Achieving Molecular Sieving of CO2 from CH4 by Controlled Dynamical Movement and Host-Guest Interactions in Ultramicroporous VOFFIVE-1-Ni by Pillar Substitution.

Engineering the building blocks in metal-organic materials is an effective strategy for tuning their dynamical properties and can affect their response to external guest molecules. Tailoring the interaction and diffusion of molecules into these structures is highly important, particularly for applications related to gas separation. Herein, we report a vanadium-based hybrid ultramicroporous material, VOFFIVE-1-Ni, with temperature-dependent dynamical properties and a strong affinity to effectively capture and separate carbon dioxide (CO2) from methane (CH4). VOFFIVE-1-Ni exhibits a CO2 uptake of 12.08 wt % (2.75 mmol g-1), a negligible CH4 uptake at 293 K (0.5 bar), and an excellent CO2-over-CH4 uptake ratio of 2280, far exceeding that of similar materials. The material also exhibits a favorable CO2 enthalpy of adsorption below -50 kJ mol-1, as well as fast CO2 adsorption rates (90% uptake reached within 20 s) that render the hydrolytically stable VOFFIVE-1-Ni a promising sorbent for applications such as biogas upgrading.

Wavy Two-Dimensional Conjugated Metal-Organic Framework with Metallic Charge Transport.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a new class of crystalline layered conducting materials that hold significant promise for applications in electronics and spintronics. However, current 2D c-MOFs are mainly made from organic planar ligands, whereas layered 2D c-MOFs constructed by curved or twisted ligands featuring novel orbital structures and electronic states remain less developed. Herein, we report a Cu-catecholate wavy 2D c-MOF (Cu3(HFcHBC)2) based on a fluorinated core-twisted contorted hexahydroxy-hexa-cata-hexabenzocoronene (HFcHBC) ligand. We show that the resulting film is composed of rod-like single crystals with lengths up to ∼4 µm. The crystal structure is resolved by high-resolution transmission electron microscopy (HRTEM) and continuous rotation electron diffraction (cRED), indicating a wavy honeycomb lattice with AA-eclipsed stacking. Cu3(HFcHBC)2 is predicted to be metallic based on theoretical calculation, while the crystalline film sample with numerous grain boundaries apparently exhibits semiconducting behavior at the macroscopic scale, characterized by obvious thermally activated conductivity. Temperature-dependent electrical conductivity measurements on the isolated single-crystal devices indeed demonstrate the metallic nature of Cu3(HFcHBC)2, with a very weak thermally activated transport behavior and a room-temperature conductivity of 5.2 S cm-1. Furthermore, the 2D c-MOFs can be utilized as potential electrode materials for energy storage, which display decent capacity (163.3 F g-1) and excellent cyclability in an aqueous 5 M LiCl electrolyte. Our work demonstrates that wavy 2D c-MOF using contorted ligands are capable of intrinsic metallic transport, marking the emergence of new conductive MOFs for electronic and energy applications.

Thiol-ene-based microfluidic chips for glycopeptide enrichment and online digestion of inflammation-related proteins osteopontin and immunoglobulin G.

Proteins, and more specifically glycoproteins, have been widely used as biomarkers, e.g., to monitor disease states. Bottom-up approaches based on mass spectrometry (MS) are techniques commonly utilized in glycoproteomics, involving protein digestion and glycopeptide enrichment. Here, a dual function polymeric thiol-ene-based microfluidic chip (TE microchip) was applied for the analysis of the proteins osteopontin (OPN) and immunoglobulin G (IgG), which have important roles in autoimmune diseases, in inflammatory diseases, and in coronavirus disease 2019 (COVID-19). TE microchips with larger internal surface features immobilized with trypsin were successfully utilized for OPN digestion, providing rapid and efficient digestion with a residence time of a few seconds. Furthermore, TE microchips surface-modified with ascorbic acid linker (TEA microchip) have been successfully utilized for IgG glycopeptide enrichment. To illustrate the use of the chips for more complex samples, they were applied to enrich IgG glycopeptides from human serum samples with antibodies against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). The dual functional TE microchips could provide high throughput for online protein digestion and glycopeptide enrichment, showing great promise for future extended applications in proteomics and the study of related diseases.

Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique class of electronic materials. However, 2D c-MOFs with band gaps in the Vis-NIR and high charge carrier mobility are rare. Most of the reported conducting 2D c-MOFs are metallic (i.e. gapless), which largely limits their use in logic devices. Herein, we design a phenanthrotriphenylene-based, D2h -symmetric π-extended ligand (OHPTP), and synthesize the first rhombic 2D c-MOF single crystals (Cu2 (OHPTP)). The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique slipped AA stacking. The Cu2 (OHPTP) is a p-type semiconductor with an indirect band gap of ≈0.50 eV and exhibits high electrical conductivity of 0.10 S cm-1 and high charge carrier mobility of ≈10.0 cm2  V-1 s-1 . Theoretical calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOF.

Reference genes for the study of herbicide stress responses in Leptochloa chinensis (L.) Nees and estimation of ACCase expression in cyhalofop-butyl resistant populations.

Cyhalofop-butyl resistance in Leptochloa chinensis (L.) Nees is a threat to rice production. Qualitative changes to the acetyl-CoA carboxylase gene (ACCase) have been reported to induce cyhalofop-butyl resistance in some weed species, but the role of ACCase in cyhalofop-butyl resistance through quantitative changes remains uncertain. The accurate assessment of transcriptional changes in the functional genes associated with herbicide resistance in L. chinensis is challenging owing to the lack of available reference genes for expression normalization. Here, we selected nine candidate reference genes in L. chinensis and assessed their transcription stability in populations susceptible and resistant to cyhalofop-butyl. Transcription stability was compared under conditions of herbicide stress and control conditions using BestKeeper, NormFinder, and geNorm. Elongation factor 1 alpha, eukaryotic initiation factor 4A, and cap-binding protein CBP20 were the most stable reference genes under cyhalofop-butyl treatment. Transcription levels of ACCase were evaluated in seven resistant populations, one of which showed higher transcription than the susceptible population after 24 h cyhalofop-butyl treatment. However, the slight up-regulation of ACCase (approximately 2.0-fold) is unlikely to be responsible for the high resistance levels in these populations of L. chinensis.

Metal-Organic-Framework-Supported Molecular Electrocatalysis for the Oxygen Reduction Reaction.

Synthesizing molecule@support hybrids is appealing to improve molecular electrocatalysis. We report herein metal-organic framework (MOF)-supported Co porphyrins for the oxygen reduction reaction (ORR) with improved activity and selectivity. Co porphyrins can be grafted on MOF surfaces through ligand exchange. A variety of porphyrin@MOF hybrids were made using this method. Grafted Co porphyrins showed boosted ORR activity with large (>70 mV) anodic shift of the half-wave potential compared to ungrafted porphyrins. By using active MOFs for peroxide reduction, the number of electrons transferred per O2 increased from 2.65 to 3.70, showing significantly improved selectivity for the 4e ORR. It is demonstrated that H2 O2 generated from O2 reduction at Co porphyrins is further reduced at MOF surfaces, leading to improved 4e ORR. As a practical demonstration, these hybrids were used as air electrode catalysts in Zn-air batteries, which exhibited equal performance to that with Pt-based materials.

Krüppel-like factor 4 regulates stemness and mesenchymal properties of colorectal cancer stem cells through the TGF-ß1/Smad/snail pathway.

Krüppel-like factor 4 (KLF4) was closely associated with epithelial-mesenchymal transition and stemness in colorectal cancer stem cells (CSCs)-enriched spheroid cells. Nonetheless, the underlying molecular mechanism is unclear. This study showed that KLF4 overexpression was accompanied with stemness and mesenchymal features in Lgr5+ CD44+ EpCAM+ colorectal CSCs. KLF4 knockdown suppressed stemness, mesenchymal features and activation of the TGF-ß1 pathway, whereas enforced KLF4 overexpression activated TGF-ß1, phosphorylation of Smad 2/3 and Snail expression, and restored stemness and mesenchymal phenotypes. Furthermore, TGF-ß1 pathway inhibition invalidated KLF4-facilitated stemness and mesenchymal features without affecting KLF4 expression. The data from the current study are the first to demonstrate that KLF4 maintains stemness and mesenchymal properties through the TGF-ß1/Smad/Snail pathway in Lgr5+ CD44+ EpCAM+ colorectal CSCs.

Acid Catalysis in Confined Channels of Metal-Organic Frameworks: Boosting Orthoformate Hydrolysis in Basic Solutions.

Enzymes use a confined docking cavity and residual groups in the cavity to regulate substrate selectivity and catalytic activity. By mimicking enzymes, we herein report that metal-organic framework (MOF) KLASCC-1, with channels and inside-channel pyridyl groups, can promote orthoformate hydrolysis in basic solutions. By studying pH-dependent hydrolysis and using an analogue MOF that lacks inside-channel pyridyl groups, we proved protonated pyridyl groups as acid catalytic sites for orthoformate hydrolysis. By using MOFs with only open pyridyl groups, we demonstrated the necessity of the confined channels. X-ray diffraction structures of KLASCC-1 with encapsulated substrates confirmed that these channels can regulate activity and size selectivity. Recycling tests and crystallographic studies confirmed that KLASCC-1 kept its framework structure in catalysis. This work shows the potentials of using MOFs for host-guest catalysis that cannot be otherwise completed and underlines the advantages of using crystal engineering to identify active sites.

