The impact of repeated temperature cycling on cryopreserved human iPSC viability stems from cytochrome redox state changes.

Human induced pluripotent stem cells (hiPSCs) are an attractive cell source for regenerative medicine. For its widespread use as a starting material, a robust storage and distribution system in the frozen state is necessary. For this system, managing transient warming during storage and transport is essential, but how transient warming affects cells and the mechanisms involved are not yet fully understood.

Bridging Titanium Nitrido Complexes Containing A Linear Ti-N-Ti Core with A Two-Coordinate Nitrido Ligand.

A series of titanium μ-nitrido complexes supported by the triamidoamine ligand Xy-NN (Xy-NN={(3,5-MeCH)NCHCH}N) is reported. The titanium azido complex [(Xy-NN)TiN] (1-N), prepared by salt metathesis of the chloride complex [(Xy-NN)TiCl] (1-Cl) with NaN, reacted with lithium metal or with alkali metal naphthalenides (alkali metal M=Na, K, and Rb) in THF to give the corresponding dinuclear μ-nitrido complexes M[(Xy-NN)Ti=N-Ti(Xy-NN)] (2-M; M=Li, Na, K, Rb). Single crystal X-ray diffraction studies of 2-Li, 2-Na, and 2-K revealed alkali metal dependent structures in the solid state.

Grubbs-Hoveyda catalysts conjugated to a β-barrel protein: Effect of halide substitution on aqueous olefin metathesis activity.

The effect of halide substitution in Grubbs-Hoveyda II catalysts (GHII catalysts) embedded in the engineered β-barrel protein nitrobindin (NB4exp) on metathesis activity in aqueous media was studied. Maleimide tagged dibromido and diiodido derivates of the GHII catalyst were synthesized and covalently conjugated to NB4exp. The biohybrid catalysts were characterized spectroscopically confirming the structural integrity.

Hydrogenolysis of Cationic Half-Sandwich Zinc Complexes Containing a Chelating Amine: Facile Cleavage of Zinc-Carbon Bond by Dihydrogen to Give Zinc Hydride Cations.

Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(L)][BAr ] (2 a, Cp*=η-CMe, L=N,N,N',N'-tetramethylethylenediamine, TMEDA; 2 b, L=N,N,N',N'-tetraethylethylenediamine, TEEDA; 2 c, Cp*=η-CMe, L=N,N,N',N'',N''-pentamethyldiethylenetriamine, PMDTA; Ar =(3,5-(CF)CH)) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(L)ZnH(thf)][BAr ] (3 a,b, m=1; 3 c, m=0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2 b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis.

Dihydrogen Cleavage by a Zinc-Zinc Bond of a Heteroleptic Dizinc(I) Cation.

Oxidative addition of dihydrogen across a metal-metal bond to form reactive metal hydrides in homogeneous catalysis is known for transition metals but not for zinc(I)-zinc(I) bond as found in Carmona's eponymous dizinconene [ZnCp*] (Cp* = η-CMe). Dihydrogen reacted with the heteroleptic zinc(I)-zinc(I) bonded cation [(L)Zn-ZnCp*][BAr] (L = TMEDA, ,,,-tetramethylethylenediamine, TEEDA, ,,,-tetraethylethylenediamine; Ar = 3,5-(CF)CH) under 2 bar at 80 °C to give the zinc(II) hydride cation [(L)ZnH(thf)][BAr] along with zinc metal and Cp*H derived from the intermediate [Cp*ZnH]. DFT calculations show that the cleavage of dihydrogen occurs through a highly unsymmetrical transition state.

Engineered Anchor Peptide LCI with a Cobalt Cofactor Enhances Oxidation Efficiency of Polystyrene Microparticles.

A typical component of polymer waste is polystyrene (PS) used in numerous applications, but degraded only slowly in the environment due to its hydrophobic properties. To increase the reactivity of polystyrene, polar groups need to be introduced. Here, biohybrid catalysts based on the engineered anchor peptide LCI_F16C are presented, which are capable of attaching to polystyrene microparticles and hydroxylating benzylic C-H bonds in polystyrene microparticles using commercially available oxone as oxidant.

Benzylic C(sp )-H Bond Oxidation with Ketone Selectivity by a Cobalt(IV)-Oxo Embedded in a β-Barrel Protein.

