Bis‐copper(II) Complex of Triply‐linked Corrole Dimer and Its Dication

Copper complexes of corroles have recently been a subject of keen interest due to their ligand non‐innocent character and unique redox properties. Here we investigated bis‐copper complex of a triply‐linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply‐linked corrole dimer 2 with Cu(acac)₂ (acac=acetylacetonate) gave bis‐copper(II) complex 2Cu as a highly planar molecule with a mean‐plane deviation value of 0.020 Å, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF₄ gave complex 3Cu , which was characterized as a bis‐copper(II) complex of a dicationic triply‐linked corrole dimer not as the corresponding bis‐copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu . Importantly, the magnetic spin–spin interaction differs depending on the redox‐state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu .     

Sol–gel synthesis of macro–mesoporous titania monoliths and their applications to chromatographic separation media for organophosphate compounds

We have developed a method of independently tailoring the macro- and mesoporous structures in titania (TiO₂) monoliths in order to achieve liquid chromatographic separations of phosphorous-containing compounds. Anatase TiO₂ monolithic gels with well-defined bicontinuous macropores and microstructured skeletons are obtained via the sol–gel process in strongly acidic conditions using poly(ethylene oxide) as a phase separator and N-methylformamide as a proton scavenger. Aging treatment of the wet gels in the mother liquor at temperatures of 100–200 °C and subsequent heat treatment at 400 °C allow the formation and control of mesoporous structures with uniform pore size distributions in the gel skeletons, without disturbing the preformed macroporous morphology. The monolithic TiO₂ rod columns with bimodal macro–mesoporous structures possess the phospho-sensitivity and exhibit excellent chromatographic separations of phosphorus-containing compounds.     

Multifunctional photo acid generator for fluorescence imaging based on self-contained photoreaction

We present N-(p-anilinesulfonyloxy)-1,8-naphthalimide (ASNI) as fluorescence imaging material based on a novel fluorescence imaging mechanism. ASNI is composed of two functional moieties in one molecule: an acid-reactive fluorescence probe and a photoacid generator (PAG). When ASNI is photoirradiated, a bond in the PAG moiety breaks and an acid is generated. The fluorescence probe moiety then detects the acid and fluoresces. We call this novel mechanism a self-contained photoreaction (SCP). The photophysical properties and photoreactivity of ASNI were measured and compared with those of a prototype PAG, N-(phenylsulfonyloxy)-1,8-naphthalimide. These were well represented by density functional theory calculations. SCP permits one-step fluorescence imaging without any wet or dry developing process.     

Membrane-Vesicle-Mediated Interbacterial Communication Activates Silent Secondary Metabolite Production

Most bacterial biosynthetic gene clusters (BGCs) are “silent BGCs” that are expressed poorly or not at all under normal culture conditions. However, silent BGCs, even in part, may be conditionally expressed in response to external stimuli in the original bacterial habitats. The growing knowledge of bacterial membrane vesicles (MVs) suggests that they could be promising imitators of the exogenous stimulants, especially given their functions as signaling mediators in bacterial cell-to-cell communication. Therefore, we envisioned that MVs added to bacterial cultures could activate diverse silent BGCs. Herein, we employed Burkholderia multivorans MVs, which induced silent metabolites in a wide range of bacteria in Actinobacteria, Bacteroidetes and Proteobacteria phyla. A mechanistic analysis of MV-induced metabolite production in Xenorhabdus innexi suggested that the B. multivorans MVs activate silent metabolite production by inhibiting quorum sensing in X. innexi. In turn, the X. innexi MVs carrying some MV-induced peptides suppressed the growth of B. multivorans, highlighting the interspecies communication between B. multivorans and X. innexi through MV exchange.     

Initiating Mobilization Is Not Associated with Symptomatic Cerebral Vasospasm in Patients with Aneurysmal Subarachnoid Hemorrhage: A Retrospective Multicenter Case-control Study

Objective: The study aim was to investigate the association between initiating mobilization within 7 days after onset and symptomatic cerebral vasospasm (SCV) in patients with aneurysmal subarachnoid hemorrhage (aSAH). Methods: This was a retrospective multicenter case-control study in Japan. Patients with a diagnosis of aSAH who underwent physical therapy with/without occupational therapy were included and categorized into 2 groups according to the presence or absence of SCV. Initiating mobilization was defined as sitting on the bed edge (at least once, with/without assist, regardless of duration) within 7 days after aSAH onset. Cox proportional hazards regression analysis was performed to evaluate the association between initiating mobilization within 7 days after onset and SCV. Results: The analysis included 510 patients. Among all included patients, 57 (11.2%) patients had SCV. In the univariate Cox proportional hazards regression analysis, initiating of mobilization was not associated with SCV (hazard ratio [HR] = 0.78; 95% confidence interval [CI] = 0.45–1.32). In the multivariate analysis, only the modified Fisher scale was significantly associated with SCV (HR = 26.23; 95% CI = 1.21–571.0). Conclusion: Initiating mobilization within 7 days after aSAH onset was not associated with SCV in patients with aSAH.     

Stereospecific [2+2] cycloaddition reactions of diphosphorus with alkenes

[2+2] Cycloaddition reactions of P₂ with alkenes were predicted to have concerted paths, that is, pseudoexcitation, distorted 2π_s+2π_s, and 2π_s+2π_a processes without any interventions of intermediates. The pseudoexcitation and/or distorted 2π_s+2π_s paths with retention of configuration of alkenes are kinetically preferred to the 2π_s+2π_a path with inversion of configuration. The reactions were predicted from the appreciable difference in the calculated enthalpies of activation to be stereospecific.     

Stable meso–meso-Linked 2NH-Corrole Radical Dimers as a Key Intermediate to Corrole Tape

While oxidation of 5,5′,15,15′-tetramesityl-10-10′-linked 3NH-corrole dimer with DDQ gave the corresponding triply linked 2NH-corrole tape, the use of an equimolar amount of p-chloranil as a milder oxidant resulted in the formation of a 10-10′-linked neutral 2NH-corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10-10′-linked bis-pyridine-coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.     

Synthesis of poly(Nε-phenoxycarbonyl-l-lysine) by polycondensation of activated urethane derivative and its application for selective modification of side chain with amines

We report a methodology for the synthesis of Nε-phenoxycarbonyl-protected poly(l -lysine) on the side chain by chain growth polycondensation of Nα,Nε-bis(phenoxycarbonyl)-l -lysine proceeded through the selective elimination of phenol and CO₂ from the Nα phenoxycarbonyl moiety at 50 °C in N,N-dimethylacetamide in the presence of a primary amine used as an initiator. After optimization of reaction condition, the addition of acetic acid during polycondensation proved effective for the realization of the predicted molecular weight and narrow dispersity of the corresponding polypeptide by adjusting the feed ratio of monomer to the amine initiator because of the suppression of interchain coupling that occurs between the amino terminus of poly(l -lysine) and the Nε-phenoxycarbonyl group on the polymer side chains. Furthermore, taking advantage of the potentially reactive Nε-phenoxycarbonyl moiety on the side chain, post-polymerization modification was effectively achieved by the nucleophilic reaction of amine compounds including primary, secondary, and aromatic amines through the formation of urea linkage, providing a useful platform for synthesis of selective side chain functionalization of poly(l -lysine) samples. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2522–2530