A series of novel praseodymium (Pr)-bonded polymers with fluorene, phthalimide and phenanthroline moieties in the main chain were synthesized via the coordination reaction and palladium-catalyzed Suzuki coupling reaction. The resistive switching devices with the configuration ITO/Polymer/Al exhibited nonvolatile write-once-read-many-times (WORM) memory behavior. The introduction of Pr complex into the polymer main chain played a key role in the memory performance of the devices.

Extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory has been the most commonly used theory to analyze the adhesion of bacteria on a solid surface. The adhesion of Shewanella oneidensis MR-1 on an electrode surface would directly affect the electricity production performance of microbial fuel cells (MFCs). In this paper, an analytical method for the adhesion between electricigens and electrode surface was established and its feasibility was verified based on the extended DLVO theory. The surface free energy of gold microarray electrodes based on glass and polymethyl methacrylate (PMMA) substrates was elucidated using contact angles, and the total interaction free energy curve of electrodes and S. oneidensis MR-1 was analyzed. Because of the potential barrier of repulsive force of gold microarray electrodes based on glass substrate was easy to cross, the architecture of S. oneidensis MR-1 aggregation on the surface was dense and stable. By contrast, on PMMA substrate, S. oneidensis MR-1 could form a loose and unstable aggregation due to the high potential barrier of repulsive force. The theoretical analysis was consistent with the experimental results by observing the scanning electron microscope images of S. oneidensis MR-1 aggregation. The extended DLVO theory could well predict the adhesion of S. oneidensis MR-1 aggregation on the surface of gold microarray electrodes based on different substrates, providing guidance for electrode design and optimization of MFCs.

The performance of the approximate spin projected (AP) coupled cluster singles and doubles (CCSD) methods based on the spin-unrestricted Hartree-Fock and Brueckner determinants, namely AP-UCCSD and AP-UBD, is benchmarked for singlet-triplet energy gaps in various open-shell species. The test set includes the TS12 set, organic diradicals, and two binuclear copper complexes. We demonstrate that chemical accuracy (1 kcal/mol) can be reached for small open-shell molecules. These methods also provide highly accurate results for larger systems, in good agreement with the established equation of motion spin-flip CCSD (EOM-SF-CCSD) results.

Here, we report the direct synthesis of ITQ-24 with SiO₂/Al₂O₃ = ca. 70–∞, a large-pore zeolite with IWR topology which was originally discovered as an alumino-germanosilicate composition in hydroxide media, using 1,1′-[1,4-phenylenebis(methylene)]bis(1-methylpyrrolidin-1-ium) ion as an organic structure-directing agent in relatively concentrated (H₂O/SiO₂ = 9.0) fluoride media.

Highly stable Ag NPs were synthesized using anionic polyacrylamide (APAM) as the template and reductant. When APAM concentration was 1.50 µM, as-prepared Ag NPs with the diameter of about 3.8 nm had a quantum yield as high as 1.51%. When adding Cu²⁺ and Hg²⁺ into the Ag NPs solution, the fluorescence was quenched effectively. The response between the fluorescence intensity and metal ions concentration allowed for a linear relation, and the detecting limitation for Cu²⁺ was lower than 1 × 10⁻⁹ mol/L.

The last few decades have seen rapid development in molecular science and technology. In this review, photofunctionalization of phthalocyanines (Pcs) is introduced from the viewpoint of biological applications and advanced materials, such as fluorescence probes, photodynamic therapy photosensitizers, photocontrollable magnetic materials, photoconductors, and heat shielding materials. These would be useful model cases for molecular functionalization.

The aim of this study is to develop a simple method to grow an ultralong hydroxyapatite nanowire coating on a substrate. The ultralong hydroxyapatite nanowire coating on a glass substrate was synthesized by a one-step calcium oleate precursor solvothermal method. The formation process of the nanowire coating on the glass substrate was investigated, and the morphology, crystal phase and apatite-forming ability were studied. Moreover, the as-prepared hydroxyapatite nanowire coating exhibited excellent apatite-forming ability in simulated body fluid. The as-prepared ultralong hydroxyapatite nanowire coating has great potential for various biomedical applications.

Herein, we have synthesized niobium carbide/carbon (NbC/C) nanocomposites by a magnesium-thermal reduction process at 600 °C in a stainless-steel autoclave. X-ray diffraction patterns indicate that the obtained product is cubic phase NbC with the calculated lattice constant a = 3.1170 Å. The obtained product shows an onset superconducting temperature at 11.4 K, which is similar to that reported for bulk NbC. In addition, the obtained product was also studied by thermogravimetric analysis (TGA). It had good oxidation resistance below 380 °C in air.

Preparation of vicinal halohydrins, in which copper or iron chlorides catalyze the ring-opening reaction of epoxides with visible light effectively, is described. The use of trichloroacetonitrile as a halogen source enables catalytic HCl generation under the mild conditions. This method can also be applied to the aziridine ring-opening reaction.