Intraoperative cell salvage is associated with reduced allogeneic blood requirements and has no significant impairment on coagulation function in patients undergoing cesarean delivery: a retrospective study.

OBJECTIVE: The aim of the study is to examine the association between Intraoperative cell salvage (ICS), allogeneic blood transfusion (ABT) and coagulation function in obstetrics. METHODS: A total of 486 pregnant women undergoing cesarean delivery, of whom 157 were enrolled in this retrospective study. Patients were divided into ICS group (n = 101, ICS used during operation) and control group (n = 56, ICS not used during operation). Clinical data, including plasma prothrombin time (PT), activated partial thromboplastin time (APTT), fibrinogen (Fib) and thrombin time (TT) levels, were collected from all patients preoperatively (within 12-24 h) and postoperatively (within 6-12 h) and analyzed by t test, two-way repeated-measures ANOVA and Spearman's correlation. RESULTS: The use of ICS is associated with lower requirement rate for ABT (P < .001), while the blood loss was similar between the two groups (P = .990). Mean volume of ICS transfusion was 432.65 mL. Compared to preoperative values, the postoperative PT and APTT levels were significantly increased, while Fib was decreased in the two groups (all P < .01). No significant difference in coagulation function was observed between groups in preoperative and postoperative phase (P > .05). Furthermore, PT, APTT and TT after surgery were not correlated with the transfused volume of salvaged blood (P > .05) while the levels of Fib were negatively correlated with the volume (P < .01). In addition, there were no transfusion reactions in both two groups. CONCLUSIONS: Intraoperative cell salvage is correlated with reduced allogeneic blood requirements but did not impair blood coagulation significantly in patients undergoing cesarean delivery.

Anthropometric indices to predict insulin resistance in women with polycystic ovary syndrome in China.

RESEARCH QUESTION: Which anthropometric index (waist-to-height ratio, waist circumference, waist-to-hip ratio and body mass index) is the best in predicting insulin resistance among Chinese women with polycystic ovary syndrome? DESIGN: A total of 1124 patients with polycystic ovary syndrome at the Reproductive Endocrinology Division of West China Second University Hospital of Sichuan University were enrolled in this study. Identification of insulin resistance was based on homeostasis model assessment of insulin resistance scores 2.77 or over. Receiver operator characteristic analysis was carried out using the four anthropometric indices as the continuous variables and insulin resistance as the categorical variable to obtain the areas under the curve. RESULT: The area under the curve for the waist-to-height ratio (0.748 ± 0.019) was greater than those for waist circumference (0.739 ± 0.019), body mass index (0.738 ± 0.017), and waist-to-hip ratio (0.659 ± 0.020) in the prediction of insulin resistance. The waist-to-height ratio also had the highest Youden indices compared with those of waist circumference, body mass index, and waist-to-hip ratio; the waist-to-height ratio cut-off was 0.49. CONCLUSION: The waist-to-height ratio with a cut-off of 0.49 was the most accurate anthropometric indicator for predicting insulin resistance among Chinese women with polycystic ovary syndrome.

Lead-Free Broadband Orange-Emitting Zero-Dimensional Hybrid (PMA)3InBr6 with Direct Band Gap.

Low-dimensional organic-inorganic hybrid metal halides have emerged as broadband light emitters for phosphor-converted white light-emitting diodes (WLEDs). Herein, we report a new zero-dimensional (0-D) lead-free metal halide (PMA)3InBr6 [PMA+: (C6H5CH2NH3)+] that crystallizes in the monoclinic system with P21/c space group. The structure consists of slightly distorted [InBr6]3- octahedra surrounded by organic PMA+ cations. The direct band gap characteristic of (PMA)3InBr6 was demonstrated by density functional theory calculation, and its relatively wide band gap of 3.78 eV was experimentally determined. Upon 365 nm ultraviolet light excitation, (PMA)3InBr6 exhibited strong broadband orange luminescence with a full-width at half-maximum of ∼132 nm resulting from self-trapped exciton emission, and the photoluminescence quantum yield was determined to be ∼35%. A WLED fabricated by combining the orange-emitting (PMA)3InBr6, a green phosphor Ba2SiO4:Eu2+, and a blue phosphor BaMgAl10O17:Eu2+ exhibited a high color-rendering index of 87.0. Our findings indicate that the organic-inorganic hybrid (PMA)3InBr6 may have potential for luminescence-based applications.

