High-Nuclear Co-Added Polyoxometalate-Based Chain: Electrocatalytic Oxygen Production.

A high-nuclear Co-added polyoxometalate (CoAP) was synthesized via a hydrothermal reaction: H14.5K9Na7.5-{[Co8(µ2-OH)(µ3-OH)2(H2O)2(Co(H2O)GeW6O26)(B-α-GeW9O34)2][BO(OH)2][Co12(µ2-OH)(µ3-OH)5(H2O)3(Co(H2O)GeW6O26)(GeW6O26)(B-α-GeW9O34)]}·46H2O (1). The polyoxoanion of 1 contains a large Co20 cluster gathered by lacunary GeW6O26 and GeW9O34 subunits. 1 represents a one-dimensional (1D) chain formed by adjacent polyoxoanions coupling through a CoO6 double bridge, showing the first example of a high-nuclear CoAP-based inorganic chain. 1 served as an efficient electrocatalyst in oxygen evolution reactions (OERs).

Porphyrin-Sensitizers and Anthracene-Annihilators Built in Isostructural Frameworks for Investigating Triplet-Triplet Annihilation Upconversion.

In this study, four isostructural pillar-layered frameworks were constructed using a porphyrin layer and an anthracene pillar, which served as the sensitizer and annihilator, respectively, in the triplet-triplet annihilation upconversion (TTA-UC) system. Framework 1 demonstrated the highest upconversion quantum yield of 1.01%. Additionally, 1 and 2 also exhibited down-conversion fluorescence resulting from the porphyrin component. A twist intramolecular charge transfer (TICT) state was observed in the bianthracene chromophore of 2, resulting in transient rotation of two anthracene rings and red-shifted emission. Both computational studies and experiments confirmed the transition from a locally excited state to a TICT state upon the inclusion of polar guest molecules into the framework.

Polypyridyl Ru(II) or cyclometalated Ir(III) functionalized architectures for photocatalysis.

The chemistry of polypyridyl Ru(II) and cyclometalated Ir(III) derivatives provides long-lasting interest to researchers due to the inherent advantage of their triplet states in a variety of photoactivities. The introduction of Ru(N^N)3 and Ir(C^N)2(X^N) modules into well-defined architectures extends the research areas of both photoactive metal complexes and network chemistry, generating a lot of new opportunities with interesting structural aesthetics and profound functional possibilities. The rapid development of research in integrating Ru(II) or Ir(III) metallotecons into the architectures has been apparent in recent years which makes this a fascinating subject for reviewing. This review focuses on the design and syntheses of Ru(N^N)3 and Ir(C^N)2(X^N) functionalized architectures of metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), metallasupramolecules, organic supramolecules and supramolecular organic frameworks (SOFs). Furthermore, the photocatalytic applications including the hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), photocatalytic oxidation and photoredox catalysis of organic transformation are also presented.

Organocatalytic Asymmetric Dearomatizing Hetero-Diels-Alder Reaction of Nonactivated Arenes.

Nonactivated arenes, such as benzene derivatives, are chemically inert due to their intrinsic aromaticity and low polarity. The catalytic asymmetric dearomatization (CADA, coined by You and co-workers) of the nonactivated arenes represents a formidable challenge. We herein demonstrated an organocatalytic asymmetric dearomatizing hetero-Diels-Alder reaction of benzene derivatives. The tunable regioselectivity of this strategy allowed delivery of a diversity of stereochemically complex polycyclic compounds and oxahelicenes with excellent stereoselectivity. The high complexity and three-dimensionality of the products are crucial for their potential applications in materials science and drug discovery. Mechanistic studies suggested that this reaction proceeds through a chiral tetra-substituted vinylidene ortho-quinone methide (VQM) intermediate, which is extremely active to overcome the loss of aromaticity of benzene derivatives with concomitant chirality transfer.

Enhanced Faraday effects of magneto-plasmonic crystals with plasmonic hexagonal hole arrays.

Magneto-optical (MO) properties of the bilayed Au/BIG and trilayered Au/BIG/Au magneto-plasmonic crystals (MPCs) were analyzed by the finite-difference time-domain method. In contrast to the low deflection angle and transmission of the smooth thin film, all the heterostructures with perforated holes in the top Au film displayed a similar trend with two strong resonant bands in Faraday rotation and transmittance in the near infrared wavelength range. The bands and electric distribution relative to the component and hole structure were revealed. The MPC with plasmonic hexagonal holes was found to own superior Faraday effects with distinctive anisotropy. The evolution of the resonant bands with the size and period of hexagonal holes, the thickness of different layers, and the incident light polarization was illustrated. The Faraday rotation of the optimized bilayed and trilayered hexagonal MPCs was improved 15.3 and 17.5 times, and the transmittance was enhanced 12.1 and 11.1 folds respectively at the resonant wavelength in comparison to the continuous Au/BIG film, indicating that the systems might find potential application in MO devices.

