Transileocolic Portal Vein Embolization Increases Remnant Liver Volume After Major Hepatectomy.

Background/aim: Transileocolic portal vein embolization (TIPE) may reduce the risk of liver failure after massive hepatectomy. However, convincing evidence of its usefulness in this regard is yet to be reported. Therefore, this study aimed to investigate the use of TIPE after massive hepatectomy.

Sulfide-Induced Dimerization Versus Demetallation of Tricopper(I) Clusters Protected by Tris-Thiolato Metalloligands.

Here, we report the reactivity of copper(I) clusters toward sulfide ions; these sulfide copper(I) clusters have attracted much attention due to their relevance to biologically active centers and their fascinating structural and photophysical properties. Treatment of the Cu Rh pentanuclear complex, [Cu{Rh(aet)}] (aet=2-aminoethanethiolate), in which a {Cu } cluster moiety is bound by two fac-[Rh(aet)] metalloligands, with NaSH in water produced the Cu Rh decanuclear complex, [CuS{Rh(aet)}], accompanied by the dimerization of [Cu{Rh(aet)}] and the incorporation of a sulfide ion at the center. While similar treatment using the analogous Cu Ir complex with fac-[Ir(aet)] metalloligands, [Cu{Ir(aet)}], produced the isostructural Cu Ir decanuclear complex, [CuS{Ir(aet)}], the use of the Cu Rh complex with fac-[Rh(apt)] metalloligands, [Cu{Rh(apt)}] (apt=3-aminopropanethiolate), resulted in the removal of one of the three Cu atoms from {Cu } to afford the Cu Rh tetranuclear complex, [Cu{Rh(apt)}].

Polymorphism and Its Influence on Catalytic Activities of Lanthanide-Glutamate-Oxalate Coordination Polymers.

To study the relationship between polymorphism and catalytic activities of lanthanide coordination polymers in the cycloaddition reactions of CO with epoxides, the monoclinic and triclinic polymorphs of [Ln(NH-Glu)(ox)]·2HO, where Ln = La (), Pr (), Nd (), Sm ), Eu (), Gd (), Tb (), and Dy (), NH-Glu = NH containing glutamate, and ox = oxalate, were synthesized and characterized. Factors determining polymorphic preference, the discrepancy between the two polymorphic framework structures, potential acidic and basic sites, thermal and chemical stabilities, active surface areas, void volumes, CO sorption/desorption isotherms, and temperature-programmed desorption of NH and CO are comparatively presented. Based on the cycloaddition of CO with epichlorohydrin in the presence of tetrabutylammonium bromide under solvent-free conditions and ambient pressure, catalytic activities of the two polymorphs were evaluated, and the relationship between polymorphism and catalytic performances has been established.

Postsynthetic Installation of Lanthanide Cubane Clusters in a 3D Hydrogen-Bonded Framework of IrZn Multicarboxylates.

Immersing single crystals of (Δ)-K[IrZnO(l-cysteinate)]·HO (K[]·HO) bearing 12 free carboxylate groups, which was newly prepared from Δ-H[Ir(l-cysteinate)], ZnBr, ZnO, and KOH, in an aqueous solution of lanthanide(III) acetate produced Ln[]·HO (; Ln = La, Ce, Pr, and Nd) and Ln[Ln(OH)(OAc)(HO)][]·HO (; Ln = Sm, Eu, Gd, Tb, Dy, Er, Ho, Tm, Yb, and Lu) in a single-crystal-to-single-crystal transformation manner. X-ray crystallography showed that the K ions in K[]·HO are completely exchanged by the Ln ions in and , retaining the 3D hydrogen-bonded framework that consists of the IrZn complex anions of []. While contained the Ln ions as isolated aqua species, the Ln ions in existed as cationic cubane clusters of [Ln(OH)(OAc)(HO)]; these were linked by [] anions through carboxylate groups in a 3D polymeric structure.

Photo-Controlled Reversible Uptake and Release of a Modified Sulfamethoxazole Antibiotic Drug from a Pillar[5]arene Cross-Linked Gelatin Hydrogel.

Pillararene cross-linked gelatin hydrogels were designed and synthesized to control the uptake and release of antibiotics using light. A suite of characterization techniques ranging from spectroscopy (FT-IR, H and C NMR, and MAS NMR), X-ray crystallographic analysis, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) was employed to investigate the physicochemical properties of hydrogels. The azobenzene-modified sulfamethoxazole (-) antibiotic was noncovalently incorporated into the hydrogel via supramolecular host-guest interactions to afford the -.

Jahn-Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment.