Hybrid Metal Halides with Multiple Photoluminescence Centers.

Very little is known about the realm of solid-state metal halide compounds comprising two or more halometalate anions. Such compounds would be of great interest if their optical and electronic properties could be rationally designed. Herein, we report a new example of metal halide cluster-assembled compound (C9 NH20 )9 [Pb3 Br11 ](MnBr4 )2 , featuring distinctly different anionic polyhedra, namely, a rare lead halide cluster [Pb3 Br11 ]5- and [MnBr4 ]2- . In accordance with its multinary zero-dimensional (0D) structure, this compound is found to contain two distinct emission centers, 565 nm and 528 nm, resulting from the formation of self-trapped excitons and 4 T1 -6 A1 transition of Mn2+ ions, respectively. Based on the high durability of (C9 NH20 )9 [Pb3 Br11 ](MnBr4 )2 upon light and heat, as well as high photoluminescence quantum yield (PLQY) of 49.8 % under 450 nm blue light excitation, white light-emitting diodes (WLEDs) are fabricated, showcasing its potential in backlight application.

Long noncoding RNA ROR promotes breast cancer by regulating the TGF-ß pathway.

BACKGROUND: Breast cancer is the leading cause of oncological mortality among women. Efficient detection of cancer cells in an early stage and potent therapeutic agents targeting metastatic tumors are highly needed to improve survival rates. Emerging evidence indicates that lncRNAs (long noncoding RNAs) are critical regulators of fundamental cellular processes in a variety of tumors including breast cancer. The functional details of these regulatory elements, however, remain largely unexplored. METHODS: In this study, lncRNA ROR (linc-ROR) was examined by real-time PCR in different breast cancer cell lines and breast tumor tissues/non-tumor tissues were collected from both breast cancer patients and healthy controls. Linc-ROR was knockdown in breast cancer cell lines and the effects on cell proliferation, migration and invasion were tested both in vitro and in vivo tumor model. Effects of linc-ROR knockdown on TGF-ß signaling pathway were investigated by Western blot. RESULTS: Our studies have suggested that linc-ROR, a critical factor for embryonic stem cell maintenance, probably acts as an oncogenic factor in breast cancer cells, causing poor prognostic outcomes. Overexpression of linc-ROR seems to be responsible for promoting proliferation and invasion of cancer cells as well as tumor growth in nude mice. The regulatory action of linc-ROR can affect the activity of the TGF-ß signaling pathway, which has been proven critical for mammary development and breast cancer. CONCLUSIONS: The results have highlighted the potential importance of linc-ROR in the progression of advanced breast cancer, and thus will stimulate efforts in the development of novel diagnostic and therapeutic strategies.

Topological Self-Assembly of Highly Symmetric Lanthanide Clusters: A Magnetic Study of Exchange-Coupling "Fingerprints" in Giant Gadolinium(III) Cages.

The creation of a perfect hollow nanoscopic sphere of metal centers is clearly an unrealizable synthetic challenge. It is, however, an inspirational challenge from the viewpoint of chemical architecture and also as finite molecular species may provide unique microscopic insight into the origin and onset of phenomena such as topological spin-frustration effects found in infinite 2D and 3D systems. Herein, we report a series of high-symmetry gadolinium(III) (S = 7/2) polyhedra, Gd20, Gd32, Gd50, and Gd60, to test an approach based on assembling polymetallic fragments that contain different polygons. Structural analysis reveals that the Gd20 cage resembles a dodecahedron; the vertices of the Gd32 polyhedron exactly reveal symmetry Oh; Gd50 displays an unprecedented polyhedron in which an icosidodecahedron Gd30 core is encapsulated by an outer Gd20 dodecahedral shell with approximate Ih symmetry; and the Gd60 shows a truncated octahedron geometry. Experimental and theoretical magnetic studies show that this series produces the expected antiferromagnetic interaction that can be modeled based on classical spins at the Gd sites. From the magnetization analyses, we can roughly correlate the derivative bands to the Gd-O-Gd angles. Such a magneto-structural correlation may be used as "fingerprints" to identify these cages.

Metallacrowns as Templates for Diabolo-like {LnCu8 } Complexes with Nearly Perfect Square Antiprismatic Geometry.

