Bidirectionally connected cores in a mouse connectome: towards extracting the brain subnetworks essential for consciousness.

Where in the brain consciousness resides remains unclear. It has been suggested that the subnetworks supporting consciousness should be bidirectionally (recurrently) connected because both feed-forward and feedback processing are necessary for conscious experience. Accordingly, evaluating which subnetworks are bidirectionally connected and the strength of these connections would likely aid the identification of regions essential to consciousness.

Superior Multielectron-Transferring Energy Storage by π-d Conjugated Frameworks.

Reversible multielectron-transfer materials are of considerable interest because of the potential impact to advance present electrochemical energy storage technology by boosting energy density. To date, a few oxide-based materials can reach an electron-transfer number per metal-cation (e ) larger than 2 upon a (de)intercalation mechanism. However, these materials suffer from degradation due to irreversible rearrangements of the cation-oxygen bonds, and are based on precious metals, for example, Ir and Ru.

Variable control of the electronic states of a silver nanocluster protonation/deprotonation of polyoxometalate ligands.

The properties of metal nanoclusters depend on both their structures and electronic states. However, in contrast to the significant advances achieved in the synthesis of structurally well-defined metal nanoclusters, systematic control of their electronic states is still challenging. In particular, stimuli-responsive and reversible control of the electronic states of metal nanoclusters is attractive from the viewpoint of their practical applications.

Amplification of weak chiral inductions for excellent control over the helical orientation of discrete topologically chiral (ML) polyhedra.

Superb control over the helical chirality of discrete (ML) polyhedra ( = 2,4,8, M = Cu or Ag) created from the self-assembly of propeller-shaped ligands (L) equipped with chiral side chains is demonstrated here. Almost perfect chiral induction (>99 : 1) of the helical orientation of the framework was achieved for the largest (ML) cube with 48 small chiral side chains (diameter: ∼5 nm), while no or moderate chiral induction was observed for smaller polyhedra ( = 2, 4). Thus, amplification of the weak chiral inductions of each ligand unit is an efficient way to control the chirality of large discrete nanostructures with high structural complexity.

Evaluation of enzymatic and magnetic properties of γ-glutamyl-[1-C]glycine and its deuteration toward longer retention of the hyperpolarized state.

Dynamic nuclear polarization (DNP) is an emerging cutting-edge method of acquiring metabolic and physiological information . We recently developed γ-glutamyl-[1-C]glycine (γ-Glu-[1-C]Gly) as a DNP nuclear magnetic resonance (NMR) molecular probe to detect γ-glutamyl transpeptidase (GGT) activity . However, the detailed enzymatic and magnetic properties of this probe remain unknown.

Tracking the crystallization behavior of high-silica FAU during AEI-type zeolite synthesis using acid treated FAU-type zeolite.

During AEI zeolite synthesis using acid treated FAU (AcT-FAU), we found the recrystallization of high-silica FAU with high crystallinity and Si/Al ratio of 6.1 using ,-dimethyl-3,5-dimethylpiperidinium hydroxide (DMDMPOH) after 2 h, followed by the crystallization of AEI FAU-to-AEI interzeolite conversion at a longer synthesis time. In order to understand the formation mechanism of high-silica FAU and generalize its direct synthesis, we have investigated this synthesis process.

On-demand retrieval of cells three-dimensionally seeded in injectable thioester-based hydrogels.

Scaffold systems that can easily encapsulate cells and safely retrieve them at the desired time are important for the advancement of cell-based medicine. In this study, we designed and fabricated thioester-based poly(ethylene glycol) (PEG) hydrogels with injectability and on-demand degradability as new scaffold materials for cells. Hydrogels can be formed within minutes thioester cross-linking between PEG molecules and can be degraded under mild conditions in response to l-cysteine molecules through thiol exchange occurring at the thioester linkage.

Development of highly efficient Friedel-Crafts alkylations with alcohols using heterogeneous catalysts under continuous-flow conditions.

The development of Friedel-Crafts alkylations with alcohols under continuous-flow conditions using heterogeneous catalysts is reported. The reactivities and durabilities of the examined catalysts were systematically investigated, which showed that montmorillonite clay is the best catalyst for these reactions. A high turnover frequency of 9.

Metal-mediated DNA base pairing of easily prepared 2-oxo-imidazole-4-carboxylate nucleotides.

