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Abstract: Treatment of Os(κ2-S2CNMe2)H(CO)(PPh3)2 with HSiMeCl2 or HSiCl3 gives in high yield Os(κ2-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 (1) or Os(κ2-S2CNMe2)(SiCl3)(CO)(PPh3)2 (2), respectively. The crystal structures of both compounds have been determined and the Os–Si distances are 2.3672(10)Å for 1 and 2.3449(12)Å for 2. In solution, and under forcing conditions, both compounds are extraordinarily unreactive towards hydroxide ions. [Copyright &y& Elsevier]

Abstract: Treatment of the six-coordinate trimethylstannyl complex, Os(SnMe3)(κ2-S2CNMe2)(CO)(PPh3)2 (1) with SnMe2Cl2 produces Os(SnMe2Cl)(κ2-S2CNMe2)(CO)(PPh3)2 (2), which in turn reacts readily with hydroxide ion to give, Os(SnMe2OH)(κ2-S2CNMe2)(CO)(PPh3)2 (3). The osmastannol complex 3 undergoes a reaction with 2 equivalents of t BuLi, in which one of the phenyl rings of a triphenylphosphine ligand is “ortho-stannylated”, without cleavage of the Os–Sn bond, to give the cyclic complex, Os(κ2(Sn,P)-SnMe2C6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (4). This novel cyclic complex is selectively functionalised at the tin atom by reaction with SnMe2Cl2 which exchanges one methyl group for chloride giving the diastereomeric mixture, Os(κ2(Sn,P)-SnMeClC6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (5a/5b). Crystal structure determination reveals that both diastereomers occur in the unit cell. The mixture, 5a/5b, undergoes reaction with hydroxide ion to give the diastereomeric osmastannol complexes, Os(κ2(Sn,P)-SnMeOHC6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (6a/6b) and with sodium borohydride to give the corresponding tin-hydride mixture, Os(κ2(Sn,P)-SnMeHC6H4PPh2)(κ2-S2CNMe2)(CO)(PPh3) (7a/7b). Crystal structure determinations for 2, 4, and 5a/5b have been obtained. [Copyright &y& Elsevier]

Abstract: Heating the five-coordinate trimethylstannyl complex, Os(SnMe3)Cl(CO)(PPh3)2, in solution with triphenylphosphine induces an ortho-stannylation of one phenyl group of a triphenylphosphine ligand and an ortho-metallation of another triphenylphosphine ligand, to produce the metallacyclic complexes, Os(κ2(Sn,P)-SnMeClC6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)(PPh3) (1) and Os(κ2(Sn,P)-SnMe2C6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)(PPh3) (2), suggesting the possible intermediacy of a complex with a coordinated stannylene ligand. Spectroscopic data indicate that only one diastereomer of 1 is formed and crystal structure determination of 1 reveals that this is the diastereomer with chloride directed towards the CO ligand. Complex 2 is converted to 1 through a redistribution reaction with SnMe2Cl2. Heating the six-coordinate trimethylstannyl complex, Os(SnMe3)Cl(CO)2(PPh3)2, in solution produces the osmium(II) methyl complex, Os(Me)(SnMe2Cl)(CO)2(PPh3)2 (3), through an exchange of methyl and chloride groups on the tin and osmium. In this rearrangement, the relative locations of the two CO ligands and the two PPh3 ligands remains unchanged. However, when the six-coordinate trimethylstannyl complex, Os(SnMe3)Cl(CO)2(PPh3)2 is heated under CO, the same exchange reaction is observed but the mono-triphenylphosphine, tricarbonyl complex, Os(Me)(SnMe2Cl)(CO)3(PPh3) (4), is produced and here the SnMe2Cl ligand is located trans to the PPh3 ligand. Crystal structure determinations for 1, 2, 3, and 4 have been obtained. [Copyright &y& Elsevier]

