Anticancer approach by targeted activation of a global inhibitor of sialyltransferases with acrolein.

Cells are covered with a thick layer of sugar molecules known as glycans. Abnormal glycosylation is a hallmark of cancer, and hypersialylation increases tumor metastasis by promoting immune evasion and inducing tumor cell invasion and migration. Inhibiting sialylation is thus a potential anticancer treatment strategy.

Evaluation of ferroelectricity in a distorted wurtzite-type structure of Sc-doped LiGaO.

Since the discovery of ferroelectricity in a wurtzite-type structure, this structural type has gathered much attention as a next-generation ferroelectric material due to its high polarization value combined with its high breakdown strength. However, the main targets of wurtzite-type ferroelectrics have been limited thus far to simple nitride/oxide compounds. The investigation of new ferroelectric materials with wurtzite-type structures is important for understanding ferroelectricity in such structures.

Tunable thermal diffusivity of silk protein assemblies based on their structural control and photo-induced chemical cross-linking.

Silk, which has excellent mechanical properties and is lightweight, serves as a structural material in natural systems. However, the structural and functional applications of silk in artificial systems have been limited due to the difficulty in controlling its properties. In this study, we demonstrate the tunable thermal diffusivity of silk-based assemblies (films) based on secondary structural control and subsequent cross-linking.

Transition from vehicle to Grotthuss proton transfer in a nanosized flask: cryogenic ion spectroscopy of protonated -aminobenzoic acid solvated with DO.

Proton transfer (PT) is one of the most ubiquitous reactions in chemistry and life science. The unique nature of PT has been rationalized not by the transport of a solvated proton (vehicle mechanism) but by the Grotthuss mechanism in which a proton is transported to the nearest proton acceptor along a hydrogen-bonded network. However, clear experimental evidence of the Grotthuss mechanism has not been reported yet.

A rational design strategy of radical-type mechanophores with thermal tolerance.

Radical-type mechanophores (RMs) are attractive molecules that undergo homolytic scission of their central C-C bond to afford radical species upon exposure to heat or mechanical stimuli. However, the lack of a rational design concept limits the development of RMs with pre-determined properties. Herein, we report a rational design strategy of RMs with high thermal tolerance while maintaining mechanoresponsiveness.

Energetic and Kinetic Origins of CALB Interfacial Activation Revealed by PaCS-MD/MSM.

The conformational dynamics of lipase B (CALB) was investigated by molecular dynamics (MD) simulation, parallel cascade selection MD (PaCS-MD), and the Markov state model (MSM) and mainly focused on the lid-opening motion closely related to substrate binding. All-atom MD simulation of CALB was conducted in water and on the interface of water and tricaprylin. CALB initially situated in water and separated by layers of water from the interface is spontaneously adsorbed onto the tricaprylin surface during MD simulation.

Therapeutic efficacy of At-radiolabeled 2,6-diisopropylphenyl azide in mouse models of human lung cancer.

Targeted α-particle therapy (TAT) is an attractive alternative to conventional therapy for cancer treatment. Among the available radionuclides considered for TAT, astatine-211 (At) attached to a cancer-targeting molecule appears very promising. Previously, we demonstrated that aryl azide derivatives could react selectively with the endogenous acrolein generated by cancer cells to give a diazo compound, which subsequently forms a covalent bond with the organelle of cancer cells .

Improved supercapacitor performances by adding carbonized C-based nanospheres to PVA/TEMPO-cellulose hydrogel-based electrolyte.

With the emergence of the energy crisis and the development of flexible electronics, there is an urgent need to develop new reliable energy supply devices with good flexibility, stable energy storage, and efficient energy transfer. Porous carbon materials have been proven to enhance the efficiency of ion transport, as the nanospaces within them serve as pathways for mass transport. However, they have been mainly investigated in the electrodes of supercapacitors and batteries.

Facile formation of barium titanium oxyhydride on a titanium hydride surface as an ammonia synthesis catalyst.

Oxyhydrides are promising compounds as supports for ammonia synthesis catalysts because they suppress hydrogen poisoning on the catalyst surface and enhance the ammonia synthesis activity. Herein, we developed a facile method for preparing BaTiOH, a perovskite oxyhydride, on a TiH surface the conventional wet impregnation method using TiH and Ba hydroxide. Scanning electron microscopy and high-angle annular dark-field scanning transmission electron microscopy observations revealed that BaTiOH crystallized as nanoparticles of 100-200 nm on the TiH surface.

Control of intramolecular singlet fission in a pentacene dimer by hydrostatic pressure.

