METTL14-mediated upregulation of lncRNA HOTAIR represses PP1α expression by promoting H3K4me1 demethylation in oxycodone-treated mice.

N6-methyladenosine (m6A) methylation is a vital epigenetic mechanism associated with drug addiction. However, the relationship between m6A modification and oxycodone rewarding is less well explored. Based on an open field test, the present study evaluated oxycodone rewarding using chromatin immunoprecipitation PCR, immunofluorescence, and RNA sequencing.

Aggregation-Induced Emission Phosphorescence Featured Au-Ag Coordination Polymer with a Diphosphine N-Heterocyclic Carbene Ligand for Highly Sensitive Detection of Cr(VI).

Luminescent materials with aggregation-induced emission (AIE) characteristics have been recognized as highly selective and sensitive probes for the detection of toxic metal ions in recent years. In this paper, a Au-Ag cluster-based coordination polymer [AuAg()(CN)(HO)] [, = 1,3-bis((diphenylphosphanyl)methyl)-4,5-dihydro-imidazolylidene] was prepared by in situ generation of the diphosphine N-heterocyclic carbene (PCP)-type ligand in the presence of the corresponding metal salts. Compound exhibited 530 nm phosphorescence under 380 nm excitation with a QY of 6.

A Phosphorescent P/N/S Hybrid Ligand Stabilized AuCu Complex Selectively Senses Ammonia and Amines.

Reaction of a P/N/S hybrid ligand dpppyatc (N,N-bis((diphenylphosphaneyl)methyl)-N-(pyridin-2-yl)-amino-thiocarbamide) with Au(tht)Cl (tht=tetrahydrothiophene) and [Cu(MeCN)]BF afforded cluster complex [AuCu(dpppyatc)](BF)Cl (1). Upon excitation at 480 nm, 1 emitted orange phosphorescence at 646 nm, which was red-shifted to ~698 nm selectively in the presence of ammonia or amine vapor. This chromic photoluminescent response toward ammonia was sensitive and reversible.

Modulating β-Keto-enamine-Based Covalent Organic Frameworks for Photocatalytic Atom-Transfer Radical Addition Reaction.

The atom-transfer radical addition (ATRA) reaction simultaneously forges carbon-carbon and carbon-halogen bonds. However, frequently-used photosensitizers such as precious transition metal complexes, or organic dyes have limitations in terms of their potential toxicity and recyclability. Three β-ketoenamine-linked covalent organic frameworks (COFs) from 1,3,5-triformylphloroglucinol and 1,4-phenylenediamines with variable transient photocurrent and photocatalytic activity have been prepared.

Schiff-base Polymer Immobilized Ruthenium for Efficient Catalytic Cross-coupling of Secondary Alcohols with 2-amino- and γ-aminobenzyl Alcohols to Give Quinolines and Pyridines.

A Schiff-base porous polymer has been impregnated with ruthenium trichloride for acceptor-free dehydrogenation coupling (ADC) of secondary alcohols with γ-amino- and 2-aminobenzyl alcohols to give pyridines and quinolines. This heterogenous catalyst exhibited high catalytic efficiency over repeated cycles with wide functional group tolerance.

A Multiple Stimuli-Responsive Ag/P/S Complex Showing Solvochromic and Mechanochromic Photoluminescence.

The reaction of CFCOOAg, 3-bdppmapy (,-bis(diphenylphosphanylmethyl)-3-aminopyridine) and HTZ (1,2,4-triazole-3-thiol) in CHCl/MeOH resulted in a dinuclear Ag/P/S complex [Ag(TZ)(3-bdppmapy)]·Sol (·Sol). Crystals of ·Sol converted to ·2MeOH in air at room temperature and further to under vacuum upon heating. The solid-state, room-temperature photoluminescent emission of ·Sol (510 nm) shifted to 494 nm (·2MeOH) and 486 nm ().

Heteroleptic copper(I) complexes [Cu(dmp)(N^P)]BF for photoinduced atom-transfer radical addition reactions.

Earth-abundant copper(I) coordination complexes of an imine-phosphine and a diimine have been developed as visible-light photocatalysts. Reaction of [Cu(MeCN)]BF with hetero-bidentate phosphinopyrazole (phpz) ligand RRCHNPPh (R = R = H (1a); R = H, R = Me (1b); R = H, R = Ph (1c); R = R = Me (1d)) and 2,9-dimethyl-1,10-phenanthroline (dmp) gave four heteroleptic bis-chelate Cu(I) complexes [Cu(dmp)(RRCHNPPh)]BF (R = R = H (2a); R = H, R = Me (2b); R = H, R = Ph (2c); R = R = Me (2d)) with distorted tetrahedral geometries. Complexes 2a-2d exhibited broad absorption in the visible spectrum and could facilitate photochemical intermolecular atom-transfer radical addition reactions of CBr, or CClBr, CHI to styrenes in yields up to 91% and with a broad substrate scope.