Abstract: Reaction between Os(SiCl3)Cl(CO)(PPh3)2 and five equivalents of MeLi produces a colourless intermediate, tentatively formulated as the lithium salt of the six-coordinate, dimethyl, trimethylsilyl-containing complex anion, Li[Os(SiMe3)(Me)2(CO)(PPh3)2]. Reaction of this material with ethanol releases methane and gives the red, coordinatively unsaturated methyl, trimethylsilyl-containing complex, Os(SiMe3)(Me)(CO)(PPh3)2 (1). An alternative synthesis of 1 is to add one equivalent of MeLi to Os(SiMe3)Cl(CO)(PPh3)2, which in turn is obtained by adding three equivalents of MeLi to Os(SiCl3)Cl(CO)(PPh3)2. Treatment of 1 with p-tolyl lithium, again gives a colourless intermediate which may be Li[Os(SiMe3)(Me)(p-tolyl)(CO)(PPh3)2], and reaction with ethanol gives the red complex, Os(SiMe3)(p-tolyl)(CO)(PPh3)2 (3). Complexes 1 and 3 are readily carbonylated to Os(SiMe3)(Me)(CO)2(PPh3)2 (2) and Os(SiMe3)(p-tolyl)(CO)2(PPh3)2 (4), respectively. Heating Os(SiMe3)Cl(CO)(PPh3)2 in molten triphenylphosphine results only in loss of the trimethylsilyl ligand and formation of the previously known complex containing an ortho-metallated triphenylphosphine ligand, Os(κ2(C,P)-C6H4PPh2)Cl(CO)(PPh3)2. In contrast, heating the five-coordinate osmium-methyl complex, Os(SiMe3)(Me)(CO)(PPh3)2 (1), in the presence of triphenylphosphine results mainly, not in tetramethylsilane elimination, but in ortho-silylation as well as ortho-metallation of different triphenylphosphine ligands giving, Os(κ2(Si,P)-SiMe2C6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)(PPh3) (5). A byproduct of this reaction is the non-silicon containing di-ortho-metallated complex, Os(κ2(C,P)-C6H4PPh2)2(CO)(PPh3) (6). A similar reaction occurs when Os(SiMe3)(Me)(CO)(PPh3)2 (1) is heated in the presence of tri(N-pyrrolyl)phosphine producing Os(κ2(Si,P)-SiMe2C6H4PPh2)(κ2(C,P)-C6H4PPh2)(CO)[P(NC4H4)3] (7) but a better synthesis of 7 is to treat 5 directly with tri(N-pyrrolyl)phosphine. Heating the six-coordinate complex, Os(SiMe3)(Me)(CO)2(PPh3)2 (2), gives two complexes both containing ortho-metallated triphenylphosphine, one with loss of the trimethylsilyl ligand, giving the known complex, Os(κ2(C,P)-C6H4PPh2)H(CO)2(PPh3), and the other with retention of the trimethylsilyl ligand, giving Os(SiMe3)(κ2(C,P)-C6H4PPh2)(CO)2(PPh3) (8). Crystal structure determinations for 5, 6, 7 and 8 have been obtained. [Copyright &y& Elsevier]

The treatment of 2-(ArNC(H))C6H4-HNC9H6N with n-BuLi and the subsequent addition of CuCl2 afforded the anilido-aldimine Cu(II) complexes 1-5 Cu[{2-[ArN=C(H)]C6H4}N(8-C9H6N)]Cl (Ar = 2,6-iPr2C6H3 (1), 2,4,6-(CH3)3C6H2 (2), 4-OCH3C6H4 (3), 4-BrC6H4 (4), 4-ClC6H4 (5)), respectively. All the copper complexes were fully characterized by IR, EPR and HR-MS spectra. The X-ray diffraction analysis reveals that 2 and 4 are mononuclear complexes, and the Cu atom is sitting in a slightly square-planar geometry. These Cu(II) complexes have exhibited excellent catalytic activity in the Chan–Lam coupling reactions of benzimidazole derivatives with arylboronic acids, achieving the highest yields of up to 96%. [ABSTRACT FROM AUTHOR]

[Display omitted] l -Glutathione (GSH) has exceptional antioxidant activities against UVA irradiation-induced oxidative stress and is used widely for combatting skin ageing. However, topical administration of GSH is challenging due to its inability to penetrate the stratum corneum (SC). This study aims to evaluate the solid lipid nanoparticles (SLNs) carrier system for improving the skin penetration and stability of GSH. The GSH-loaded SLNs (GSH-SLNs) were prepared by the double emulsion technique and were optimized by a full factorial design. The optimized GSH-SLNs formulation had a mean particle size of 305 ± 0.6 nm and a zeta potential of + 20.1 ± 9.5 mV, suitable for topical delivery. The ex-vivo penetration study using human skin demonstrated a 3.7-fold improvement of GSH penetration across SC with GSH-SLNs when compared with aqueous GSH. GSH-SLNs prolonged antioxidant activity on UVA irradiated fibroblast cells when compared to GSH solution, preventing UVA-induced cell death and promoting cell growth for times over 48 h. This research has illustrated that as a carrier system, SLNs were able to enhance the physicochemical stability, skin penetration, and drug deposition in the viable epidermis and dermis layers of the skin for GSH, while also maintaining the ability to protect human skin fibroblast cells against oxidative stress caused by UVA irradiation. This delivery system shows future promise as a topical delivery platform for the topical delivery of GSH and other chemically similar bioactive compounds for improving skin health. [ABSTRACT FROM AUTHOR]

