A Phosphorescent P/N/S Hybrid Ligand Stabilized Au2Cu 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)4]BF4 afforded cluster complex [Au2Cu(dpppyatc)2](BF4)2Cl (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. Complex1 could detect ammonia in aqueous solution down to concentrations of 2 ppm (w/w).

The epigenetically regulated PP1α expression by KDM1A may contribute to oxycodone conditioned place preference in mice.

The lysine-specific demethylase 1 (KDM1A) is reported to be a regulator in learning and memory. However, the effect of KDM1A in oxycodone rewarding memory has yet to be studied. In our study, rewarding memory was assessed by using conditioned place preference (CPP) in male mice. Next generation sequencing and chromatin immunoprecipitation-PCR were used to explore the molecular mechanisms. Oxycodone significantly decreased PP1α mRNA and protein levels in hippocampal neurons. Oxycodone significantly increased KDM1A and H3K4me1 levels, while significantly decreased H3K4me2 levels in a time- and dose-dependent manner. Behavioral data demonstrated that intraperitoneal injection of ORY-1001 (KDM1A inhibitor) or intra-hippocampal injection of KDM1A siRNA/shRNA blocked the acquisition and expression of oxycodone CPP and facilitated the extinction of oxycodone CPP. The decrease of PP1α was markedly blocked by the injection of ORY-1001 or KDM1A siRNA/shRNA. Oxycodone-induced enhanced binding of CoRest with KDM1A and binding of CoRest with the PP1α promoter was blocked by ORY-1001. The level of H3K4me2 demethylation was also decreased by the treatment. The results suggest that oxycodone-induced upregulation of KDM1A via demethylation of H3K4me2 promotes the binding of CoRest with the PP1α promoter, and the subsequent decrease in PP1α expression in hippocampal neurons may contribute to oxycodone reward.

Modulating ß-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 ß-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. A COF bearing electron-deficient Cl atoms displayed the highest photocatalytic activity toward the ATRA reaction of polyhalogenated alkanes to give halogenated olefins under visible light at room temperature. This heterogeneous photocatalyst exhibited good functional group tolerance and could be recycled without significant loss of activity.

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 CF3COOAg, 3-bdppmapy (N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine) and HTZ (1,2,4-triazole-3-thiol) in CH2Cl2/MeOH resulted in a dinuclear Ag/P/S complex [Ag2(TZ)2(3-bdppmapy)2]·xSol (1·xSol). Crystals of 1·xSol converted to 1·2MeOH in air at room temperature and further to 1 under vacuum upon heating. The solid-state, room-temperature photoluminescent emission of 1·xSol (510 nm) shifted to 494 nm (1·2MeOH) and 486 nm (1). Grinding solids of 1·2MeOH in air resulted in amorphous 1G characterized by solid-state emission at 468 nm, which converted to 1GR with 513 nm emission upon MeOH treatment. Grinding 1GR in air returned 1G, and this interconversion was reproducible over five cycles. The solid-state photoluminescence of 1G changed in response to vapors containing low-molecular weight alcohols but remained unchanged after exposure to other volatile organic compounds (VOCs) or to water vapor. Test papers impregnated with 1G could detect methanol in vapors from aqueous solutions at concentrations above 50%. Complex 1G is, therefore, an example of a stimuli-responsive molecular sensor for the detection of alcohols.

Heteroleptic copper(I) complexes [Cu(dmp)(N

Earth-abundant copper(I) coordination complexes of an imine-phosphine and a diimine have been developed as visible-light photocatalysts. Reaction of [Cu(MeCN)4]BF4 with hetero-bidentate phosphinopyrazole (phpz) ligand R1R2C3HN2PPh3 (R1 = R2 = H (1a); R1 = H, R2 = Me (1b); R1 = H, R2 = Ph (1c); R1 = R2 = Me (1d)) and 2,9-dimethyl-1,10-phenanthroline (dmp) gave four heteroleptic bis-chelate Cu(I) complexes [Cu(dmp)(R1R2C3HN2PPh3)]BF4 (R1 = R2 = H (2a); R1 = H, R2 = Me (2b); R1 = H, R2 = Ph (2c); R1 = R2 = 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 CBr4, or CCl3Br, CHI3 to styrenes in yields up to 91% and with a broad substrate scope. The absorption, emission, redox potential and photocatalytic activity were dependent on the substituents on the phpz ligand. Mechanistic studies supported an atom-transfer radical addition (ATRA) mechanism.

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

A heterobimetallic coordination polymer [Au4(dppmt)4(AgCl)2]n (1) incorporating an in situ generated P-S ligand (dppmtH) was synthesized from the solvothermal reaction of Au(tht)Cl, AgCl, and dpppyatc in CH3CN/CH2Cl2 (dppmtH = (diphenylphosphino)methanethiol, tht = tetrahydrothiophene, dpppyatc = N,N-bis((diphenylphosphaneyl)methyl)-N-(pyridin-2-yl)-amino-thiocarbamide). The structure of 1 contains a one-dimensional helical Au-Au chain in which the unique [Au4Ag2S2] cluster units are connected by [Au2(dppmt)2] dimers. Upon excitation at 343 nm, 1 exhibited cyan (495 nm) phosphorescent emission at quantum yield (QY) = 22.3% and τ = 0.78 µs (λex = 375 nm). Coordination polymer 1 exhibited a rapid, selective, reversible, and visible vapor-chromic response on exposure to methanol (MeOH) vapor with its emission shifting to a more intense green (530 nm, λex = 388 nm) with QY = 46.8% and τ = 1.24 µs (λex = 375 nm). A polymethylmethacrylate film containing 1 served as a reversible chemical sensor for the sensitive detection of MeOH in air.