Treatment of nickel(II) nitrate with the iridium(III) metalloligand -[Ir(apt)] (apt = 3-aminopropanethiolate) gave the trinuclear complex [Ni{Ir(apt)}](NO) ([](NO)), in which the nickel center has a formal oxidation state of +III. Chemical or electrochemical oxidation and reduction of [](NO) generated the corresponding trinuclear complexes [Ni{Ir(apt)}](NO) ([](NO)) and [Ni{Ir(apt)}](NO) ([](NO)) with one-electron oxidated and reduced states, respectively. Single-crystal X-ray crystallography revealed that the nickel center in [](NO) is situated in a highly distorted octahedron due to Jahn-Teller effect, while the nickel center in each of [](NO) and [](NO) adopts a normal octahedral geometry.

Silver(I) Sulfide Clusters Protected by Rhodium(III) Metalloligands with 3-Aminopropanethiolate.

The two homochiral AgRh nanoclusters, Δ/Λ-[AgS{Rh(apt)}] ([]) and Δ/Λ-[AgS{Rh(apt)}] ([]), in which AgS and AgS cluster cores, respectively, are protected by -[Rh(apt)] metalloligands, were newly synthesized from -[Rh(apt)] (Hapt = 3-aminopropanethiol) and Ag in water in combination with sulfide sources. While [] was produced by using d-penicillamine as a sulfide source, the use of HS as a sulfide source afforded [] without causing any precipitation of AgS. Cluster [] was convertible to [] via the reaction with Ag, which led to a turn-on-type switch in photoluminescence from nonemissive [] to emissive [].

Serendipitous formation of oxygen-bridged CuII6M (M = Mn, Co) double cubanes showing electrocatalytic water oxidation.

Hydroxido-bridged CuII6M double-cubane clusters (M = Mn, Co) supported by D-penicillaminedisulfide were unexpectedly formed by treating a D-penicillaminato CuII2PtII2 complex with MBr in water. The clusters displayed heterogeneous electrocatalytic activities for water oxidation dependent on the central M shared by two Cu cubane units.

A chromotropic PtPdCo coordination polymer with dual electrocatalytic activity for water reduction and oxidation.

Here, we present a heterometallic coordination polymer that exhibits heterogeneous electrocatalytic activities for both water reduction and water oxidation. Treatment of the PtII2PdII2 tetranuclear complex [Pd{Pt(NH)(D-pen)}] ([1]; D-Hpen = D-penicillamine) with CoX (X = Cl, Br) provided (PtII2PdII2CoII2) coordination polymers [Co(HO)(1)]X ([2]X), in which the PtII2PdII2 units of [1] are linked by [Co(μ-HO)(HO)] moieties in a 3D network structure. [2]X showed a colour change from orange to dark green upon dehydration, reflecting the geometrical conversion of the Co centres in [Co(μ-HO)(HO)] from an octahedron to a tetrahedron by the removal of aqua ligands.

A mesoporous ionic solid with 272 Au Ag Cu complex cations in a super huge crystal lattice.

Here, we report a unique mesoporous ionic solid () generated from a cationic Au Ag Cu dodecanuclear complex with d-penicillamine depending on the homochirality and crystallization conditions. crystallizes in the cubic space group of 432 with an extremely large cell volume of 2 171 340 Å, containing 272 Au Ag Cu complex cations in the unit cell. In , the complex cations are connected to each other through CH⋯π interactions in a zeotype framework, the topology of which is the same as that of the metal-organic framework in MIL-101, with similar but much larger two types of polyhedral pores with internal diameters of 38.

Heterometallation of Photoluminescent Silver(I) Sulfide Nanoclusters Protected by Octahedral Iridium(III) Thiolates.

The recently-increasing interest in coinage metal clusters stems from their photophysical properties, which are controlled via heterometallation. Herein, we report homometallic Ag S clusters protected by octahedral fac-[Ir(aet) ] (aet=2-aminoethanethiolate) molecules and their conversion to heterometallic Ag M S (M=Cu, Au) clusters. The reactions of fac-[Ir(aet) ] with Ag and penicillamine produced [Ag S {Ir(aet) } ] ([1] ), where a spherical Ag S cluster is covered by fac-[Ir(aet) ] octahedra through thiolato bridges.

Resection and reconstruction of pancreatic artery aneurysms caused by the compression of the celiac trunk by the median arcuate ligament: a report of two cases.

Background: Some patients with the compression of the celiac trunk by the median arcuate ligament (MAL) suffer pancreatic artery aneurysms (PAAs) due to excessive blood flow from the superior mesenteric artery. These aneurysms are in peril because they are prone to rupture irrespective of size. Here, we present two cases of resection and reconstruction of PAAs caused by the compression of the celiac trunk by the MAL.