Singlet fission (SF), which produces two triplet excitons from a singlet exciton, has been identified as a novel nanointerface for efficient (photo)energy conversion. This study aims to control exciton formation in a pentacene dimer through intramolecular SF using hydrostatic pressure as an external stimulus. We reveal the hydrostatic-pressure-induced formation and dissociation processes of correlated triplet pairs (TT) in SF by means of pressure-dependent UV/vis and fluorescence spectrometry and fluorescence lifetime and nanosecond transient absorption measurements.

Overcoming the entropy of polymer chains by making a plane with terminal groups: a thermoplastic PDMS with a long-range 1D structural order.

Due to its unique physical and chemical properties, polydimethylsiloxane (PDMS) is widely used in many applications, in which covalent cross-linking is commonly used to cure the fluidic polymer. The formation of a non-covalent network achieved through the incorporation of terminal groups that exhibit strong intermolecular interactions has also been reported to improve the mechanical properties of PDMS. Through the design of a terminal group capable of two-dimensional (2D) assembly, rather than the generally used multiple hydrogen bonding motifs, we have recently demonstrated an approach for inducing long-range structural ordering of PDMS, resulting in a dramatic change in the polymer from a fluid to a viscous solid.

The factors that govern the allosteric chemical sensing of polythiophene chemosensors: scope and limitation toward signal-amplification sensing.

The newly designed polythiophene chemosensors (PT1 and PT2) were synthesized the Suzuki-Miyaura polymerization with appropriate yields. The photophysical properties of PTs thus obtained were examined by means of UV/vis, fluorescence, excitation spectroscopy, and time-correlated single-photon-counting method. The π-π* transitions around 400-600 nm and the emissions in the range of 400-650 nm were observed.

Kinetic and deuterium isotope analyses of ammonia electrochemical synthesis.

The mechanism of electrochemical promotion of ammonia formation was investigated by kinetic and deuterium isotope analyses using a cell with a Pt (anode)|BaCeYO (BCY)|Fe (cathode) configuration on the introduction of a gaseous mixture of H(D)-N to the cathode at 550 °C. To clarify the mechanism of electrochemical ammonia synthesis, the reaction orders for hydrogen, , and nitrogen, , were investigated. The values of and did not change after applying a negative voltage, which indicates that the reaction mechanism at rest potential is the same as that with cathodic polarization.

Green route for ammonium nitrate synthesis: fertilizer for plant growth enhancement.

Soil fertility management is of great importance for farmers. The use of synthetic nitrogen (N)-fertilizer increased by 20 fold in the last 50 years to feed the increasingly hungry population. This study aims to enrich the plant soil with nitrogen content (NHNO fertilizer in soil) using the low-temperature and low-pressure plasma [without H and catalyst].

Targeted 1,3-dipolar cycloaddition with acrolein for cancer prodrug activation.

Cytotoxic anticancer drugs used in chemotherapy are often antiproliferative agents that preferentially kill rapidly growing cancer cells. Their mechanism relies mainly on the enhanced proliferation rate of cancer cells and is not genuinely selective for cancer cells. Therefore, these drugs can also significantly affect healthy cells.

Nanoporous ultra-high-entropy alloys containing fourteen elements for water splitting electrocatalysis.

High-entropy alloys (HEAs) are near-equimolar alloys comprising five or more elements. In recent years, catalysis using HEAs has attracted considerable attention across various fields. Herein, we demonstrate the facile synthesis of nanoporous ultra-high-entropy alloys (np-UHEAs) with hierarchical porosity dealloying.

metal-catalyzed SeCT therapy by a proapoptotic peptide.

Selective cell tagging (SeCT) therapy is a strategy for labeling a targeted cell with certain chemical moieties a catalytic chemical transformation in order to elicit a therapeutic effect. Herein, we report a cancer therapy based on targeted cell surface tagging with proapoptotic peptides (Ac-GGKLFG-X; X = reactive group) that induce apoptosis when attached to the cell surface. Using either Au-catalyzed amidation or Ru-catalyzed alkylation, these proapoptotic peptides showed excellent therapeutic effects both and .

Control of dominant conduction orbitals by peripheral substituents in paddle-wheel diruthenium alkynyl molecular junctions.

Control of charge carriers that transport through the molecular junctions is essential for thermoelectric materials. In general, the charge carrier depends on the dominant conduction orbitals and is dominantly determined by the terminal anchor groups. The present study discloses the synthesis, physical properties in solution, and single-molecule conductance of paddle-wheel diruthenium complexes having diarylformamidinato supporting ligands (DArF: -R-CH-NCHN-CH-R-) and two axial thioanisylethynyl conducting anchor groups, revealing unique substituent effects with respect to the conduction orbitals.