Artificial metalloenzymes have emerged as biohybrid catalysts that allow to combine the reactivity of a metal catalyst with the flexibility of protein scaffolds. This work reports the artificial metalloenzymes based on the β-barrel protein nitrobindin NB4, in which a cofactor [Co X(Me TACD-Mal)] X (X=Cl, Br; Me TACD=N,N ,N''-trimethyl-1,4,7,10-tetraazacyclododecane, Mal=CH CH CH NC H O ) was covalently anchored via a Michael addition reaction. These biohybrid catalysts showed higher efficiency than the free cobalt complexes for the oxidation of benzylic C(sp )-H bonds in aqueous media.

Cationic tetranuclear macrocyclic CaCo complexes as highly active catalysts for alternating copolymerization of propylene oxide and carbon dioxide.

We found that a cationic hetero tetranuclear complex including a calcium and three cobalts exhibited high catalytic activity toward alternating copolymerization of propylene oxide (PO) and carbon dioxide (CO). The tertiary anilinium salt [PhNMeH][B(CF)] was the best additive to generate the cationic species while maintaining polymer selectivity and carbonate linkage, even under 1.0 MPa CO.

Heterobimetallic Hydrides with a Germanium(II)-Zinc Bond.

In the presence of TMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine), zinc dihydride reacted with germanium(II) compounds (BDI-H)Ge (1) and [(BDI)Ge][B(3,5-(CF ) C H ) ] (3) (BDI-H = HC{(C=CH )(CMe)(NAr) }, BDI = [HC(CMeNAr) ]; Ar = 2,6- Pr C H ) by formal insertion of the germanium(II) center into the Zn-H bond of polymeric [ZnH ] to give neutral and cationic zincagermane with a H-Ge-Zn-H core [(BDI-H)Ge(H)-(H)Zn(tmeda)] (2) and [(BDI)Ge(H)-(H)Zn(tmeda)][B(3,5-(CF ) C H ) ] (4), respectively. Compound 2 eliminated [ZnH ] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2-d exchanged with [ZnH ] and [ZnD ] in the presence of TMEDA to give a mixture of 2 and 2-d .

FhuA: From Iron-Transporting Transmembrane Protein to Versatile Scaffolds through Protein Engineering.

Protein engineering has emerged as a powerful methodology to tailor the properties of proteins. It empowers the design of biohybrid catalysts and materials, thereby enabling the convergence of materials science, chemistry, and medicine. The choice of a protein scaffold is an important factor for performance and potential applications.

Hydroboration and Deoxygenation of CO Mediated by a Gallium(I) Cation.

Hydroboration of CO to formoxy borane occurs under ambient conditions in acetonitrile using pinacolborane HBpin in the presence of gallium(I) cation [(MeTACD)Ga][BAr] (; MeTACD = ,',″,'''-tetramethyl-1,4,7,10-tetraazacyclododecane; Ar = CH-3,5-Me). Slow turnover was accompanied by side reactions including ligand scrambling of HBpin to give BH(CHCN) and crystalline Bpin. When was reacted with CO alone, the formation of the gallium(III) carbonato complex [(MeTACD)Ga(κ-OCO)][BAr] () along with CO was observed.

Formate complexes of tri- and tetravalent titanium supported by a tris(phenolato)amine ligand.

Titanium(III) and titanium(IV) formate complexes supported by the sterically encumbering tris(phenolato)amine ligand (H(ON) = tris(4,6-di--butyl-2-hydroxybenzyl)amine) are described. Salt metathesis of the chlorido precursor [(ON)TiCl] (1-Cl) with sodium formate in a 2 : 1 ratio in THF gave a dimer of sodium dititanium triformate units with 12-membered ring [Na{(ON)Ti}(μ-OCHO-η:η')] (3-Na) when crystallized from acetonitrile. Complex 3-Na was also prepared by reacting the previously reported terminal formate complex [(ON)Ti(OCHO)] (2) with excess sodium formate.

Solvent-Dependent Oxidative Addition and Reductive Elimination of H Across a Gallium-Zinc Bond.

