A New Potent Antimicrobial Metalloporphyrin.

A series of bis-acryl functionalized porphyrins and their corresponding metalloporphyrins (M=Co, Mn) were synthesized and investigated for their antimicrobial properties through MIC screening and bacteria time-kill kinetic studies. The Mn(III) 4-(bis)methylphenyl-substituted-porphyrins showed superior batericidal activities even in the dark with low hemotoxicity and good cytotoxicity profile.

Impact of cirrhosis in patients undergoing laparoscopic liver resection in a nationwide multicentre survey.

BACKGROUND: The aim was to analyse the impact of cirrhosis on short-term outcomes after laparoscopic liver resection (LLR) in a multicentre national cohort study. METHODS: This retrospective study included all patients undergoing LLR in 27 centres between 2000 and 2017. Cirrhosis was defined as F4 fibrosis on pathological examination. Short-term outcomes of patients with and without liver cirrhosis were compared after propensity score matching by centre volume, demographic and tumour characteristics, and extent of resection. RESULTS: Among 3150 patients included, LLR was performed in 774 patients with (24·6 per cent) and 2376 (75·4 per cent) without cirrhosis. Severe complication and mortality rates in patients with cirrhosis were 10·6 and 2·6 per cent respectively. Posthepatectomy liver failure (PHLF) developed in 3·6 per cent of patients with cirrhosis and was the major cause of death (11 of 20 patients). After matching, patients with cirrhosis tended to have higher rates of severe complications (odds ratio (OR) 1·74, 95 per cent c.i. 0·92 to 3·41; P = 0·096) and PHLF (OR 7·13, 0·91 to 323·10; P = 0·068) than those without cirrhosis. They also had a higher risk of death (OR 5·13, 1·08 to 48·61; P = 0·039). Rates of cardiorespiratory complications (P = 0·338), bile leakage (P = 0·286) and reoperation (P = 0·352) were similar in the two groups. Patients with cirrhosis had a longer hospital stay than those without (11 versus 8 days; P = 0·018). Centre expertise was an independent protective factor against PHLF in patients with cirrhosis (OR 0·33, 0·14 to 0·76; P = 0·010). CONCLUSION: Underlying cirrhosis remains an independent risk factor for impaired outcomes in patients undergoing LLR, even in expert centres.

ANTECEDENTES: El objetivo de este estudio fue analizar el impacto de la cirrosis en los resultados a corto plazo después de la resección hepática laparoscópica (laparoscopic liver resection, LLR) en un estudio de cohortes multicéntrico nacional. MÉTODOS: Este estudio retrospectivo incluyó todos los pacientes sometidos a LLR en 27 centros entre 2000 y 2017. La cirrosis se definió como fibrosis F4 en el examen histopatológico. Los resultados a corto plazo de los pacientes con hígado cirrótico (cirrhotic liver CL) (pacientes CL) y los pacientes con hígado no cirrótico (non-cirrhotic liver, NCL) (pacientes NCL) se compararon después de realizar un emparejamiento por puntaje de propension del volumen del centro, las características demográficas y del tumor, y la extensión de la resección. RESULTADOS: Del total de 3.150 pacientes incluidos, se realizó LLR en 774 (24,6%) pacientes CL y en 2.376 (75,4%) pacientes NCL. Las tasas de complicaciones graves y mortalidad en el grupo de pacientes CL fueron del 10,6% y 2,6%, respectivamente. La insuficiencia hepática posterior a la hepatectomía (post-hepatectomy liver failure, PHLF) fue la principal causa de mortalidad (55% de los casos) y se produjo en el 3,6% de los casos en pacientes CL. Después del emparejamiento, los pacientes CL tendieron a tener tasas más altas de complicaciones graves (razón de oportunidades, odds ratio, OR 1,74; i.c. del 95% 0,92-0,41; P = 0,096) y de PHLF (OR 7,13; i.c. del 95% 0,91-323,10; P = 0,068) en comparación con los pacientes NCL. Los pacientes CL estuvieron expuestos a un mayor riesgo de mortalidad (OR 5,13; i.c. del 95% 1,08-48,6; P = 0,039) en comparación con los pacientes NCL. Los pacientes CL presentaron tasas similares de complicaciones cardiorrespiratorias graves (P = 0,338), de fuga biliar (P = 0,286) y de reintervenciones (P = 0,352) que los pacientes NCL. Los pacientes CL tuvieron una estancia hospitalaria más larga (11 versus 8 días; P = 0,018) que los pacientes NCL. La experiencia del centro fue un factor protector independiente de PHLF (OR 0,33; i.c. del 95% 0,14-0,76; P = 0,010) pacientes CL. CONCLUSIÓN: La presencia de cirrosis subyacente sigue siendo un factor de riesgo independiente de peores resultados en pacientes sometidos a resección hepática laparoscópica, incluso en centros con experiencia.

