Anomalous System Size Dependence of Large Deviation Functions for Local Empirical Measure

We study the large deviation function for the empirical measure (the time-averaged density) of diffusing particles at one fixed position. We find that the large deviation function exhibits anomalous system size dependence in systems with translational symmetry if and only if they satisfy the following conditions: (i) there exists no macroscopic flow, and (ii) their space dimension is one or two. We investigate this anomaly by using a contraction principle. We also analyze the relation between this anomaly and the so-called long-time tail behavior on the basis of phenomenological arguments.     

Synthesis of Adamantane Derivatives. Xxiii. Facile Photo-Ring-Cleavage of 4-Homoadamantanone to Bicyclo[3.3.1] -Nonan-3 -Endo-Acetate

Type I (α-) and II cleavages are two of the best known photochemical processes of alkanone.² Extensive and intensive investigations have been done on both types of reactions in order to clarify the influence of structural changes on the reactivity, specificity, and efficiency of photoreactions of alkanones.³ The type I cleavage of medium-ring alkanones is believed to produce a radical pair, the fate of which will be determined by the ready formation of transition states for transfer of Ha, Hb, and recyclization. We now wish to report     

First-principles calculations of stable local structures and electronic structures of magnesium secondary battery cathode materials,MgCo2−xMnxO4 (x = 0, 0.5), in second charged state after first discharge

Journal of Solid State Electrochemistry - The stable structures associated with the second charge of MgCo2−xMnxO4 (x = 0, 0.5), where Mg is removed from the stable first-discharge...     

Enormously extended π-electronic conjugation system of dimeric octaethylporphyrin transmitted with anthracene

Based on the fact that anthracene (Anth) possesses much higher similarity in electron-releasing ability to porphyrin nucleus than the other polyacenes, the dimeric octaethylporphyrin (OEP) derivatives 4 and 5 (OEP–Anth–OEP) were synthesized and their structure–property relationships were examined, as compared with related OEP dimers 1–3. Among them, the derivative 4 showed enormously high electronic communication between two terminal OEP rings, potentially providing a suitable unit of the electronic structure for molecular design of the OEP devices operating with less energy and with higher sensitivity to outside stimuli.     

Single-mode single-polarization holey fiber using anisotropic fundamental space-filling mode

We present the single-mode single-polarization regime of a circular-hole holey fiber consisting of a core with large elliptical holes. The elliptical holes in the core, which produce large anisotropies, split the fundamental mode into two orthogonally polarized fundamental modes, often referred to as slow and fast modes. This fiber can guide only one polarization state of the fundamental mode when a fundamental space-filling mode index of the cladding region is designed to lie between these indices of the slow and fast modes of the core region. We demonstrate one design example of this fiber and show that the single-polarization regime can be achieved over a wide wavelength range.     

Single‐Crystal‐like Nanoporous Spinel Oxides: A Strategy for Synthesis of Nanoporous Metal Oxides Utilizing Metal‐Cyanide Hybrid Coordination Polymers

Development of a new method to synthesize nanoporous metal oxides with highly crystallized frameworks is of great interest because of their wide use in practical applications. Here we demonstrate a thermal decomposition of metal‐cyanide hybrid coordination polymers (CPs) to prepare nanoporous metal oxides. During the thermal treatment, the organic units (carbon and nitrogen) are completely removed, and only metal contents are retained to prepare nanoporous metal oxides. The original nanocube shapes are well‐retained even after the thermal treatment. When both Fe and Co atoms are contained in the precursors, nanoporous Fe?Co oxide with a highly oriented crystalline framework is obtained. On the other hand, when nanoporous Co oxide and Fe oxide are obtained from Co‐ and Fe‐contacting precursors, their frameworks are amorphous and/or poorly crystallized. Single‐crystal‐like nanoporous Fe?Co oxide shows a stable magnetic property at room temperature compared to poly‐crystalline metal oxides. We further extend this concept to prepare nanoporous metal oxides with hollow interiors. Core‐shell heterostructures consisting of different metal‐cyanide hybrid CPs are prepared first. Then the cores are dissolved by chemical etching using a hydrochloric acid solution (i.e., the cores are used as sacrificial templates), leading to the formation of hollow interiors in the nanocubes. These hollow nanocubes are also successfully converted to nanoporous metal oxides with hollow interiors by thermal treatment. The present approach is entirely different from the surfactant‐templating approaches that traditionally have been utilized for the preparation of mesoporous metal oxides. We believe the present work proves a new way to synthesize nanoporous metal oxides with controlled crystalline frameworks and architectures.     

Characterization of Radical SAM Adenosylhopane Synthase,HpnH, which Catalyzes the 5′‐Deoxyadenosyl Radical Addition to Diploptene in the Biosynthesis of C35 Bacteriohopanepolyols

Adenosylhopane is a crucial intermediate in the biosynthesis of bacteriohopanepolyols, which are widespread prokaryotic membrane lipids. Herein, it is demonstrated that reconstituted HpnH, a putative radical S‐adenosyl‐l ‐methionine (SAM) enzyme, commonly encoded in the hopanoid biosynthetic gene cluster, converts diploptene into adenosylhopane in the presence of SAM, flavodoxin, flavodoxin reductase, and NADPH. NMR spectra of the enzymatic reaction product were identical to those of synthetic (22R)‐adenosylhopane, indicating that HpnH catalyzes stereoselective C?C formation between C29 of diploptene and C5′ of 5′‐deoxyadenosine. Further, the HpnH reaction in D₂O‐containing buffer revealed that a D atom was incorporated at the C22 position of adenosylhopane. Based on these results, we propose a radical addition reaction mechanism catalyzed by HpnH for the formation of the C₃₅ bacteriohopane skeleton.     

Chemo‐ and Enantioselective Oxidative α‐Azidation of Carbonyl Compounds

We report high‐performance I⁺/H₂O₂ catalysis for the oxidative or decarboxylative oxidative α‐azidation of carbonyl compounds by using sodium azide under biphasic neutral phase‐transfer conditions. To induce higher reactivity especially for the α‐azidation of 1,3‐dicarbonyl compounds, we designed a structurally compact isoindoline‐derived quaternary ammonium iodide catalyst bearing electron‐withdrawing groups. The nonproductive decomposition pathways of I⁺/H₂O₂ catalysis could be suppressed by the use of a catalytic amount of a radical‐trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late‐stage α‐azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α‐azidation of 1,3‐dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.     

Ir(III)‐Catalyzed C7‐Position‐Selective Oxidative CH Alkenylation of Indolines with Alkenes in Air

An efficient method for C7‐position‐selective alkenylation of N‐substituted indolines with alkenes is reported. Various 7‐alkenylindolines were obtained in moderate to excellent yields in air in the presence of catalytic amounts of [Cp*IrCl₂]₂, AgOTf, and Cu(OAc)₂. The protocol relies on the use of a carbonyl or carbamoyl group on the nitrogen atom of indoline as a directing group and is potentially applicable to the synthesis of 7‐alkenylindoles and 7‐alkylindoles.