Background: Previous studies on dynamic impingement of nerve root in cervical spondylotic radiculopathy (CSR) have focused on effect of cervical spine motion (CSM) on dimensional changes of intervertebral foramen. However, there are few studies to investigate effect of CSM on displacement of posterolateral intervertebral disc until now. The present study aimed to investigate effect of CSM on displacement of posterolateral annulus fibrosus (AF) in CSR with contained posterolateral disc herniation. Methods: A C5–C6 CSR finite element model with unilateral contained posterolateral disc herniation was generated based on validated C5–C6 normal finite element model. Forward and backward displacement distributions of posterolateral AFs in CSR model and normal model were compared. Changes in forward and backward displacement magnitudes of posterolateral AFs of the herniated side and the healthy side in CSR model, with respect to those of the ipsilateral posterolateral AFs in normal model, were compared. The comparisons were performed under flexion, extension, lateral bendings and axial rotations. Results: There was no difference in deformation trend of posterolateral AF between CSR model and normal model. Bilateral posterolateral AFs mainly moved forward during flexion and backward during extension. Left posterolateral AF mainly moved backward and right posterolateral AF forward during left lateral bending and left axial rotation. Left posterolateral AF mainly moved forward and right posterolateral AF backward during right lateral bending and right axial rotation. However, with respect to forward and backward displacement magnitudes of the ipsilateral posterolateral AFs in normal model, those of the herniated side increased relatively significantly compared with those of the healthy side in CSR model. Conclusions: Flexion, lateral bending to the healthy side and axial rotation to the healthy side make posterolateral AF of the herniated side mainly move forward, whereas extension, lateral bending to the herniated side and axial rotation to the herniated side make it mainly move backward. These data may help select CSM or positions to diagnose and treat CSR with contained posterolateral disc herniation. Increase in deformation amplitude of posterolateral AF of the herniated side may also be the reason for dynamic impingement of nerve root in CSR with contained posterolateral disc herniation. [ABSTRACT FROM AUTHOR]

A Pd-catalysed amination method is used to convert seco -CBI, a synthetic analogue of the alkylating subunit of the duocarmycin natural products, from the phenol to amino form. This allows efficient enantioselective access to the more potent S enantiomer of aminoCBI and its incorporation into analogues of DNA minor groove cross-linking agents. Evaluation in a panel of nine human tumour cell lines shows that the bifunctional agents containing aminoCBI are generally less cytotoxic than their phenolCBI analogues and more susceptible to P-glycoprotein-mediated resistance. However, all bifunctional agents are potent cytotoxins, some in the sub-pM IC 50 range, with in vitro properties that compare favourably with established microtubule-targeted ADC payloads. [ABSTRACT FROM AUTHOR]

Objective: To compare the results of ureteroscopic lithotripsy (URSL) with retroperitoneal laparoscopic ureterolithotomy (RPLU) as two minimally invasive techniques in the management of proximal ureteral stones larger than 12 mm. Patients and methods: From January 2009 to October 2013, patients with impacted unilateral upper ureteral stones larger than 12 mm were enrolled including 182 males and 93 females with a medium age of 40 years (22-72 years). Patients were randomized to receive URSL (139 cases) with semirigid ureteroscope or RPLU (136 cases). Results: Stone size was similar in RPLU and URSL groups (13.8 ± 1.9 vs 13.6 ± 1.4 mm, P = 0.312). Operating time and hospitalizing days in URSL group were significantly shorter than those in RPLU group ( P < 0.001), whereas stone clearance rate was significantly higher in RPLU group (97.1 vs 89.9 %, P = 0.017). Ureteral strictures happened higher in URSL group (5 patients, 3.6 %) than RPLU group (2 patients, 1.5 %) with no statistical significance, while the strictures requiring surgical intervention were significantly higher in URSL group (4 cases) (2.9 vs 0 %, P = 0.046). Conclusion: RPLU could provide better stone clearance rate than semirigid URSL for upper ureteral impacted stones larger than 12 mm. It may also reduce the chance of surgical intervention for postoperative ureteral stricture. [ABSTRACT FROM AUTHOR]