Lanthanide-Anderson Polyoxometalates Frameworks: Efficient Sulfide Photooxidation.

Three polyoxometalate-based metal-organic frameworks were synthesized by the thermal reaction of pyridyl-Anderson polyoxometalate linker and lanthanide ions. With the help of [Ru(bpy)3]2+ photosensitizer, these frameworks exhibited excellent photocatalytic sulfide oxidation performance with sulfoxide selectivity. The reactive oxygen species as well as the photooxidation mechanism were also explored.

An Isolable Vinylidene ortho-Quinone Methide: Synthesis, Structure and Reactivity.

Commonly, an elusive intermediate is generated from a precursor and then trapped and consumed in a reaction. Vinylidene ortho-quinone methides (VQMs) have been demonstrated as transient axially chiral intermediates in asymmetric catalysis due to their orthogonal π-bonds forming an allene motif. The current understanding of VQMs is primarily based on time-resolved absorption, trapping experiments and computational studies. Herein, we report the first isolation and comprehensive characterization of a VQM, including crystallographic analysis. The disturbed aromaticity of the VQM led to its high reactivity as an electrophile or a 4π-component capable of asymmetric dearomatization of an electron-deficient phenyl group. Notably, the VQM could be isolated in enantiomerically enriched form, and the subsequent transformation was stereospecific, indicating that the generation of the VQM was involved in the enantiodetermining step. This study paves the way for the direct application of VQMs as starting materials.

Primary intraspinal benign tumors treated surgically: an analysis from China.

PURPOSE: The purpose of this study was to review the clinical features in a cohort of Chinese patients with primary intraspinal benign tumors. METHODS: This retrospective study included a consecutive series of patients with intraspinal benign lesions who received surgery between January 2014 and October 2018 at our hospital. We collected each patient's clinical data, including age, gender, presenting symptoms, the spinal level (cervical, thoracic, lumbar, or sacral), and location (intramedullary or extramedullary) of the tumor. RESULTS: A total of 66 patients were included in this study, of whom 24 were men and 42 (63.6%) were women. The mean age was 52.5 years (range, 21-76 years). The most common symptom was sensory deficits. The most common tumor type, found in 56.1% patients, was schwannoma, followed by meningioma in 33.3% patients. The commonly performed surgery included decompression of spinal canal and excision of spinal lesions. CONCLUSION: Primary intraspinal benign tumors occur in elderly and female population and at the thoracic region. Schwannoma and meningioma are the two with higher incidence. The surgical outcome in terms of tumor excision and functional recovery is good.

Organocatalytic Enantioselective Construction of Chiral Azepine Skeleton Bearing Multiple-Stereogenic Elements.

Enantioselective construction of molecules bearing multiple stereogenic elements is increasingly related to the synthesis of enantiopure natural products, pharmaceuticals, and functional materials. However, atom-economical and enantioselective approaches to install multiple stereogenic elements in a small molecular template by limited chemical transformation remain challenging. We describe an organocatalytic enantioselective method for the preparation of polychiral molecules bearing four types of stereogenic elements in fused azepines via vinylidene ortho-quinone methide (VQM)-mediated intramolecular electrophilic aromatic substitution. This method was proved robust with a wide range of substrate scope (46-92 % yield), with excellent diastereoselectivity (>20:1 dr) and enantioselectivity achieved (up to 97 % ee). Optical properties and Ru3+ -induced fluorescence responses of these compounds suggest their potential applications in optoelectronic materials and heavy metal ion detection.

Safe range of shortening the middle thoracic spine, an experimental study in canine.

PURPOSE: To determine the safe range of shortening the spinal column at middle thoracic spine and to observe the changes in blood-spinal cord barrier (BSCB), microglia/macrophage activation and inducible nitric oxide synthase (iNOS) activity after shortening-induced spinal cord injury. METHODS: Dogs were allocated to four groups. Group A (control) underwent laminectomy of T7 without shortening the spinal column. Groups B, C and D had 1/3, 1/2, and 2/3 of T7 resected, respectively, followed by spinal shortening. Somatosensory evoked potential (SSEP) and hind-limb function were recorded periodically for 14 days after operation. Spinal cord blood flow (SCBF) and BSCB were detected at the acute phase of shortening. Microglia/macrophage reactions and iNOS activity were observed by immunohistochemistry. RESULTS: Shortening of 1/3 of a vertebral height caused no significant changes in SSEP and hind-limb function after operation, whereas shortening of 1/2 of the height caused SSEP abnormality and paraparesis, and severe neurologic deficit of hind-limb was observed when the shortening reached 2/3 of the height. SCBF increased temporarily and showed a trend of recovery when the shortening was within 1/2 of a vertebral segment height. When it reached 1/2 or 2/3 of the height, SCBF at 6 h post-operation was 86.33% or 74.95% of the baseline, and an increasing BSCB permeability was observed. In the subsequent 7 days, obvious activation of macrophage and increased number of iNOS-positive cells were observed. CONCLUSION: It is safe to shorten the spinal cord within 1/3 of a vertebral height in middle thoracic spine under two-segment laminectomy in canine. The BSCB disruption, macrophage activation, and increased iNOS activity were observed in the acute phase of the injury. These slides can be retrieved under Electronic Supplementary Material.