We report the production of the long-lived hexafluorobenzene tetracation, which is the smallest aromatic tetracation ever investigated, by 0.8 µm femtosecond laser pulses. The yield of tetracation relative to trication radical is 0.11. Using the time-of-flight mass spectrometer equipped with the fast ion gate and the curved field reflectron, we estimate the lower limit of the lifetime of tetracation to be 9 µs. Confinement of multiple positive charges in a small organic molecule is unexpected; however, our finding is an answer of this fundamental concern.

A photochromic diarylethene derivative having pyrazole and benzothiophene was synthesized and its photochromic behavior and thermal properties were investigated. Upon irradiation with UV light, two kinds of colored isomers were generated at once. One of the colored isomers was thermally stable, the other returned to the initial colorless isomer by heating. We found that the diarylethene derivative exhibits dual-mode photochromism of T- and P-types.

Calcium molybdate nanoparticles were synthesized using a liposome based on egg phosphatidylcholine and cholesterol. The molybdate ion was encapsulated into the liposome, and then a calcium chloride solution was added to the liposome suspension. The molybdenum release kinetics from the liposome to the bulk solution was determined to be 8 ppb h⁻¹. The calcium ion caused aggregation of the liposomes at a higher concentration (>2.5 mM). By using a 1 mM calcium solution, the nanosized calcium molybdate (∼20 nm) precipitated on the liposome surfaces.

A facile and versatile synthesis of ynamines via C(sp)–N bond formation was established. We installed an electron-withdrawing phosphoryl group onto the ynamines to isolate them by column chromatography. Phosphoryl ynamines were synthesized by treatment of bromo(phosphoryl)ethyne with diarylamine in the presence of K₃PO₄. Single-crystal X-ray analysis indicated double-bond characters of N–C, C≡C, and C–P bonds in the N–C≡C–P moiety. Phosphoryl ynamines could be used as terminal ynamine precursors in dephosphorylation/copper-catalyzed click reaction to form the corresponding 4-amino-1,2,3-triazoles in moderate yields.

Zebrafish were exposed to a gold nanorod solution (0.5 mM) for 10 min. Mucous membranes were collected either on ITO plate or blotting membrane. The adsorption and retention of gold nanorods in mucous membranes were evaluated by mass spectrometry of gold ions desorbed from the nanorods. Nanorods modified with cationic polymers were retained in mucous membranes for at least seven days, while anionic and nonionic polymer-modified nanorods were desorbed within three days. These results demonstrate the feasibility of using gold nanorods as a fish tag.

Despite recent great advances in the area of mechanochromic luminescence (MCL), the control over the direction for the mechanical-stimuli-induced shift of the emission maximum still remains a challenging task. Herein, triphenylimidazolylbenzothiadiazoles as a new class of solid-state emissive fluorophores are developed. The switching between bathochromically and hypsochromically shifted MCL has been achieved for the crystals of a bromo-substituted derivative simply by changing the crystallization solvent.

Porous Ni₃Al intermetallic nano-compound was successfully prepared by a chemical method at 600 °C in a LiCl-CaH₂ system. The prepared powder had a crystal structure completely identical to Ni₃Al phase with a porous network structure formed by interconnected nanoparticles. The BET surface areas were as high as 13.1–13.6 m²/g, corresponding to the estimated particle sizes of 59.0–61.3 nm. The surface areas were higher than previous reports (0.1–4.5 m²/g) obtained by conventional physical methods.

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is a promising polymer material widely used for the production of ion-exchange membranes. In this study, quaternization was performed by reacting brominated PPO with 2-(dimethylamino)ethyl methacrylate, resulting in chemical modification to allow cross-linking. The PPO-based ionomer was then filled into a polyethylene porous substrate to prepare a pore-filled anion-exchange membrane (PFAEM) having excellent electrochemical and mechanical properties. In addition, the chemical stability of the PFAEMs could be greatly improved by cross-linking using an appropriate cross-linker. The prepared membranes were also applied to an all-vanadium redox flow battery to evaluate their performances, and as a result, it was confirmed that the best energy efficiency (87.3%) was superior to that of the commercial membrane (84.8%).

Distance dependent fluorescence quenching and mechanisms are studied on a silver nanoparticle (AgNP) surface. The longer the distance between fluorophore and AgNP surface, the less quenching. The relationship fits the quantum efficiency energy transfer equation where a Nanoparticle-Based Energy Transfer (NSET) quenching model dominates with the distance dependent factor of d^4.42 and an estimated NSET radius of 14.4 nm. Within a 10 nm range, the quenching is a result of the combination of Forster Resonance Energy Transfer and NSET.

Derivatives of a tris-fused donor composed of two tetrathiafulvalenes (TTFs) and one extended TTF with an anthraquinoid spacer (TTFAQ) (3) were successfully synthesized. Cyclic voltammetry of the tetrakis(n-hexylthio) derivative (3Dd) indicated the coexistence of two different reduction processes from 3Dd²⁺ to 3Dd. A coin-type cell composed of the positive electrode incorporating the tetramethyl-3 (3Bb) showed relatively stable cycle-life performance (75% of the initial discharge capacity after 50 cycles).

