by TyG index quartiles. Four distinct trajectories of TyG indexes were identified- low (16.17%), moderate (40.01%), high (34.60%), and very high (9.30%). Among these, moderate, high, and very high TyG index trajectories had a greater risk of future incident adverse CV events than low TyG index trajectories after multivariate adjustments for traditional risk factors. Particularly, a similar association was noticed in the TyG index and the occurrence of coronary heart disease.Conclusions: The findings of this study suggest that both baseline and trajectories of TyG index have a significant association with the occurrence of adverse CV events in patients with T2DM. (Trial registration: URL: http://www.clinicaltrials.gov. Unique identifier: NCT00000620)

Electrocatalytic CO

Metal-rich chalcogenides with unique network architectures are rare but are of considerable interest because of their intriguing physical properties. In this work, a novel quaternary thioantimonate, Rb

Despite the fact that nonlinear optical (NLO) crystals such as AgGaS

Sinus of Valsalva aneurysm, a rare cardiac anomaly, can be life-threatening if it ruptures. Transcatheter closure has emerged as an effective alternative to surgical management; however, it has rarely been reported in patients with previous mechanical aortic valve replacements. We describe the case of a 45-year-old man who presented with a ruptured aneurysm of the noncoronary sinus of Valsalva 14 years after the implantation of a mechanical aortic valve. The ruptured aneurysm was closed by transcatheter means with use of a double-disc perimembranous ventricular septal defect occluder. The patient remained asymptomatic one year after the procedure. Our case suggests that transcatheter closure with use of this type of occluder is a viable method for successfully repairing ruptured sinus of Valsalva aneurysms in patients who have mechanical aortic valves.

Inorganic chalcohalides are attracting a tremendous amount of attention because of their remarkable structural variety and desirable physical properties. Although great advances have been made in recent years, functional inorganic chalcohalides with two-dimensional neutral layers are still rare. Herein, two novel chalcohalides CdSnSX

Transcatheter closure (TCC) has emerged as the first-line treatment for coronary artery fistulas. However, limited data exist regarding the long-term outcomes and technical aspects of this procedure. We aimed to report the long-term outcomes and technical aspects of TCC of large coronary-cameral fistulas (CCFs).All patients with large CCFs who underwent attempted TCC using the patent ductus arteriosus (PDA) occluder or Amplatzer vascular plug (AVP), from June 2002 to December 2017, were retrospectively reviewed. A total of 23 patients with large CCFs underwent attempted TCC using the PDA occluder or AVP. Most CCFs originated from the right coronary artery and drained predominantly into the right heart chamber. Procedural success was achieved in 21 (91.3%) patients. Devices were deployed using the arteriovenous loop in 15, transarterial approach in 4, and arterio-artery loop approach in 2 patients. Procedural complications included coronary spasm in one and side branch occlusion in one patient. Among these 21 patients with successful device implantation, follow-up angiograms or computed tomography angiograms were obtained in 14 (66.7%) patients at a median of 11.0 (range, 9.8-16.3) months. Late complications included thrombosis of residual fistula segment without myocardial infarction (MI) in one, coronary thrombosis resulting in MI in one, and recanalization necessitating re-intervention in one patient. No death and device embolization occurred.TCC of large CCFs using the PDA occluder or AVP is an effective therapy in anatomically suitable candidates, with favorable long-term outcomes. Given that potentially hazardous complications may occur late after the procedure, long-term periodic evaluation is mandatory.

•The basaltic lavas in the CVB delineate a composition-space variation pattern.•The North CVB basalts may relate to melting of depleted asthenospheric mantle.•Metasomatized lithosphere has contributed to the genesis of the South CVB basalts.

Lithium elemental and isotopic disequilibrium has frequently been observed in the continental and oceanic mantle xenoliths, but its origin remains controversial. Here, we present a combined elemental and Li isotopic study on variably metasomatised peridotite xenoliths entrained in the Cenozoic basalts from Shangzhi in Northeast (NE) China that provides insight into this issue. Li concentration (0.3–2.7 ppm) and δ7Li (mostly 2‰–6‰) in olivine from the Shangzhi peridotites are similar to the normal mantle values and show roughly negative correlations with the indices of melt extraction (such as modal olivine and whole rock MgO). These features are consistent with variable degrees of partial melting. In contrast, clinopyroxene from the Shangzhi xenoliths shows significant Li enrichment (0.9–6.1 ppm) and anomalously light δ7Li (− 13.8‰ to 7.7‰) relative to normal mantle values. Such features can be explained by Li diffusion from silicate melts or Li-rich fluids occurring over a very short time (several minutes to several hours). Moreover, the light Li isotopic compositions preserved in some bulk samples also indicate that these percolated melts/fluids have not had enough time to isotopically equilibrate with the bulk peridotite. We thus emphasize that Li isotopic fractionation in the Shangzhi mantle xenoliths is mainly related to Li diffusion from silicate melts or Li-rich fluids that took place shortly before or coincident with their entrainment into the host magmas.

Electrocatalytic CO2 reduction reaction (CO2 RR) toward formate production can be operated under mild conditions with high energy conversion efficiency while migrating the greenhouse effect. Herein, an integrated 3D open network of interconnected bismuthene arrays (3D Bi-ene-A/CM) is fabricated via in situ electrochemically topotactic transformation from BiOCOOH nanosheet arrays supported on the copper mesh. The resulted 3D Bi-ene-A/CM consists of 2D atomically thin metallic bismuthene (Bi-ene) in the form of an integrated array superstructure with a 3D interconnected and open network, which harvests the multiple structural advantages of both metallenes and self-supported electrodes for electrocatalysis. Such distinctive superstructure affords the maximized quantity and availability of the active sites with high intrinsic activity and superior charge and mass transfer capability, endowing the catalyst with good CO2 RR performance for stable formate production with high Faradaic efficiency (≈90%) and current density (>300 mA cm-2 ). Theoretical calculation verifies the superior intermediate stabilization of the dominant Bi plane during CO2 RR. Moreover, by further coupling anodic methanol oxidation reaction, an exotic electrolytic system enables highly energy-efficient and value-added pair-electrosynthesis for concurrent formate production at both electrodes, achieving substantially improved electrochemical and economic efficiency and revealing the feasibility for practical implementation.