Suite of Organoplatinum(II) Triangular Metallaprism: Aggregation-Induced Emission and Coordination Sequence Induced Emission Tuning.

A series of triangular metallaprisms with a kinetically inert Pt-N bond have been synthesized from the stepwise assembly of a Pt-corner, linear linker 4,4'-bipy (4,4'-bipy = 4,4'-bipyridine) and triangular ligand [tpb or tpt, tpb = tris(4-pyridyl)benzene, tpt = tris(4-pyridyl)triazine]. The use of an unsymmetrical [Pt(HL)]-corner (H2L = 2,6-diphenylpyridine) leads to novel isostructural products. Phenyl rotation at the metal-corners endows these complexes with good aggregation-induced emission (AIE) function, with varied activities across the isostructural complexes. The coordination sequence of electron-deficient ligand tpt also imparts significant influence on the complex emission. These organoplatinum triangular metallaprisms thus provide a good model to study the influence of building blocks and coordination sequence on the luminescence of supramolecules.

Organocatalytic Enantioselective Selenosulfonylation of a C-C Double Bond To Form Two Stereogenic Centers in an Aqueous Medium.

Organocatalytic selenosulfonylation of the C-C double bond of α,ß-unsaturated ketones to construct two contiguous stereogenic centers in an aqueous medium was described. A series of α-selenyl and ß-sulfonyl ketones with various functional groups were synthesized in good yields and enantioselectivities with saturated NaCl solution as the solvent. In addition, this protocol had been successfully scaled up to a decagram scale via a simple workup procedure.

Metal-free difunctionalization of alkynes to access tetrasubstituted olefins through spontaneous selenosulfonylation of vinylidene ortho-quinone methide (VQM).

A metal-free difunctionalization of alkynes to access tetrasubstituted olefins through spontaneous selenosulfonylation of vinylidene ortho-quinone methide (VQM) was described herein. The reaction was conducted under mild conditions without any catalysts or additives. Preliminary mechanism studies revealed that the formation of VQM was the key for this alkyne di-functionalization reaction. The reaction could be applied in the enantioselective asymmetric synthesis of axially chiral styrene. Furthermore, the selenosulfonylation adducts can be transformed into useful naphtho[2,1-b]furan and benzofuran scaffolds.

Iridium-mediated regioselective B-H/C-H activation of carborane cage: a facile synthetic route to metallacycles with a carborane backbone.

One-pot reactions of carborane carboxylic acids (L), [Cp*IrCl2]2, and silver salt are reported, which lead to regioselective B-H or C-H bond activation at ambient temperature in good yields. This process is demonstrated for three carborane (o-, m-, p-) dicarboxylates, and metal-mediated B-H functionalization of a p-carborane derivative is accomplished for the first time. Two metal-induced self-assembly routes to tetra-nuclear metallacycles 3 and 5 were performed through B(4, 7)/H and B(2, 10)/H activation, respectively, and the two metallacycles were found to be stable and to exist in solution as discrete complexes. Different activation modes in the carborane cage were ascribed to the characteristic structure of the products and the electronic density differences. The analogous reaction of o-carborane monocarboxylate with the same metal precursor gave the C-H activation complex 6, indicating that the B-H bond is more stable than the C-H bond in this carborane cage. The selective activation was confirmed by DFT calculation results. In this study, a facile and efficient synthetic route has been developed through specific B-H bond activation to construct carborane-based metallacycles that are unavailable by conventional methods.

Neuroprotective effects of ginsenoside Rg1 on oxygen-glucose deprivation reperfusion in PC12 cells.