Metal-mediated DNA base pairs, which consist of two ligand-type artificial nucleobases and a bridging metal ion, have attracted increasing attention in recent years as a different base pairing mode from natural base pairing. Metal-mediated base pairing has been extensively studied, not only for metal-dependent thermal stabilisation of duplexes, but also for metal assembly by DNA templates and construction of functional DNAs that can be controlled by metals. Here, we report the metal-mediated base paring properties of a novel 2-oxo-imidazole-4-carboxylate (Im) nucleobase and a previously reported 2-oxo-imidazole-4-carboxamide (Im) nucleobase, both of which can be easily derived from a commercially available uridine analogue.

Facile and wide-range size tuning of conjugated polymer nanoparticles for biomedical applications as a fluorescent probe.

Conjugated polymer nanoparticles (Pdots) are expected to be novel bioimaging and sensing probes. However, the size tuning required to control biological interactions has not been well established. Herein, we achieved a size-tunable synthesis of Pdots ranging from 30 to 200 nm by controlling the hydrolysis rate of the stabilising agent and evaluated their cellular imaging properties.

Free-standing conductive hydrogel electrode for potentiometric glucose sensing.

Flexible conductive polymer hydrogels are attracting attention as an electrode material. Electrochemical biosensors with conductive polymer hydrogels have been developed because they have some advantages such as biocompatibility, high conductivity, 3D nanostructure, solvated surface, and enlarged interface. Conductive polymer hydrogels bearing receptor molecules such as enzymes in its 3D nanostructure enable the detection of target analytes with high sensitivity.

Organoruthenium-catalyzed chemical protein synthesis to elucidate the functions of epigenetic modifications on heterochromatin factors.

The application of organometallic compounds for protein science has received attention. Recently, total chemical protein synthesis using transition metal complexes has been developed to produce various proteins bearing site-specific posttranslational modifications (PTMs). However, in general, significant amounts of metal complexes were required to achieve chemical reactions of proteins bearing a large number of nucleophilic functional groups.

Nifekalant versus Amiodarone for Out-Of-Hospital Cardiac Arrest with Refractory Shockable Rhythms; a Post Hoc Analysis.

Introduction: It is still unclear that which anti-arrhythmics are adequate for treating refractory dysrhythmia. This study aimed to compare amiodarone and nifekalant in management of out-of-hospital cardiac arrest cases with refractory shockable rhythm.

Methods: This was a post hoc analysis of cases registered in a nationwide, multicentre, prospective registry that includes 288 critical care medical centres in Japan.

Generation of organo-alkaline earth metal complexes from non-polar unsaturated molecules and their synthetic applications.

Organomagnesium compounds, represented by the Grignard reagents, are one of the most classical yet versatile carbanion species which have widely been utilized in synthetic chemistry. These reagents are typically prepared oxidative addition of organic halides to magnesium metals, halogen-magnesium exchange between halo(hetero)arenes and organomagnesium reagents or deprotonative magnesiation of prefunctionalized (hetero)arenes. On the other hand, recent studies have demonstrated that the organo-alkaline earth metal complexes including those based on heavier alkaline earth metals such as calcium, strontium and barium could be generated from readily available non-polar unsaturated molecules such as alkenes, alkynes, 1,3-enynes and arenes through unique metallation processes.

Pit aspiration causes an apparent loss of xylem hydraulic conductivity in a subalpine fir (Abies mariesii Mast.) overwintering at the alpine timberline.

Conifers growing at the alpine timberline are exposed to combinatorial stresses that induce embolism in xylem during winter. We collected branches of Abies mariesii Mast. at the timberline on Mt Norikura of central Japan to evaluate the seasonal changes in the loss of xylem hydraulic conductivity (percent loss of hydraulic conductivity; PLC).

A comprehensive study on the effect of backbone stereochemistry of a cyclic hexapeptide on membrane permeability and microsomal stability.

Backbone stereochemistry of cyclic peptides has been reported to have a great influence on microsomal stability and membrane permeability, two important factors that determine oral bioavailability. Here, we comprehensively investigated the correlation between the backbone stereochemistry of cyclic hexapeptide stereoisomers and their stability in liver microsomes, as well as passive membrane permeability.

Peptoid-based reprogrammable template for cell-permeable inhibitors of protein-protein interactions.

