Laparoscopic extraperitoneal approach for lateral lymph node dissection for patients with metachronous lateral pelvic lymph node metastases following surgery for rectal cancer: a case series and short-term outcomes.

Background: There have been few reports of a totally extraperitoneal approach for laparoscopic lateral lymph node dissection (LLND) for patients with metachronous lateral pelvic lymph node metastases following surgery for rectal cancer. Therefore, this study reports the short-term outcomes of LLND via an extraperitoneal approach.

Methods: A total of 10 patients underwent LLND through a laparoscopic extraperitoneal approach in our hospital since October 2018.

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.

Prediction model of the risk for lateral local recurrence in locally advanced rectal cancer without enlarged lateral lymph nodes: Lessons from a Japanese multicenter pooled analysis of 812 patients.

Aim: Although the oncological impact of lateral lymph node dissection on enlarged lateral lymph nodes has been gradually accepted over the last decade, that on lateral lymph nodes without swelling remains doubtful. This study aimed to develop a prediction model for the future risk of lateral local recurrence and to clarify the value of adding lateral lymph node dissection in locally advanced rectal cancer without enlarged lateral lymph nodes.

Methods: This retrospective, multi-institutional study recruited 812 patients with cStage II/III low rectal cancer without enlarged lateral lymph nodes <7 mm.

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.

Feasibility and learning curve for robotic surgery in a small hospital: A retrospective cohort study.

Robotic surgery rates, typified by the use of the da Vinci Surgical System, have increased in recent years. However, robotic surgery is mostly performed in large hospitals and has not been fully implemented in small hospitals. Therefore, we aimed to verify the feasibility of robotic surgery in small hospitals and verify the number of cases in which perioperative preparation for robotic surgery is stable by creating a learning curve in small hospitals.

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.

Clinical features and oncological outcomes of intestinal cancers associated with ulcerative colitis and Crohn's disease.

Background: Patients with longstanding inflammatory bowel disease are at high risk of developing intestinal cancers. In this study, we aimed to elucidate the differences between intestinal cancers associated with ulcerative colitis and Crohn's disease.

Methods: Intestinal cancers in ulcerative colitis and Crohn's disease patients treated between 1983 and 2020 at 43 Japanese institutions were retrospectively analyzed.

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).