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.

Metal-salen molecular cages as efficient and recyclable heterogeneous catalysts for cycloaddition of CO2 with epoxides under ambient conditions.

A salen based molecular cage, salen@cage, was synthesized and complexed with Co and Al to yield metal-salen molecular cages, Co(ii)@cage, Co(iii)@cage and Al(iii)@cage. These cages were demonstrated to be efficient heterogeneous catalysts for the cycloaddition of CO2 with styrene oxide, achieving full conversion at 25 °C and 1 atm CO2. Good to excellent yields of various cyclic carbonates were also achieved under mild conditions. Al(iii)@cage can be reused up to five times without any significant loss of its high catalytic activity. The capability to access a variety of heterogeneous organometallic catalysts with salen@cage offers new prospects for practical CO2 utilization and chemical manufacturing.

A new 3-D coordination polymer as a precursor for CuI-based thermoelectric composites.

Two complexes, [Cu6I6(L1)3]n (I) and [Cu4I4(L2)2]n (II) (L1 = 1,4-bis(phenylthio)but-2-yne; L2 = 1,4-bis(phenylthio)butane), as precursors for thermoelectric composites were prepared using a literature procedure. During the preparation of I, an unexpected 3-D polymorph [Cu4I4(L1)2]n (1) with a triclinic space group and an infinite [CuI]n staircase structure was obtained. This new polymorph (1) exhibited the same structure at both room temperature and 173 K. Complexes 1 and II were therefore pyrolysed to composites 2 and 3, respectively, at 400 °C under a nitrogen gas flow. Composite 3 was pale in color with a low carbon content (0.05 wt%) and easily disassembled during handling. By comparison, the high carbon containing (10.2 wt%) composite 2 can be compressed into a robust, light pellet (density 3.58 g cm-3), which showed a moderate to high Seebeck coefficient (543-1308 µV K-1) over the temperature range 70-240 °C.

Gastro-intestinal surgery and fertility.

In France, 10 to 15% of couples in the overall population have a fertility problem. Preservation of sexual and reproductive function should be a major concern for all patients capable of procreation who undergo treatment for gastro-intestinal disease. The gastro-intestinal diseases most often responsible for fertility disorders include chronic inflammatory diseases, intestinal cancer and hereditary diseases, such as the Lynch syndrome and familial adenomatous polyposis. Obesity is responsible for a 20% loss of fertility but the effects of bariatric surgery on fertility are controversial. Nonetheless, in the light of progress in surgical techniques and better knowledge of gastro-intestinal disease the negative impact of surgery on fertility warrants attention. Effectively, fertility can be preserved after certain major gastro-intestinal operations such as cytoreductive surgery with intraperitoneal chemotherapy, total coloprotectomy with ileo-anal anastomosis and rectosigmoid resection, as long as the patient's age permits and resection of the reproductive organs is not necessary.

A thermoelectric copper-iodide composite from the pyrolysis of a well-defined coordination polymer.

Coordination polymer 1 was prepared from CuI and a flexible [SNS] ligand L in acetonitrile. The thermal decomposition of 1 yielded a CuI-rich thermoelectric carbon composite 2, which is relatively light, thermally stable and robust. Composite 2 possesses high Seebeck coefficients (700-950 µV K-1) from rt to 204 °C after an optimization cycle.