One-Dimensional Heterobimetallic Au/Ag Coordination Polymer Showing a Selective, Reversible, and Visible Vapor-Chromic Photoluminescent Response toward Methanol.

A heterobimetallic coordination polymer [Au(dppmt)(AgCl)] () incorporating an generated P-S ligand (dppmtH) was synthesized from the solvothermal reaction of Au(tht)Cl, AgCl, and dpppyatc in CHCN/CHCl (dppmtH = (diphenylphosphino)methanethiol, tht = tetrahydrothiophene, dpppyatc = ,-bis((diphenylphosphaneyl)methyl)--(pyridin-2-yl)-amino-thiocarbamide). The structure of contains a one-dimensional helical Au-Au chain in which the unique [AuAgS] cluster units are connected by [Au(dppmt)] dimers. Upon excitation at 343 nm, exhibited cyan (495 nm) phosphorescent emission at quantum yield (QY) = 22.

A Novel Photoluminescent Ag/Cu Cluster Exhibits a Chromic Photoluminescence Response towards Volatile Organic Vapors.

A new Ag/Cu bimetallic cluster [AgCu(bdppthi)(C≡CPh)(EtOH)](ClO) (, bdppthi = ,-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) exhibited strong phosphorescent (PL) emission at 644 nm upon excitation at 400 nm. Removal of the coordinated EtOH molecules in resulted in derivative , which exhibited significant red-shifted emission at 678 nm. The structure and PL of was restored on exposure to EtOH vapor.

Covalent Grafting of a Nickel Thiolate Catalyst onto Covalent Organic Frameworks for Increased Photocatalytic Activity.

Covalent organic frameworks (COFs) have recently emerged as prospective photoactive materials with noble Pt as a cocatalyst for photocatalytic hydrogen evolution. In this work, a series of SH-group-functionalized covalent organic frameworks, TpPa-1-SH-X, is prepared by reaction of p-phenylenediamine (Pa) and 1,3,5-triformylphloroglucinol (Tp) with p-NH C H SH as a modulating agent. The reaction of TpPa-1-SH-X with Ni acetylacetonate Ni(acac) gave nickel thiolate-immobilized TpPa-1 (TpPa-1-SNi-X).

Visible-light-driven C(sp)-H arylation of phenols with arylbromides enabled by electron donor-acceptor excitation.

We have developed a catalyst-free visible-light-driven C(sp)-H arylation of unprotected phenols with arylbromides to give 2-arylated phenols. This reaction proceeds through the excitation of an electron donor-acceptor complex between a phenolate and an arylbromide, electron transfer, and debrominative C(sp)-C(sp) coupling.

Nickel-Catalyzed Etherification of Phenols and Aryl Halides through Visible-Light-Induced Energy Transfer.

Notwithstanding some progress in nickel-catalyzed etherification of alkanols and arylhalides, the ability of such a Ni-catalyzed transformation employing phenols to diaryl ethers is unsuccessful due to phenolates with much lower reduction potentials, which suppress the oxidation of nickel(II) intermediates into requisite Ni(III) species. We herein report visible-light-initiated, nickel-catalyzed O-arylation of phenols with arylhalides using -BuNH(-Pr) as the base and thioxanthen-9-one as the photosensitizer under visible light. This photocoupling exhibits a broad substrate scope.

A Photoluminescent Ag Cu Cluster Stablized by a PNNP Ligand and Phenylacetylides Selectively and Reversibly Senses Ammonia in Air and Water.

A photoluminescent bimetallic cluster [Ag Cu (bdppthi) (C≡CPh) (MeOH) (H O)](ClO ) (1, bdppthi=N,N'-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH in air or water. The sensing of NH was rapid and recoverable, with detection limits of 53 ppm (v/v) in N and 21 μmol/L (0.

A photoluminescent Au(I)/Ag(I)/PNN coordination complex for relatively rapid and reversible alcohol sensing.

Trinuclear complex [Au2Ag(dppmaphen)2(CN)2]PF6 photoluminesces on exposure to low molecular weight alcohols. This emission is likely due to C-Hπ interactions between the analyte and -PPh2 group, that inhibits non-radiative relaxation of the photoexcited state. Photoluminescene was quenched by removing the analyte under a stream of N2 or replacing it with H2O.

Photocatalyst- and Transition-Metal-Free Visible-Light-Promoted Intramolecular C(sp)-S Formation.