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

A new Ag/Cu bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(EtOH)2](ClO4)4 (1, bdppthi = N,N'-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) exhibited strong phosphorescent (PL) emission at 644 nm upon excitation at 400 nm. Removal of the coordinated EtOH molecules in 1 resulted in derivative 1a, which exhibited significant red-shifted emission at 678 nm. The structure and PL of 1 was restored on exposure to EtOH vapor. Cluster 1a also exhibited a vapor-chromic PL response towards other common organic solvent vapors including acetone, MeOH and MeCN. A PMMA film of 1a was developed as a reusable visible sensor for MeCN.

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-NH2 C6 H4 SH as a modulating agent. The reaction of TpPa-1-SH-X with NiII acetylacetonate Ni(acac)2 gave nickel thiolate-immobilized TpPa-1 (TpPa-1-SNi-X). The highest hydrogen evolution rate was 10.87 mmol h-1 g-1 , which was an enhancement of 16.47, 3.83, and 1.84 times than that of the parent TpPa-1, covalent-bond-free [(p-NH2 C6 H4 S)2 Ni]n /TpPa-1-SH-10, and 3 wt % Pt-deposited TpPa-1, respectively. This enhanced photocatalytic hydrogen evolution is ascribed to enhanced crystallinity, the use of NiII thiolate as a cocatalyst and covalent bonding between the cocatalyst and TpPa-1.

Ni(II)-Mediated Photochemical Oxidative Esterification of Aldehydes with Phenols.

The photopromoted, Ni-catalyzed acceptorless dehydrogenation esterification of phenols and aromatic aldehydes has been achieved in an oxidant- and external photosensitizer-free manner. This reliable and atom-economical transformation was tolerant to a wide range of functional groups and proceeded efficiently to give various aryl benzoates in moderate to high yields. Additionally, this photocatalytic system displayed high activity for the hydrogen-evolution cross coupling of aliphatic aldehydes and phenols employing dual nickel and aromatic aldehyde catalysis.

Visible-light-driven C(sp2)-H arylation of phenols with arylbromides enabled by electron donor-acceptor excitation.

We have developed a catalyst-free visible-light-driven C(sp2)-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(sp2)-C(sp2) 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 t-BuNH(i-Pr) as the base and thioxanthen-9-one as the photosensitizer under visible light. This photocoupling exhibits a broad substrate scope.

A Photoluminescent Ag10 Cu6 Cluster Stablized by a PNNP Ligand and Phenylacetylides Selectively and Reversibly Senses Ammonia in Air and Water.

A photoluminescent bimetallic cluster [Ag10 Cu6 (bdppthi)2 (C≡CPh)12 (MeOH)2 (H2 O)](ClO4 )4 (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 NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 µmol/L (0.36 ppm, w/w) for NH3 ⋅ H2 O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water.

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. This on/off switching was clearly visible, relatively rapid and recyclable.

Photocatalyst- and Transition-Metal-Free Visible-Light-Promoted Intramolecular C(sp2)-S Formation.

A photocatalyst- and transition-metal-free visible-light-induced cyclization of ortho-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(sp2) Coupling Using Thioxanthen-9-one as a Photoredox Catalysis.

An efficient method has been developed for photocatalytic P(O)-C(sp2) 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 N-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. This review details recently reported Ru catalysts employed for these reactions, describing the scope of each methodology, proposed reaction mechanisms, regioselectivity of coupling and applications in synthesis.

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(sp2) Coupling through Visible-Light Sensitization.

An efficient method for visible-light-initiated, nickel-catalyzed Sonogashira C(sp)-C(sp2) 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. The efficacy measures included the visual analogue scale (VAS) pain score, range of motion (ROM), Hospital for Special Surgery (HSS) score, and short form 36 Health Survey (SF-36) as well as related influencing factors between the two groups. RESULTS: All patients were followed up; the follow-up time of KBD-TKA was 14-132 months, with an average of 72.68 ± 37.55 months; OA-TKA was 15-120 months, with an average of 49.2 ± 28.91 months. There was no difference in pre-operative VAS score (7.29 vs. 7.24) and SF-36 (PCS) score (4.87 vs. 5.49) between KBD-TKA and OA-TKA (P > 0.05), while compared with OA, KBD-TKA had significantly worse pre-operative ROM (75.48° vs. 82.87°), HSS score (36.40 vs. 41.84), and SF-36 (MCS) score (26.28 vs. 28.73) (P < 0.05). At the final follow-up, there was no significant difference in VAS score (1.13 vs. 1.16), ROM (105.79 vs. 105.79), and HSS score (92.06 vs. 92.25) between KBD-TKA and OA-TKA (P > 0.05), while compared with OA, KBD-TKA had significantly worse SF-36 (PCS) score (36.90 vs. 42.00) and SF-36 (MCS) score (55.16 vs. 59.70) (P < 0.05). In a multivariate regression, controlling for multiple potential confounders, diagnosis of KBD was associated with poor quality of life after surgery, whereas pre-operative pain was specifically associated with post-operative pain. However, preoperative gender, age, BMI, and the angles of knee prosthesis (before and after surgery) were not associated with post-operative outcome. CONCLUSION: Patients with KBD undergoing primary TKA have excellent outcomes, comparable with OA at the final follow-up, in spite of worse pre-operative ROM, HSS score, and SF-36(MCS) score. However, KBD patients are worse than OA in terms of general health. Pre-operative age, gender, BMI, and the angles of knee prosthesis were not the factors influencing the clinical efficacy of TKA. The diagnosis of KBD was an independent risk factor for poor quality of life after TKA. Pre-operative pain was a clinically important predictor of outcome.