H adds reversibly across the metal-metal bond of [(BDI)Ga(H)-Zn(tmeda)(thf)][BAr ] (BDI=[HC{C(CH )N(2,6-iPr -C H )} ] , TMEDA=N,N,N',N'-tetramethylethylenediamine, BAr =[B(C H -3,5-(CF ) ) ] ). Due to the stabilising effect of solvent coordination, hydrogenation products [(BDI)GaH ] and [(tmeda)ZnH(thf)][BAr ] are favoured in THF solution, but THF-free mixtures of [(BDI)GaH ] and [(tmeda)ZnH(OEt )][BAr ] are predisposed towards entropically driven dehydrogenation to [(BDI)Ga(H)-Zn(tmeda)][BAr ] in fluorobenzene solution.

Reversible Oxidative Addition of Zinc Hydride at a Gallium(I)-Centre: Labile Mono- and Bis(hydridogallyl)zinc Complexes.

In the presence of TMEDA (N,N,N',N'-tetramethylethylenediamine), partially deaggregated zinc dihydride as hydrocarbon suspensions react with the gallium(I) compound [(BDI)Ga] (I, BDI={HC(C(CH )N(2,6-iPr -C H )) } ) by formal oxidative addition of a Zn-H bond to the gallium(I) centre. Dissociation of the labile TMEDA ligand in the resulting complex [(BDI)Ga(H)-(H)Zn(tmeda)] (1) facilitates insertion of a second equiv. of I into the remaining Zn-H to form a thermally sensitive trinuclear species [{(BDI)Ga(H)} Zn] (2).

Strontium Hydride Cations Supported by a Large NNNNN Type Macrocycle: Synthesis, Structure, and Hydrofunctionalization Catalysis.

The use of the 15-membered NNNNN macrocyclic ligand MePACP (MePACP = 1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane) allowed the isolation of two cationic strontium hydride complexes by hydrogenolysis of benzyl precursors. Treatment of sparingly soluble [(MePACP)Sr(CHPh)] with dihydrogen gave free MePACP, toluene, and oligomeric strontium hydride [SrH], while hydrogenolysis in the presence of 1 equiv of the benzyl cation [(MePACP)Sr(CHPh)][B(CH-3,5-Me)] enabled isolation of the thermally unstable trihydride cation [(MePACP)Sr(μ-H)][B(CH-3,5-Me)]. When the benzyl cation [(MePACP)Sr(CHPh)][BAr] (Ar = CH-3,5-Me or CH-4-Bu) was reacted with dihydrogen or -octylsilane, dihydride complexes [(MePACP)Sr(μ-H)][BAr] containing a dinuclear core bridged by two hydride ligands were obtained.

Strategies Employed by Forensic Community Mental Health Nurses to Resolve Difficulties in Supporting Offenders With Mental Disorders Under the Medical Treatment and Supervision Act in Japan.

Objective: This study aimed to identify the strategies used by forensic community mental health nurses to resolve difficulties in supporting offenders with mental disorders under the Medical Treatment and Supervision Act in Japan.

Method: Interviews were conducted with 13 nurses, and the data were analyzed using content analysis.

Results: The study identified the strategies for difficulties in (a) assessing and managing risk potential of forensic service patients, (b) addressing offending behavior, (c) managing the transition of patients, (d) supporting patients to understand the impact of justice processes and applying knowledge of legislation to nursing, and (e) promoting the role of forensic community mental health nurses within the multidisciplinary team.

A Brønsted Acidic Gallium Hydride: Facile Interconversion of NNNN-Macrocycle Supported [Ga ] and [Ga H].

Protonolysis of [Cp*M] (M=Ga, In, Tl) with [(Me TACD)H][BAr ] (Me TACD=N,N',N'',N'''-tetramethyl-1,4,7,10-tetraazacyclododecane; [BAr ] =[B{C H -3,5-(CH ) } ] ) provided monovalent salts [(Me TACD)M][BAr ], whereas [Cp*Al] yielded trivalent [(Me TACD)AlH][BAr ] . Protonation of [(Me TACD)Ga][BAr ] with [Et NH][BAr ] gave an unusually acidic (pK (CH CN)=24.5) gallium(III) hydride dication [(Me TACD)GaH][BAr ] .

Formation and Reactivity of a Hexahydridosilicate [SiH ] Coordinated by a Macrocycle-Supported Strontium Cation.