• Ru(II) Schiff-base complexes showed high activity in acceptorless dehydrogenative reaction. • The primary alcohols were selectively oxidized to give the corresponding aldehydes. • The secondary alcohols were smoothly to afford the ketones in good to excellent yields. • The present catalytic system displayed wide substrate scope and operated under mild conditions. The catalytic performance of ruthenium carbonyl complexes containing Schiff base ligands [RN CH(C 10 H 6 O)] 2 Ru(CO) 2 [R = C 6 H 5 (1); 4-CH 3 C 6 H 4 (2) ; 4-OCH 3 C 6 H 4 (3); R = 2,6-(CH 3) 2 C 6 H 3 (4); 4-ClC 6 H 4 (5); 4-BrC 6 H 4 (6); 4-CF 3 C 6 H 4 (7)] were explored in acceptorless dehydrogenative oxidation of alcohols with the releasing of hydrogen as the only by-product. All the Ru complexes 1–7 demonstrated good catalytic activities in oxidation of secondary alcohols to furnish the corresponding ketone products in excellent yields. Moreover, these Ru complexes displayed good selectivity in oxidation of primary alcohols to affording the aldehydes as the final products in 37–96 % yields. Among the complexes, the complex 7 , which having an electron-withdrawing group (-CF 3) showed the best catalytic activity. A series of schiff base supported ruthenium(II) complexes were found to be efficient catalysts in acceptorless dehydrogenative oxidation of both primary and secondary alcohols to give the corresponding ketones and aldehydes, respectively, in moderate to excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: Quaternary salt analogues based on the DNA minor groove binder and adenine N3 alkylating agent 5-amino-1-(chloromethyl)-1,2-dihydro-3H-benz[e]indole (aminoCBI) show remarkable effects on the body weight of mice (a long-term failure to gain weight relative to matched controls with no loss of appetite or perceptible deterioration in health) following administration of a single (non-toxic) dose between about 0.5–5μmol/kg. The nature of the quaternizing group was not important, but a related hydroxyCBI analogue was much less effective. Compounds where the chloro group was replaced by a hydrogen or hydroxy group (thus abrogating DNA alkylating capability) showed no weight control activity. It is speculated, based on other studies, that the marked long-term weight control effect is due to inhibition of bile flow into the intestine and reduced absorption of triglycerides, together with accelerated cell death in spleen and white adipose tissues due to drug accumulation there. This class of compound may serve as interesting tools for further study of these phenomena. [Copyright &y& Elsevier]

Four ruthenium(II) complexes 1—4 [RN=CH‐(2,4‐(tBu)2C6H2O)]RuH(PPh3)2(CO) (R = C6H5, 1; R = 4‐MeC6H4, 2; R = 4‐ClC6H4, 3; R = 4‐BrC6H4, 4) bearing Schiff base ligands were prepared by treating RuHClCO(PPh3)3 with RN=CH‐(2,4‐(tBu)2C6H2OH (L1—L4) in the presence of triethylamine. Their structures were fully characterized by elemental analysis, IR, NMR spectroscopy and X‐ray crystallography. These Ru(II) complexes exhibit high catalytic performance and good functional‐group compatibility in the acceptorless dehydrogenation of secondary alcohols, affording the corresponding ketones in 82%—94% yields. [ABSTRACT FROM AUTHOR]

• A piconol ligand based cluster was synthesized and it is stable to air and moisture. • The Ru clusters were found to be efficient catalysts for C H oxidation of hydrocarbons with TBHP as the oxidant. • The catalytic system displayed good functional group compatibility and was carried out at room temperature. Trinuclear ruthenium clusters supported by piconol ligands [6-C 8 H 6 N-PyCR1R2O](μ 2 H)Ru 3 (CO) 9 (R1 = R2 = CH 3 (1); R1 = R2 = CH 2 CH 3 (2); R1, R2 = -(CH 2) 4 - (3); R1 = CH 3 , R2 = Ph (4)) have been proved to be efficient catalysts for the oxidation of saturated C H bonds. Cluster 1 was found to be the most active of the four, which can catalyze the oxidation of various hydrocarbons, with tert ‑butyl hydroperoxide as the oxidant in CH 3 CN/H 2 O at room temperature, to afford the corresponding ketones in excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