The present study was aimed to investigate the protective effects of ginsenoside Rg1 (GRg1), an important component of ginseng, in oxygen-glucose deprivation/reperfusion (OGDR) and to elucidate the related mechanisms. PC12 cells were used as the model of OGDR. GRg1 administration was started 12 h before OGD and lasted for 12 h. After OGD, the cells were incubated in drug-free and full culture medium under normoxic condition for 24 h. Cell viability was then measured using MTT assay. Cell morphology was studied under a microscope. The expressions of survivin, caspase-3 and Terminal dUTP nick-end labeling (TUNEL) were measured by immunocytology. Results showed that pretreatment with GRg1 significantly increased the viability and survivin expression, and decreased the expressions of caspase-3 and TUNEL in a dose-dependent manner. In addition, it dramatically increased the number of cells and improved the cellular morphology. These results demonstrate the effect of GRg1 in preventing OGDR-induced PC12 cell apoptosis and partly reveal the mechanisms of the protective effect. It is suggested that GRg1 has potential beneficial effects in ischemic diseases.

Self-assembly of molecular Borromean rings from bimetallic coordination rectangles.

In contrast to conventional stepwise synthesis of molecular Borromean rings, a self-assembly synthetic method which proceeds without the aid of a template has been developed. In the formation of molecular rectangles, by adjustment of the long-arm length of the rectangles, a series of size-dependent Borromean-link frameworks were constructed. Both the shortest length of two arms and the relative proportion of the length of the long arm to that of the short arm play a key role in the formation of Borromean rings. DFT calculations were used to provide theoretical support for the formation of discrete interlocked frameworks.

Cp*Rh-based heterometallic metallarectangles: size-dependent Borromean link structures and catalytic acyl transfer.

A series of Cp*Rh-based functional metallarectangles have been synthesized from metallaligands. Enlargement of one linker leads to the isolation of two novel Borromean link architectures. All these complexes are intact in solution, as evident from ESI-MS spectroscopic analysis. Arising from the combination of open Cu centers and favorable cavity space, {(Cp*Rh)4(bpe)2[Cu(opba)·2MeOH]2}4(OTf)·6MeOH shows extraordinary catalytic abilities with high efficiency and wide substrate selectivity in the acyl-transfer reaction.

A novel primary culture method for rat choroidal epithelial cells.

OBJECTIVE: To establish a method for the culture of primary choroidal epithelial cells. METHODS: This descriptive experimental study was carried out in Xi`an Jiaotong University, Xi`an, China from September 2009 to August 2012. Choroidal epithelial cells were isolated from the choroid plexus tissues of the lateral ventricles from neonatal rats (n=36). The tissues were dissociated into small cell aggregates by a mechanical method, and cultured on plastic culture dishes containing Dulbecco`s modified Eagle`s medium with 10% fetal bovine serum and 10 ng/ml epidermal growth factor at 37 degrees C in an incubator with 5% humidified carbon dioxide. The cultured cells were examined by phase contrast microscope, electron microscopy, and immunocytochemistry. RESULTS: The cells showed typical morphologic characteristics of epithelial phenotypes with a cobblestone appearance in monolayer 7-9 days post-seeding. The electron microscopy spotted typical choroidal epithelial cells with microvilli on the cytomembrane, organelles in the cytoplasm, and tight junctions welding 2 adjacent cells. They were positive against anti-transthyretin immunostaining. CONCLUSION: This culture technique, which does not require complex equipment and operation skills, might be a simple and efficient method for obtaining choroidal epithelial cells in sufficient number and purity from mixed primary cultures of rat tissue.

Anderson-type polyoxometalates for catalytic applications.

Anderson-type polyoxometalates have exhibited remarkable catalytic capabilities in a wide range of reactions. This discourse delves into the distinct categories of Anderson POMs and their respective catalytic reactions, which are examined in separate segments. These encompass the straightforward {XMo6} POMs, the organic grafting {XMo6} POMs, and the integration of POMs into POM cluster organic frameworks. It is important to highlight that specific catalytic functionalities can solely be accomplished via the utilization of Anderson-type POMs, thus emphasizing their indispensable role in future explorations.

Organocatalytic asymmetric deoxygenation of sulfones to access chiral sulfinyl compounds.

Over the past decades, many efficient methodologies have been developed that allow for the enantioselective synthesis of chiral sulfinyl compounds. However, the enantioselective deoxygenation of hexavalent sulfones for the formation of chiral sulfinyl compounds still remains one of the major challenges in the fields of asymmetric synthesis and organosulfur chemistry. Here we have demonstrated that a synergistic combination of organocatalysis and the incorporation of a cyano group into the sulfone generates a chiral sulfinic species as an active intermediate. A wide range of chiral sulfinates with high enantioselectivities could then be acquired using alcohols as nucleophiles, and the subsequent transformations allowed the collective preparation of a variety of chiral sulfinyl compounds. Density functional theory calculations revealed that the catalytic cycle involves a quinuclidine-assisted stepwise 1,2-cyano group transfer, base-assisted intermolecular substitution with alcohol and regeneration of the active catalyst. The enantioselectivity was determined by the cyano migration step.