Self-assembly of cyclic hexamers of γ-cyclodextrin in a metallosupramolecular framework with d-penicillamine.

Cyclodextrins are widely used cyclic oligosaccharides of d-glucose whose hydrophilic exterior is covered by hydroxyl groups and whose hydrophobic interior is surrounded by lipophilic moieties. Because of this structural feature, cyclodextrin molecules commonly aggregate into dimensional structures intermolecular hydrogen bonds, and their aggregation into closed oligomeric architectures has been achieved only the attachment of functional substituent groups to the cyclodextrin rings. Here, we report the first structurally characterized self-assembly of non-substituted γ-cyclodextrin molecules into cyclic hexamers, which was realized in a chiral coordination framework composed of complex-anions with d-penicillamine rather than l- or dl-penicillamine.

Intermediate snapshots of a 116-nuclear metallosupramolecular cage-of-cage in a homogeneous single-crystal-to-single-crystal transformation.

Soaking crystals of an AuI72CdII40NaI4 cage-of-cage in aqueous Co(NO3)2 afforded an analogous AuI72CoII44 cage-of-cage, accompanied by the exchange of NaI and CdII by CoII with retention of the single crystallinity. The homogeneous progress of the transformation led to the direct observation of intermediate species by single-crystal X-ray crystallography.

Transformations of empty Cu core to CuCuO and CuS cores oxide and sulfide insertions.

[Cu4(LRh)4]8- ([1]8-; LRh = Δ-[Rh(l-cysteinate)3]3-), with an empty tetrahedral {CuI4}4+ core, was converted to [Cu4O(LRh)4]8- ([2]8-), with a mixed-valent {CuI2CuII2O}4+ core, in aqueous NaOH. A solid sample of the latter compound was converted back to [1]8- by heating under vacuum, while treatment of [1]8- with aqueous NaSH caused conversion to [Cu6S(LRh)4]8- ([3]8-), with a stable octahedral {CuI6S}4+ core.

Racemic Tartrate/Malate Anions Combine with Racemic Complex Cations to Form Optically Active Ionic Crystals.

Spontaneous resolution has attracted continuing attention in various research fields since Pasteur's work on the crystallization behavior of racemic tartrate. Here, a unique example of this phenomenon is reported, involving ionic crystals generated from racemic RR/SS- tartrate or R/S-malate and racemic ΔΔ/ΛΛ-[Ag Rh (2-aminoethanethiolato) ] (ΔΔ/ΛΛ-[1] ) in water. RR- and SS-tartrate selectively recognize the ΛΛ and ΔΔ isomers of [1] to produce ionic crystals of (ΛΛ-[1]) (RR-tartrate) and (ΔΔ-[1]) (SS-tartrate) , respectively, which can undergo spontaneous resolution.

Insertion of a Hydride Ion Into a Tetrasilver(I) Cluster Covered by S-Donating Rhodium(III) Metalloligands.

Here, we report a tetrahedral silver(I) cluster of {Ag} covered by Δ-[Rh(l-cys)] (l-Hcys = l-cysteine), which is converted to an {AgH} cluster via the inclusion of a H ion. The 1:1 reaction of Δ-[Rh(l-cys)] with Ag gave a sulfur-bridged AgRh octanuclear structure in [Ag{Rh(l-cys)}] ([]), in which a tetrahedral {Ag} core is bound by four Δ-[Rh(l-cys)] units through thiolato groups. DFT calculations revealed that a superatomic orbital exists in {Ag} as the lowest unoccupied molecular orbital, contributing to the appearance of a characteristic charge-transfer transition in the visible region for [].

A Dynamic Combinatorial Library of Cyclic AuNi Complexes with Cysteine/Penicillamine Showing Solvent-Controlled Crystallization.

A dynamic combinatorial library (DCL) is a set of molecular species existing in equilibrium in solution that can undergo self-assembly via reversible chemical bonds. Here, we report a unique DCL system that shows the independent crystallization of products from solvents with slightly different polarities. The reaction of a 1:1 mixture of [Au(dppm)(dl-cys)] and [Au(dppm)(dl-pen)] with Ni in solution gave a DCL containing 10 cyclic AuNi molecules of [AuNi(dppm)(dl-cys/dl-pen)].

Single-Crystal-to-Single-Crystal Installation of Ln (OH) Cubanes in an Anionic Metallosupramolecular Framework.