The cationic benzyl complex [(Me TACD)Sr(CH Ph)][A] (Me TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C H -3,5-Me ) ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me TACD) Sr (thf) (μ-κ  : κ -SiH )][A] (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH that is trapped by two strontium hydride cations [(Me TACD)SrH(thf) ] . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me TACD)Sr(SiH )(thf) ][A], with release of H .

Aerobic oxygenation of α-methylene ketones under visible-light catalysed by a CeNi complex with a macrocyclic tris(salen)-ligand.

A hetero-tetranuclear CeNi complex with a macrocyclic ligand catalysed the aerobic oxygenation of a methylene group adjacent to a carbonyl group under visible-light radiation to produce the corresponding α-diketones. The visible-light induced homolysis of the Ce-O bond of a bis(enolate) intermediate is proposed prior to aerobic oxygenation.

Deaggregation of Zinc Dihydride by Lewis Acids Including Carbon Dioxide in the Presence of Nitrogen Donors.

Thermally sensitive polymeric zinc dihydride [ZnH] can conveniently be prepared by the reaction of ZnEt with [AlH(NEt)]. When reacted with CO (1 bar) in the presence of chelating N-donor ligands L = ,,','-tetramethylethylenediamine (TMEDA), ,,','-tetramethyl-1,3-propanediamine (TMPDA), -pentamethyldiethylenetriamine (PMDTA), and 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (MeTACD), insertion into the Zn-H bond readily occurred. Depending on the denticity , formates [(L)Zn(OCHO)] were isolated and structurally characterized, either as a molecule (L = TMEDA, TMPDA, PMDTA) or a charge-separated ion pair [(L)Zn(OCHO)][OCHO] (L = MeTACD).

Reductive elimination of [AlH] from a cationic Ga-Al dihydride.

Oxidative addition of TMEDA-supported [AlH] to [{BDI}Ga] (BDI = {HC(C(CH)(2,6-iPr-CH))}) provides [{BDI}Ga(H)-Al(H)(tmeda)][B(CH-3,5-Me)] (TMEDA = ,,''-tetramethylethylenediamine) with a covalent metal-metal bond. The reaction is readily reversed by substituting TMEDA for an N-heterocyclic carbene or dissolving in THF.

Effects of Thoracic Epidural Anesthesia on Systemic and Local Inflammatory Responses in Patients Undergoing Lung Cancer Surgery: A Randomized Controlled Trial.

Objective: Inflammatory responses play major roles in the development of acute lung injury following lung cancer surgery. The authors tested the hypothesis that thoracic epidural anesthesia (TEA) during surgery could attenuate both systemic and local inflammatory cytokine productions in patients undergoing lung cancer surgery.

Design: A prospective randomized controlled trial.

Scandium Reduced Arene Complex: Protonation and Reaction with Azobenzene.

The reactivity of the reduced anthracene complex of scandium [Li(thf) ][Sc{N(tBu)Xy} (anth)] (2-anth-Li) (Xy=3,5-Me C H ; anth=C H , thf=tetrahydrofuran) toward Brønsted acid [NEt H][BPh ] and azobenzene is reported. While a stepwise protonation of 2-anth-Li with two equivalents of [NEt H][BPh ] afforded the scandium cation [Sc{N(tBu)Xy} (thf) ][BPh ] (3), reduction of azobenzene gave a thermolabile, anionic scandium reduced azobenzene complex [Li(thf)][Sc{N(tBu)Xy} (η -PhNNPh)] (4), which slowly lost one of the anilide ligands to form the neutral scandium azobenzene complex dimer [Sc{N(tBu)Xy}(μ-η :η -Ph N )] (5). Exposure of 3 to CO produced the scandium carbamate complex [Sc{κ -O CN(tBu)(Xy)} ][BPh ] (6) as a result of CO insertion into the Sc-N bonds.

Dihydrogen cleavage by a dimetalloxycarbene-borane frustrated Lewis pair.

A frustrated Lewis pair of dititanoxycarbene [(Ti(N[Bu]Ar))(μ-CO)] (Ar = 3,5-MeCH) and B(CF) cleaved dihydrogen under ambient conditions to give the zwitterionic formate [(Ti(N[Bu]Ar))(μ-OCHO-ηO:ηO')(B(CF))] and the hydrido borate [Ti(N[Bu]Ar)][HB(CF)].