• Cheap and readily available ligands, air- and moisture-stable catalysts. • Highly efficient for benzylic C-H oxidation. • Mild reaction conditions, broad substrate scope, environmentally benign methodology. Thermal reactions of Ru 3 (CO) 12 with two equivalents of N,O-bidentate ligands L1H - L7H (naphthyl-substituted Schiff-bases) afforded the corresponding Ru(II) carbonyl complexes [ L 2 Ru(CO) 2 ] 1a-1g in good yields. All the Ru complexes were well characterized by elemental analysis, FT-IR, NMR and HR-MS. The molecular structures of 1c, 1e and 1g were reconfirmed by X-ray crystallography. These complexes showed high activity in the selective oxidation of benzylic C-H bonds with tert -butylhydroperoxide (TBHP) under mild conditions to give aryl ketones in 60 %–98 % yields. This catalytic protocol proceeds at room temperature with low catalyst loading (1.0 mol%), displays broad functional-group compatibility and has potential application for industry-scale reactions. [Display omitted] [ABSTRACT FROM AUTHOR]

• Easily synthesized ligands and air- and moisture-stable Ni complexes. • Both aldehydes and ketones were efficiently hydrosilylated to the corresponding alcohols. • The present catalytic reaction carried out in room temperature and displayed excellent functional group tolerance. Treatment of Ni(OAc) 2 ⋅4H 2 O with 8-hydroxylquinoline-imine ligands [2-(ArN=HC)-8-OH]C 9 H 5 N (Ar = 2,6- i Pr 2 C 6 H 3 , L1H ; Ar = 2,4,6-(Me) 3 C 6 H 2 , L2H ; Ar = 4-MeC 6 H 4 , L3H and Ar = 4-ClC 6 H 4 , L4H) in refluxing EtOH afforded the dual-ligand coordinated nickel complexes [L 2 Ni] 1 - 4 , respectively. All the four nickel complexes were characterized by IR, elemental analysis and high-resolution mass spectrometry. Furthermore, the molecular structures of complexes 3 and 4 were confirmed by X-ray diffraction analysis. Complexes 1 - 4 were found to be efficient catalysts for hydrosilylation of aldehydes and ketones with PhSiH 3 as the hydrogen source. Various aromatic and aliphatic ketones and aldehydes were proven to be suitable substrates for such catalytic property, affording the corresponding alcohols in good to excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] Four nickel complexes incorporating N,N,N -quinolinyl anilido-imine ligands based on ortho -C 6 H 4 F(CH = NAr) and 8-aminoquinoline, Ni[{2-[ArN = C(H)]C 6 H 4 }N(8-C 9 H 6 N)]Br (Ar = 2,6- i Pr 2 C 6 H 3 (1a), 2,4,6-(CH 3) 3 C 6 H 2 (1b), 4-BrC 6 H 4 (1c)) and Ni[{2-[ArN = C(H)]C 6 H 4 }N(8-C 9 H 6 N)] 2 (Ar = 4-ClC 6 H 4 (1d)) were synthesized and structurally characterized by HR-MS, IR, NMR spectroscopy and X-ray crystallography. These nickel(II) complexes were used in Suzuki-Miyaura coupling and exhibited moderate to excellent catalytic activity with a low catalyst loading of 2.0 mol%. [ABSTRACT FROM AUTHOR]