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K [Rh Zn O(l-cys) ] (K [1]; l-H cys=l-cysteine) in a water/ethanol solution containing Ln(OAc) (Ln =lanthanide ion) results in the exchange of K by Ln with retention of the single crystallinity, producing Ln [1] (2 ) and Ln [Ln (OH) (OAc) (H O) ][1] (3 ) for early and late lanthanides, respectively. While the Ln ions in 2 exist as disordered aqua species, those in 3 form ordered hydroxide-bridged cubane clusters that connect [1] anions in a 3D metal-organic framework through coordination bonds with carboxylate groups.

Modulating the Magnetic Properties of Copper(II)/Nitroxyl Heterospin Complexes by Suppression of the Jahn-Teller Distortion.

A series of six-coordinate [Cu(L)L][BF] (L = 2,6-bis{1-oxyl-4,4,5,5-tetramethyl-4,5-dihydro-1-imidazol-2-yl}pyridine) complexes are reported. Ferromagnetic coupling between the Cu and L ligand spins is enhanced by an L coligand with distal methyl substituents, which is attributed to a sterically induced suppression of its Jahn-Teller distortion.

Charge-Separation-Type Ionic Crystals with Mixed AuCo and AuNiCo Hexanuclear Complexes.

Treatment of a digold(I) metalloligand, [Au(dppe)(d-Hpen)] (HL; d-Hpen = d-penicillamine, dppe = 1,2-bis(diphenylphosphino)ethane), with a 1:1 mixture of Co(OAc) and Ni(OAc) under aerobic conditions resulted in the formation of three types of hexanuclear complexes: [Co(L)], [NiCo(L)], and [Ni(L)]. The addition of NaNO, MNO (M = K, Rb, Cs), and M(NO) (M = Ca, Sr, Ba) to the reaction mixture led to co-crystallization of [Co(L)] and [NiCo(L)] as a solid solution to form the charge-separation (CS)-type ionic crystals , , and , respectively, while [Ni(L)] independently crystallized as a single species (). In , [Co(L)] and [NiCo(L)] cations assemble in a 1:2 ratio to form a cationic supramolecular octahedron accommodating 4 HO ions, while 10 nitrate ions are packed in each hydrophilic tetrahedral interstice of the crystal to form an anionic adamantane cluster.

Heterochiral-to-Homochiral Structural Transformation in Metallosupramolecular Ionic Crystals.

Here, we report a unique transformation from heterochiral to homochiral structures in ionic crystals composed of complex cations and complex anions. Treatment of an anionic AuCo complex, ΛΛ-[AuCo(d-pen)] ([]; Hpen = penicillamine), with M = Mn, Co, Ni, Zn in water in the presence of 1,10-phenanthroline (phen) commonly gave ionic crystals formulated as [M(phen)(HO)][Na(HO)][{M(phen)(HO)}()] (), in which [M(phen)(HO)] and [M(phen)(HO)] adopt Δ and Λ configurations, respectively. While , , and were all stable in each mother liquor, was converted to [Mn(phen)][]·phen () containing the Λ configurational [Mn(phen)] under the same conditions.

Homoleptic versus heteroleptic trinuclear systems with mixed l-cysteinate and d-penicillaminate regulated by a diphosphine linker.

Controlled generation of homoleptic versus heteroleptic AuI2M (M = NiII, ZnII) trinuclear complexes, which is achieved by a slight change in the diphosphine P^P linker of digold(i) metalloligands, [Au2(P^P)(d-pen)2]2- (L1P^P; d-pen = d-penicillaminate) and [Au2(P^P)(l-cys)2]2- (L2P^P; l-cys = l-cysteinate), is reported. The reactions of a 1 : 1 mixture of L1dppm and L2dppm (dppm = bis(diphenylphosphino)methane) with M = NiII, ZnII gave the homoleptic AuI2M complexes, [M(L1dppm)] and [M(L2dppm)], which co-crystallized to form [M(L1dppm)]·[M(L2dppm)] (1M). Similar reactions using L1dppe and L2dppe (dppe = bis(diphenylphosphino)ethane), instead of L1dppm and L2dppm, led to the selective production and crystallization of the heteroleptic AuI2M complex, [M(L3dppe)] (2M; L3dppe = [Au2(dppe)(l-cys)(d-pen)]2-), accompanied by the scrambling of L1dppe and L2dppe.

Gas Adsorption, Proton Conductivity, and Sensing Potential of a Nanoporous Gadolinium Coordination Framework.

The new nanoporous framework [Gd(-nitro-BPDC)(NO)(OH)(HO)]·(solvent) (; -nitro-BPDC = 2,2'-dinitrobiphenyl-4,4'-dicarboxylate) has been designed and synthesized through a simple one-pot reaction. In addition to its exceptional thermal and water stabilities, exhibited multifunctional properties. A sudden CO uptake to a maximum of 4.