The development of inhibitors of intracellular protein-protein interactions (PPIs) is of great significance for drug discovery, but the generation of a cell-permeable molecule with high affinity to protein is challenging. Oligo(-substituted glycines) (oligo-NSGs), referred to as peptoids, are attractive as potential intracellular PPI inhibitors owing to their high membrane permeability. However, their intrinsically flexible backbones make the rational design of inhibitors difficult.

Revisiting molecular adsorption: unconventional uptake of polymer chains from solution into sub-nanoporous media.

Adsorption of polymers from the solution phase has been extensively studied to cope with many demands not only for separation technologies, but also for the development of coatings, adhesives, and biocompatible materials. Most studies hitherto focus on adsorption on flat surfaces and mesoporous adsorbents with open frameworks, plausibly because of the preconceived notion that it is unlikely for polymers to enter a pore with a diameter that is smaller than the gyration diameter of the polymer in solution; therefore, sub-nanoporous materials are rarely considered as a polymer adsorption medium. Here we report that polyethylene glycols (PEGs) are adsorbed into sub-nanometer one-dimensional (1D) pores of metal-organic frameworks (MOFs) from various solvents.

Accessing Divergent Main-Chain-Functionalized Polyethylenes via Copolymerization of Ethylene with a CO/Butadiene-Derived Lactone.

Carbon dioxide (CO) has been used as a sustainable comonomer in the synthesis of different functional polymers including polycarbonates, polyurea, and polyurethane. Until today, despite the great interest, little success has been made for incorporating CO into the most widely used polyethylene materials. Herein, we report the incorporation of CO to polyethylenes through the copolymerization of ethylene with a CO/butadiene-derived lactone, 3-ethylidene-6-vinyltetrahydro-2-pyran-2-one (EVP).

An IrL complex with anion binding pockets: photocatalytic - isomerization molecular recognition.

A molecular host with photosensitizing centers provides photo-responsive host-guest properties based on its molecular recognition ability. Here, we construct a self-assembled photoactive Ir() cage-shaped complex that contains anion binding pockets on its rim. The anion recognition ability of the complex enables efficient catalysis of the visible-light-induced - isomerization of an anionic styrene derivative.

Correction: modulation of ubiquitin chains by -methylated non-proteinogenic cyclic peptides.

[This corrects the article DOI: 10.1039/D0CB00179A.].

Biosynthesis of alkyne-containing natural products.

Alkyne-containing natural products are important molecules that are widely distributed in microbes and plants. Inspired by the advantages of acetylenic products used in the fields of medicinal chemistry, organic synthesis and material science, great efforts have focused on discovering the biosynthetic enzymes and pathways for alkyne formation. Here, we summarize the biosyntheses of alkyne-containing natural products and introduce biosynthetic strategies for alkyne-tagged compound production.

The first year of - a new journal was born.

News from Hiroaki Suga, the Editorial Board Chair of .

The origin of unidirectional charge separation in photosynthetic reaction centers: nonadiabatic quantum dynamics of exciton and charge in pigment-protein complexes.

Exciton charge separation in photosynthetic reaction centers from purple bacteria (PbRC) and photosystem II (PSII) occurs exclusively along one of the two pseudo-symmetric branches (active branch) of pigment-protein complexes. The microscopic origin of unidirectional charge separation in photosynthesis remains controversial. Here we elucidate the essential factors leading to unidirectional charge separation in PbRC and PSII, using nonadiabatic quantum dynamics calculations in conjunction with time-dependent density functional theory (TDDFT) with the quantum mechanics/molecular mechanics/polarizable continuum model (QM/MM/PCM) method.

Asymmetric synthesis, structures, and chiroptical properties of helical cycloparaphenylenes.

Planar chiral carbon nanorings and nanobelts (CNRs and CNBs), the sidewall segment molecules of chiral-type carbon nanotubes (CNTs), have attracted attention owing to their characteristic chiroptical properties. From the appropriate CNTs, axially or planar chiral CNRs and CNBs have been designed and synthesized, but multiply helical sidewall segments were almost unexplored due to the difficulty in simultaneous control of multiple chiralities. In this article, we have succeeded in the perfectly diastereo- and enantiocontrolled catalytic synthesis of a cycloparaphenylene with four helical and two planar chiralities showing good chiroptical responses as chiral organic molecules.