Treatment of Cu(OAc) 2 ·H 2 O with salicylaldimine Schiff-base (C 9 H 6 N)N=CH(3,5- t Bu 2 C 6 H 2 OH) (L1H) , (Et 2 N)(CH 2) 2 N=CH(3,5- t Bu 2 C 6 H 2 OH) (L2H) , (2-C 5 H 4 N)CH 2 N=CH(3,5- t Bu 2 C 6 H 2 OH) (L3H) in refluxing ethanol afforded three mononuclear copper complexes [(L1)Cu(OAc)] (1), (L2)Cu(OAc) (2) and (L3)Cu(OAc) (3), respectively. The three new complexes were fully characterized using elemental analysis, IR and HR-MS, and X-ray diffraction analysis. They all exhibited efficient catalytic activity in the oxidation of primary and secondary alcohols into the corresponding carbonyl derivatives with hydrogen peroxide (H 2 O 2) as the oxidation agent. The catalytic system is operationally simple, clean and generates water as the only by-product.Three new mononuclear copper complexes supported by tridentate salicylaldimine Schiff-base ligands were successfully synthesized and their catalytic activity for the oxidation reaction of primary and secondary alcohols in the presence of H 2 O 2 as an oxidant reagent was researched. [Display omitted] Treatment of Cu(OAc) 2 ·H 2 O with salicylaldimine Schiff-base (C 9 H 6 N)N = CH(3,5- t Bu 2 C 6 H 2 OH) (L1H) , (Et 2 N)(CH 2) 2 N = CH(3,5- t Bu 2 C 6 H 2 OH) (L2H) , (2-C 5 H 4 N)CH 2 N = CH(3,5- t Bu 2 C 6 H 2 OH) (L3H) in refluxing ethanol afforded three mononuclear copper complexes [(L1)Cu(OAc)] (1), (L2)Cu(OAc) (2) and (L3)Cu(OAc) (3), respectively. The three new complexes were fully characterized using elemental analysis, IR and HR-MS, and X-ray diffraction analysis. They all exhibited efficient catalytic activity in the oxidation of primary and secondary alcohols into the corresponding carbonyl derivatives with hydrogen peroxide (H 2 O 2) as the oxidation agent. The catalytic system is operationally simple, clean and generates water as the only by-product. [ABSTRACT FROM AUTHOR]

The organocobalt complexes containing functionally substituted cyclopentadienyl ligands (η5-RC5H4)Co(PPh3)2 (1a, R=EtO2C; 1b, R=MeCO) were synthesized by reactions of the corresponding functionalized cyclopentadienides RC5H4Na with (PPh3)3CoCl in 65 and 85% yields, respectively. The ligand exchange reaction of 1a with PhC&z.tbnd6;CPh afforded (η5-EtO2CC5H4)Co(PPh3)( η2-PhC&z.tbnd6;CPh) (2a) in 72% yield, whereas (η5-RC5H4)Co(PPh3)2 (1a, R=EtO2C; 1b, R=MeCO; 1c, R=H) reacted with C60 through ligand exchange to give (η5-RC5H4)Co(PPh3)(η2-C60) (3a, R=EtO2C; 3b, R=MeCO; 3c, R=H) in 34–68% yields. 3a could be also obtained similarly by ligand exchange reaction of 2a with C60 in 83% yield. In addition, reaction of 2a or 3a with excess iodine I2 produced (η5-EtO2CC5H4)Co(PPh3)(I)2 (4a) in 90–91% yields. The new compounds 1a, 1b, 2a, 3a–3c and 4a were characterized by 1H-NMR, 31P-NMR, IR, UV–Vis spectra and elemental analysis, whereas the reverse saturable absorption properties of the organocobalt fullerene complexes 3a and 3c along with C60 were studied by Z-scan method. [Copyright &y& Elsevier]

• A series of novel trinuclear ruthenium complexes were synthesized and well characterized. • All the Ru complexes are easily to prepared and stable to air and moisture. • The present catalytic system showed high efficiency for oxidation of secondary alcohols to give the ketones in good to excellent yields. A series of novel trinuclear ruthenium carbonyl complexes [ µ - ƞ 2-2-OC 6 H 4 -CH=N-Ar)] 2 Ru 3 (CO) 8 [Ar = Ph (8), C 6 H 4 -4-Me (9), C 6 H 4 -4-CF 3 (10), C 6 H 4 -4-Cl (11), C 6 H 3 -2,6-Me 2 (12), C 6 H 3 -2,6-Et 2 (13)] and [ µ - ƞ 2-2-OC 6 H 4 -CH=N-C 6 H 3 -2,6- i Pr 2 ]Ru 3 (CO) 9 (14) were designed and synthesized. All the seven novel complexes were fully characterized by elemental analysis, IR and NMR spectroscopy. Molecular structures of 8, 11, 13 and 14 were further confirmed by single-crystal X-ray diffraction. The catalytic performance of these complexes in the oxidation of secondary alcohols was explored and it was found the combination of such complexes and N -methylmorpholine-N-oxide (NMO) exhibits high catalytic activities for the oxidation of secondary alcohols, giving the corresponding carbonyl compounds in excellent yields. A series of novel trinuclear ruthenium carbonyl complexes supported by salicylaldimine ligands were successfully synthesized and their catalytic activity for oxidation of secondary alcohols was studied. Image, graphical abstract [ABSTRACT FROM AUTHOR]