Cyclic monoterpenes trapped in a polyaromatic capsule: unusual selectivity, isomerization, and volatility suppression.

Cyclic monoterpenes (CMTs) are intractable natural products with high volatility and strong odors so that there has been no molecular receptor capable of selectively and tightly trapping CMTs in both solution and the solid state. We herein report that a polyaromatic capsule acts as a functional nanoflask for CMTs with the following five features: (i) the capsule can selectively bind menthone from mixtures with other saturated CMTs in water. In contrast, (ii) treatment of the capsule with mixtures of menthone and π-conjugated CMTs gives rise to ternary host-guest complexes with high pair-selectivity.

Pressure-driven, solvation-directed planar chirality switching of cyclophano-pillar[5]arenes (molecular universal joints).

Planar chiral cyclophanopillar[5]arenes with a fused oligo(oxyethylene) or polymethylene subring (s), existing as an equilibrium mixture of subring-included (in) and -excluded (out) conformers, respond to hydrostatic pressure to exhibit dynamic chiroptical property changes, leading to an unprecedented pressure-driven chirality inversion and the largest ever-reported leap of anisotropy () factor for the with a dodecamethylene subring. The pressure susceptivity of s, assessed by the change in per unit pressure, is a critical function of the size and nature of the subring incorporated and the solvent employed. Mechanistic elucidations reveal that the in-out equilibrium, as the origin of the 's chiroptical property changes, is on a delicate balance of the competitive inclusion of subrings solvent molecules as well as the solvation of the excluded subring.

Single-molecule junctions of multinuclear organometallic wires: long-range carrier transport brought about by metal-metal interaction.

Here, we report multinuclear organometallic molecular wires having (2,5-diethynylthiophene)diyl-Ru(dppe) repeating units. Despite the molecular dimensions of 2-4 nm the multinuclear wires show high conductance (up to 10 to 10 ) at the single-molecule level with small attenuation factors () as revealed by STM-break junction measurements. The high performance can be attributed to the efficient energy alignment between the Fermi level of the metal electrodes and the HOMO levels of the multinuclear molecular wires as revealed by DFT-NEGF calculations.

Ground- and excited-state dynamic control of an anion receptor by hydrostatic pressure.

Stimulus-responsive supramolecular architectures have become an attractive alternative to conventional ones for many applications in sensing, drug-delivery and switchable memory systems. Herein, we used an anion receptor (: host) as a hydrostatic-pressure-manipulatable fluorescence foldamer and halide anions as chiral (binaphthylammonium) and achiral (tetrabutylammonium) ion pairs ( or X and TBA·X; X = Cl, Br), and then investigated their (chir)optical properties and molecular recognition behavior under hydrostatic pressures. The conformational changes and optical properties of in various organic solvents were revealed by UV/vis absorption and fluorescence spectra and fluorescence lifetimes upon hydrostatic pressurization.

On single-electron magnesium bonding formation and the effect of methyl substitution.

The complexes formed between MgX (X = F, H) molecules and alkyl radicals Y [Y = CH, CHCH, CH(CH), and C(CH)] have been characterized by using quantum chemical methods. The binding distance in all cases is less than the sum of vdW radii of Mg and C, indicating the formation of a non-covalent interaction, namely single-electron magnesium bond. Energy decomposition analysis reveals that electrostatic and polarization contributions are the major components responsible for the stability of the studied complexes.

Solution-mediated nanometric growth of α-FeO with electrocatalytic activity for water oxidation.

This paper describes a simple, low-temperature, and environmentally friendly aqueous route for the layer-by-layer nanometric growth of crystalline α-FeO. The formation mechanism involves alternative sequences of the electrostatic adsorption of Fe ions on the surface and the subsequent onsite oxidation to Fe. A combination analysis of X-ray diffraction, scanning electron microscopy, UV-Vis spectroscopy, and X-ray photoelectron spectroscopy revealed that α-FeO is directly formed without post-growth annealing designed chemical reactions with a growth rate of 1.

Controlled assembly of filamentous viruses into hierarchical nano- to microstructures at liquid/liquid interfaces.

Recently, viruses have been regarded as useful molecular assemblies for materials applications rather than as disease-causing agents. The orderly assembled structures of the viruses are highly related to the resultant properties and functions of the assemblies; however, methods to control the assembly are still limited. Here, we demonstrated the assembly of filamentous viruses into hierarchical nano- to microstructures at liquid/liquid interfaces through emulsification in a controlled manner.