A series of diabolo-like nonanuclear {LnIII CuII8 } (Ln=Tb, Dy, Ho, Er, Tm, Yb, and Y) clusters were prepared in which the LnIII ion is capped by two 8-MC-4 metallacrown ligands to form a nearly ideal square antiprismatic (SAP) coordination geometry with D4d symmetry. Despite the lack of crystallographic symmetry, these molecules engender the lanthanide ions with highly axial mJ states. The axial/equatorial nature of the crystal field in environments close to ideal SAP geometry is very subtle and influenced by the nature of the ligand lone pairs. Slow magnetic relaxation behaviour was observed for the DyIII , ErIII , TmIII , and YbIII analogues, and the obtained effective energy barriers are not consistent with excitations on the LnIII ion, suggesting a more nuanced situation.

Filling the Missing Links of M3n Prototype 3d-4f and 4f Cyclic Coordination Cages: Syntheses, Structures, and Magnetic Properties of the Ni10Ln5 and the Er3n Wheels.

In this paper, we proposed a number rule for 3d-4f and 4f cyclic coordination cages (CCCs); that is, CCCs consisting of vertex-sharing M4(µ3-OH)4 (M = 3d transition metal or 4f lanthanide ions) units should have 3 × n metal centers (abbreviated M3n), where n represents the number of the M4(µ3-OH)4 subunits. Under this number rule we reasoned that some species of CCCs, for example, the pentadecanuclear 3d-4f wheel and the pure 4f wheels with 9 or 18 centers, should practically have existed. However, there are no such complexes reported in the literature. To realize such CCCs we employed a mixed-ligand approach, that is, to simultaneously use the primary and the ancillary ligands for syntheses. This approach successfully leads to the isolation of two families of CCCs, namely, the Ni10Ln5 (Ln = Gd and Y) mixed-metal wheels and the Er3n (n = 4, 5, and 6) pure 4f metal wheels. These two families of CCCs unambiguously fill the missing links of the M3n prototype CCCs. Moreover, dominated ferromagnetic interaction indicates high ground-spin state for the Gd5Ni10 wheel. The ferromagnetic interactions between the nickel centers are verified using the diamagnetic Y(III) analogue, which reveals an averaged coupling constant (J = 2.7 cm-1), while accompanied by a large negative zero-field splitting parameter (D = -6.1 cm-1) for single Ni(II) ions. Interestingly, the Y(III)-diluted Er12 wheel shows slow magnetic relaxation behavior, presumably indicating the magnetically anisotropic nature of the erbium(III) ions.

[Pregnant Outcomes of Multiparae in Women with Advanced Age (≥35 years)after the 2008 Wenchuan Earthquake].

OBJECTIVE: To evaluate pregnancy outcomes of multiparae in women with advanced age (≥35 yr.) after the 2008 Wenchuan earthquake. METHODS: Clinical data of 542 pregnant women with prenatal care in Wenchuan during 20082013 were reviewed,comparing preconception conditions,pregnant rates,pregnant complications,and perinatal outcomes between those younger ( n=176) and older ( n=366) than 35 years. RESULTS: In the 542 women,622 conceptions were reported,with 517 deliveries and 522 live births. The women with advanced age had lower cumulative pregnancy rate (twoyear),higher incidence of hypertensive disorders of pregnancy,gestational diabetes,multiple pregnancy,fetal distress,low birth weight and birth defects than their younger counterparts. The younger women also had higher term live birth rate and lower miscarriage rate. But the differences showed no statistical significance. CONCLUSION: Prenatal care brings similar pregnant outcomes to multiparae in women with advance aged and younger aged.

Hydrophobicity-Driven Self-Assembly of an Eighteen-Membered Honeycomb Lattice with Almost Classical Spins.

The design and synthesis of model compounds that do not exist naturally is one of the important targets in modern coordination chemistry. Herein, an eighteen-membered honeycomb structure with equal numbers of MnII (s=5/2) and GdIII (s=7/2) metal centers has been prepared, for the first time, by using a hydrophobic force-directed self-assembling process. Due to the weakly coupled GdIII pairs, the magnetic properties are mainly determined by eight-membered chains in the experimentally considered temperature range. These [Mn4 Gd4 ] "finite-size" chains, albeit with large Hilbert space, can be fully resolved by the high-temperature series expansion and the powerful finite-temperature Lanczos method, which reveal that the exchange-couplings between the metal centers are antiferromagnetic and consistent with the magnetization measurement. Interestingly, from the surface-engineering point of view, the [Mn4 Gd4 ] chains are "precisely" assembled into a 2D honeycomb pattern, which is potentially desirable in the design of weakly coupled qubits.