A photocatalyst- and transition-metal-free visible-light-induced cyclization of -halothiobenzanilides has been developed. Upon irradiation with visible light, substrates undergo dehalogenative cyclization to 2-aryl benzothiazoles with high efficiency and selectivity. This photocyclization exhibits a high tolerance to various functional groups, is applicable for the synthesis of 2-alkyl benzothiazoles, and is easy to set up for gram-scale reaction.

Visible-Light-Induced Nickel-Catalyzed P(O)-C(sp) Coupling Using Thioxanthen-9-one as a Photoredox Catalysis.

An efficient method has been developed for photocatalytic P(O)-C(sp) coupling of (hetero)aryl halides with H-phosphine oxides or H-phosphites under the irradiation of visible light or sunlight. The thioxanthen-9-one/nickel dual catalysis mediates this phosphonylation to give arylphosphine oxides and arylphosphonates in moderate to excellent yields. This transformation is widely tolerant to a range of functional groups and proceeds efficiently on a gram scale.

Acceptorless dehydrogenative coupling with Ru-based catalysts for the synthesis of -heteroaromatic compounds.

Ru-Catalyzed acceptorless dehydrogenative coupling (ADC) and auto-transfer-hydrogenative (ATH) reactions are effective, versatile transformations for the constructions of N-heteroaromatic compounds from alcohols. Water and hydrogen are the by-products and the starting alcohols are less toxic, more readily available and more easily handled than their halogenated counterparts. A variety of homogeneous ruthenium catalysts, alcohols and partner-substrates such as amines, ammonia, amidines and nitriles, have been used to build N-heteroaromatic compounds in one-pot, multi-step syntheses.

Acyl Radicals from α-Keto Acids Using a Carbonyl Photocatalyst: Photoredox-Catalyzed Synthesis of Ketones.

Acyl radicals have been generated from α-keto acids using inexpensive and commercially available 2-chloro-thioxanthen-9-one as the photoredox catalyst under visible light illumination. These reactive species added to olefins or coupled with aryl halides via a bipyridyl-stabilized Ni(II) catalyst, enabling easy access to a diverse range of ketones. This reliable, atom-economical, and eco-friendly protocol is compatible with a wide range of functional groups.

Nickel-Catalyzed Sonogashira C(sp)-C(sp) Coupling through Visible-Light Sensitization.

An efficient method for visible-light-initiated, nickel-catalyzed Sonogashira C(sp)-C(sp) coupling has been developed via an energy-transfer mode. Thioxanthen-9-one as a photosensitizer could significantly accelerate the arylation of alkynes with a wide range of (hetero)aryl halides in high yields. The cross-coupling reaction undergoes the stepwise oxidative addition of an arylhalide to nickel(0), transmetalation of the resulting aryl-Ni(II) halide species with Zn(II) acetylide into aryl-Ni(II) acetylide species, energy transfer from the excited state of thioxanthen-9-one to aryl-Ni(II) acetylide, and reductive elimination to the aryl alkyne.

A comparative study of clinical effect of total knee arthroplasty in the treatment of primary osteoarthritis and osteoarthritis of Kashin-Beck disease.

Objective: To evaluate the clinical efficacy of total knee arthroplasty (TKA) in the treatment of primary osteoarthritis (OA) and osteoarthritis of Kashin-Beck disease (KBD).

Methods: This study enrolled 77 KBD patients (77 knees, KBD-TKA) and 75 OA patients (75 knees, OA-TKA) who underwent TKA from September 2008 to June 2018. Clinical assessments for each patient were performed pre-operatively and last follow-up.

Hantzsch Ester as a Visible-Light Photoredox Catalyst for Transition-Metal-Free Coupling of Arylhalides and Arylsulfinates.

Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE , single electron transfer (SET) in donor-acceptor complex (DAC) from *HE to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE to sulfone by the DAC method.

Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols.

The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of β-alkylated secondary alcohols, α-alkylated ketones and α,β-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines.

Reversible dielectric switching behavior of a 1D coordination polymer induced by photo and thermal irradiation.

Solvothermal reaction of Zn(NO3)2 with 2,9-bis-(2-pyridine-3-yl-vinyl)-[1,10]phenanthroline (3-bpep) and furan-2,5-dicarboxylic acid (2,5-H2FDC) afforded a one-dimensional (1D) coordination polymer {[Zn2(3-bpep)2(2,5-FDC)2]·1.5H2O}n (1), which undergoes regioselective photocycloaddition to yield another 1D coordination polymer {[Zn2(3-bpep)(trans,rctt-3-bpbpycb)0.5(2,5-FDC)2]·H2O}n (2) in a single-crystal-to-single-crystal manner under UV light irradiation.