Dimerization of Terminal Aryl Alkynes Catalyzed by Iron(II) Amine-Pyrazolyl Tripodal Complexes with E/Z Selectivity Controlled by tert-Butoxide.

The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KO t Bu or NaO t Bu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.

Self-assembled [2]catenane in trapezoidal metallacycles with [Cp*Ir]-corners.

A series of trapezoidal metallacycles were synthesized by the selective combination of a rigid with a flexible arm. [2]Catenane 3 was obtained by self-assembly when the cavity size of the trapezoidal rings was optimised.

Hydrogen-Bonding Interactions in Luminescent Quinoline-Triazoles with Dominant 1D Crystals.

Quinoline-triazoles 2-((4-(diethoxymethyl)-1H-1,2,3-triazol-1-yl)methyl)quinoline (1), 2-((4-(m-tolyl)-1H-1,2,3-triazol-1-yl)methyl)quinoline (2) and 2-((4-(p-tolyl)-1H-1,2,3-triazol-1-yl)methyl)quinoline (3) have been prepared with CuAAC click reactions and used as a model series to probe the relationship between lattice H-bonding interaction and crystal direction of growth. Crystals of 1-3 are 1D tape and prism shapes that correlate with their intermolecular and solvent 1D lattice H-bonding interactions. All compounds were thermally stable up to about 200 C and blue-green emissive in solution.

A Robust Hybrid Zn-Battery with Ultralong Cycle Life.

Advanced batteries with long cycle life and capable of harnessing more energies from multiple electrochemical reactions are both fundamentally interesting and practically attractive. Herein, we report a robust hybrid zinc-battery that makes use of transition-metal-based redox reaction (M-O-OH → M-O, M = Ni and Co) and oxygen reduction reaction (ORR) to deliver more electrochemical energies of comparably higher voltage with much longer cycle life. The hybrid battery was constructed using an integrated electrode of NiCo2O4 nanowire arrays grown on carbon-coated nickel foam, coupled with a zinc plate anode in alkaline electrolyte. Benefitted from the M-O/M-O-OH redox reactions and rich ORR active sites in NiCo2O4, the battery has concurrently exhibited high working voltage (by M-O-OH → M-O) and high energy density (by ORR). The good oxygen evolution reaction (OER) activity of the electrode and the reversible M-O ↔ M-O-OH reactions also enabled smooth recharging of the batteries, leading to excellent cycling stabilities. Impressively, the hybrid batteries maintained highly stable charge-discharge voltage profile under various testing conditions, for example, almost no change was observed over 5000 cycles at a current density of 5 mA cm-2 after some initial stabilization. With merits of higher working voltage, high energy density, and ultralong cycle life, such hybrid batteries promise high potential for practical applications.

Nickel-Catalyzed Facile [2+2+2] Cyclotrimerization of Unactivated Internal Alkynes to Polysubstituted Benzenes.

A catalytic [2+2+2] cyclotrimerization of unactivated internal alkynes providing cyclotrimerization products in excellent yields with high regioselectivity is described. The transformation is accomplished by using a simple catalytic mixture comprising Ni(acac)2 , an imidazolium salt and a Grignard reagent at room temperature or 60 °C for 20 min or 1 h.

Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO2 utilizing pinacolborane at r.t. and 1 atm CO2, with the combination of [Ru(CNCBn)(CO)2(H)][PF6] and KOCO2tBu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

Building better lithium-sulfur batteries: from LiNO3 to solid oxide catalyst.

Lithium nitrate (LiNO3) is known as an important electrolyte additive in lithium-sulfur (Li-S) batteries. The prevailing understanding is that LiNO3 reacts with metallic lithium anode to form a passivation layer which suppresses redox shuttles of lithium polysulfides, enabling good rechargeability of Li-S batteries. However, this view is seeing more challenges in the recent studies, and above all, the inability of inhibiting polysulfide reduction on Li anode. A closely related issue is the progressive reduction of LiNO3 on Li anode which elevates internal resistance of the cell and compromises its cycling stability. Herein, we systematically investigated the function of LiNO3 in redox-shuttle suppression, and propose the suppression as a result of catalyzed oxidation of polysulfides to sulfur by nitrate anions on or in the proximity of the electrode surface upon cell charging. This hypothesis is supported by both density functional theory calculations and the nitrate anions-suppressed self-discharge rate in Li-S cells. The catalytic mechanism is further validated by the use of ruthenium oxide (RuO2, a good oxygen evolution catalyst) on cathode, which equips the LiNO3-free cell with higher capacity and improved capacity retention over 400 cycles.

Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) .

Utilisation of gold nanoparticles on amine-functionalised UiO-66 (NH2-UiO-66) nanocrystals for selective tandem catalytic reactions.

Colloidal deposition of gold nanoparticles (Au NPs) onto NH2-UiO-66 nanocrystals has been demonstrated with the resulting hybrid catalyst proving robust and versatile for one-pot, heterogeneous conversions involving the selective oxidation of primary alcohols in tandem with Knoevenagel condensation reactions. Within these systems, structure-property correlations have been established to confirm that the active sites for the oxidation and condensation reactions are intrinsically correlated with the Au NPs and pendant amine groups respectively.

Multicomponent (Ce, Cu, Ni) oxides with cage and core-shell structures: tunable fabrication and enhanced CO oxidation activity.

Solvothermal synthesis of Cu2O cubes from Cu(OAc)2 in ethanol provided templates for tunable formation of novel multicomponent composites: hollow CeO2-Cu2O (), core-shell NiO@Cu2O () and hollow CeO2-NiO-Cu2O (). Composites catalyze the oxidation of CO at a lower temperature than the parent Cu2O cubes.

Cyclopentadienyl nickel(ii) N,C-chelating benzothiazolyl NHC complexes: synthesis, characterization and application in catalytic C-C bond formation reactions.

Cyclopentadienyl (Cp) Ni(ii) complexes [CpNiL][PF6] containing hybrid N,C chelating benzothiazolyl NHC ligands (L1 = 1-(2-benzothiazolyl)-3-methylimidazol-2-ylidene, ; L2 = 1-(2-benzothiazolyl)-3-allylimidazol-2-ylidene, ; L3 = 1-(2-benzothiazolyl)-3-benzylimidazol-2-ylidene, ) have been synthesized and fully characterized. The catalytic activity of in some C-C bond formation reactions has been examined. They are efficient catalysts for the homo-coupling of benzyl bromide in the presence of MeMgCl at r.t. with good functional group tolerance. Complex is active in the catalytic oxidative homo-coupling of Grignard reagents with 1,2-dichloroethane as an oxidant at r.t.

A zwitterionic 1D/2D polymer co-crystal and its polymorphic sub-components: a highly selective sensing platform for HIV ds-DNA sequences.

Polymorphic compounds {[Cu(dcbb)2(H2O)2]·10H2O}n (2, 1D chain), [Cu(dcbb)2]n (3, 2D layer) and their co-crystal {[Cu(dcbb)2(H2O)][Cu(dcbb)2]2}n (4) have been prepared from the coordination reaction of a 2D polymer [Na(dcbb)(H2O)]n (1, H2dcbbBr = 1-(3,5-dicarboxybenzyl)-4,4'-bipyridinium bromide) with Cu(NO3)2·3H2O at different temperatures in water. Compounds 2-4 have an identical metal-to-ligand stoichiometric ratio of 1 : 2, but absolutely differ in structure. Compound 3 features a 2D layer structure with aromatic rings, positively charged pyridinium and free carboxylates on its surface, promoting electrostatic, π-stacking and/or hydrogen-bonding interactions with the carboxyfluorescein (FAM) labeled probe single-stranded DNA (probe ss-DNA, delineates as P-DNA). The resultant P-DNA@3 system facilitated fluorescence quenching of FAM via a photoinduced electron transfer process. The P-DNA@3 system functions as an efficient fluorescent sensor selective for HIV double-stranded DNA (HIV ds-DNA) due to the formation of a rigid triplex structure with the recovery of FAM fluorescence. The system reported herein also distinguishes complementary HIV ds-DNA from mismatched target DNA sequences with the detection limit of 1.42 nM.