A series of ruthenium complexes ( Ru1-Ru4 ) bearing new NNN-pincer ligands were synthesized in 58-78% yields. All of the complexes are air and moisture stable and were characterized by IR, NMR, and high-resolution mass spectra (HRMS). In addition, the structures of Ru1-Ru3 were confirmed by X-ray crystallographic analysis. These Ru(II) complexes exhibited high catalytic efficiency and broad functional group tolerance in the N-methylation reaction of amines using CH 3 OH as both the C1 source and solvent. Experimental results indicated that the electronic effect of the substituents on the ligands considerably affects the catalytic reactivity of the complexes in which Ru3 bearing an electron-donating OMe group showed the highest activity. Deuterium labeling and control experiments suggested that the dehydrogenation of methanol to generate ruthenium hydride species was the rate-determining step in the reaction. Furthermore, this protocol also provided a ready approach to versatile trideuterated N -methylamines under mild conditions using CD 3 OD as a deuterated methylating agent.

Objective: To explore the clinical effect of percutaneous pedicle screw anchored vertebral augmentation(PPSAVA) in the treatment of asymptomatic Kümmell disease without neurological symptoms., Methods: The clinical data of 20 patients with Kümmell disease without neurological symptoms treated with PPSAVA in our hospital from January 2019 to December 2021 were analyzed retrospectively, including 5 males and 15 females, aged 56 to 88 (74.95±9.93) years old. and the course of disease was 7 to 60 days with an average of (21.35±14.46) days. All patients were treated with PPSAVA. The time of operation, the amount of bone cement injected and the leakage of bone cement were recorded. The visual analogue scale(VAS), Oswestry disability index(ODI), vertebral body angle(VBA), anterior edge height and midline height of vertebral body were compared among the before operation, 3 days after operation and during the final follow-up. The loosening and displacement of bone cement were observed during the final follow-up., Results: All the 20 patients completed the operation successfully. The operation time was 30 to 56 min with an average of (41.15±7.65) min, and the amount of bone cement injection was 6.0 to 12.0 ml with an average of (9.30±1.49) ml. Bone cement leakage occurred in 6 cases and there were no obvious clinical symptoms. The follow-up time was 6 to 12 months with an average of (8.43±2.82) months. The VBA, anterior edge height and midline height of of injured vertebral body were significantly improved 3 days after operation and the final follow-up( P <0.05), and the VBA, anterior edge height and midline height of of injured vertebral body were lost in different degrees at the final follow-up ( P <0.05). The VAS and ODI at 3 days after operation and at the final follow-up were significantly lower than those at preoperatively( P <0.05), but the VAS score and ODI at the final follow-up were not significantly different from those at 3 d after operation( P >0.05). At the last follow-up, no patients showed loosening or displacement of bone cement., Conclusion: PPSAVA is highly effective in treating Kümmell disease without neurological symptoms, improving patients' pain and functional impairment, and reducing the risk of cement loosening and displacement postoperatively.

The disorganized vasculatures in tumors represent a substantial challenge of intratumor nanomedicine delivery to exert the anticancer effects. Herein, we rationally designed a glutathione (GSH)-activated nitric oxide (NO) donor loaded bioinspired lipoprotein system (NO-BLP) to normalize tumor vessels and then promote the delivery efficiency of sequential albumin-bound paclitaxel nanoparticles (PAN) in tumors. NO-BLP exhibited higher tumor accumulation and deeper penetration versus the counterpart liposomal formulation (NO-Lipo) in 4T1 breast cancer tumors, thus producing notable vascular normalization efficacy and causing a 2.33-fold increase of PAN accumulation. The sequential strategy of NO-BLP plus PAN resulted in an 81.03% inhibition of tumor growth in 4T1 tumors, which was better than the NO-BLP monotherapy, PAN monotherapy, and the counterpart NO-Lipo plus PAN treatment. Therefore, the bioinspired lipoprotein of NO-BLP provides an encouraging platform to normalize tumor vessels and promote intratumor delivery of nanomedicines for effective cancer treatment.