A heterometallic trinuclear complex with three metal-metal bonds, which is constituted of three kinds of metal-ligand units bridged by two sulfido ligands, reacts with a 2-electron donor to afford an adduct accompanied with elongation of the metal-metal bonds. Cyclic voltammograms of the complexes showed that the adduct releases the 2-electron donor after electrochemical 1-electron reduction.

Novel calamitic liquid crystals with asymmetrically substituted structure base on the dibenzo[c,h][2,6]naphthyridine (DBN) moiety as an electron-deficient core, 2-(4-decylphenyl)dibenzo[c,h][2,6]naphthyridine (C10-Ph-DBN), 2-chloro-8-decyl-DBN (Cl-DBN-C10) and 2-decyl-8-phenyl-DBN (Ph-DBN-C10), were synthesized and their carrier transport properties were investigated. The lower ordered smectic phase of SmA emerged in a very wide temperature range of 130 °C in all DBN derivatives, which allowed us to study the carrier transport properties in SmA phase in detail for the first time: we purified Cl-DBN-C10 enough to evaluate the carrier transport property in the SmA phase by time-of-flight method. It showed the temperature and electric field dependence of the mobility, indicating the energetic disorder of transport levels. We analyzed it within the framework of the Gaussian disorder model for electrons and obtained a Gaussian width of the density of states to 109 meV in the SmA. This is the first experimental result analyzed for the SmA phase in calamitic liquid crystals with non-negligible dipole moment.

Synthesis of the western polyene fragment of corallopyronin A is documented. The α-hydroxy skipped diene structure is stereoselectively synthesized by our method consisting of enantioselective allenylation of an aldehyde, hydroboration of the resulting 1,1-disubstituted allene and Migita-Kosugi-Stille coupling. The developed approach could become a general platform for α-hydroxy skipped dienes embedded in a number of biologically active natural products because all eight stereoisomers of the α-hydroxy skipped diene are potentially available from the same aldehyde through these three stereodivergent reactions.

The titled macrocyclic arene ether ketone compound affords peculiarly organized crystals of dimeric molecular aggregated motif including exquisitely aligned water molecules. In the crystal, four water molecules are incorporated into the cavity between two macrocyclic molecules forming chair-formed ketone-hybridized cyclic water hexamer with two ketonic oxygen atoms of the dimerized macrocyclic molecules. The hydrogens of the water molecules situated outside of the hexamer connect with the remaining ketonic carbonyl oxygens in the dimerized macrocyclic molecules and all six oxygens of the hexamer bind to other macrocyclic molecules at the periphery, forming several kinds of effective hydrogen bonding loop networks.

Reactions of molybdenum-silyl hydrido complex 2 ([MoH₃{Si(Ph)[Ph₂PCH₂CH₂P(Ph)C₆H₄-o]₂}]) with 1.5 equiv of 1-alkynes RC≡CH occur readily at room temperature giving σ-acetylide complexes ([MoH₂{Si(Ph)[Ph₂PCH₂CH₂P(Ph)C₆H₄-o]₂}(C≡CR)]: R = Ph (3a), t-Bu (3b)), in which the acetylide ligands ligate at the site opposite to the Si atom.

Phosphotriester- or phosphodiester polyphosphoesters (PPEs) bearing phosphorylcholine (PC) groups were newly synthesized and coated on hydroxyapatite (HAp) to form nonfouling mineral substrate surface as a human tooth model to address the problem of biofilm formation and mineral resorption. PC-immobilized phosphodiester PPEs (PEB–PC) preferably adsorbed on HAp leading to the inhibition of HAp resorption under acidic conditions. In addition, the HAp surface with immobilized PEB–PC has the ability to suppress bacterial adhesion and inhibit biofilm formation.

Direct ascorbic acid (AsA) fuel cells based on SWCNT and PEDOT*PSS composite anodes were studied. The open circuit voltage was 0.55 V against Pt-black air cathode. The maximum power density (4.9 mWcm⁻²) using SWCNT alone was enhanced to 11.3 mWcm⁻² by coating SWCNT with PEDOT*PSS. Cell performances among various anode materials of SWCNT, carbon powder, Pt-black and composites with PEDOT*PSS are discussed in terms of specific surface areas and roles of conducting polymers.

We investigate cluster-growth processes in a magnetron-sputtering cluster source by employing silver as a target metal. An optical emission spectrum of discharge plasma is measured along with a mass spectrum of silver cluster cations as a function of discharge power. The former quantifies the number of silver atoms sputtered, while the latter provides a size distribution of clusters produced. A scenario of cluster growth is discussed based on a simple statistical model.

Both high purity ⁶Li and ⁷Li are indispensable materials in the nuclear industry. We propose a new strategy for ⁶Li enrichment. Comparing with traditional extraction enrichment, scrubbing is the main process of lithium isotope enrichment for new strategies, rather than the extraction. ⁶Li reaches 9.42% after 20-stage scrubbing. The method provides a green and efficient process. This makes it possible to replace the lithium amalgam method for separation of lithium isotopes and may shed light on separation of the other stable isotopes.

The steric structures of luminescent compounds play a key role in controlling the thermal and optical properties. In order to improve the thermal properties of a strong luminescent Eu(III) coordination polymer [Eu(hfa)₃(dpedot)]_n (hfa: hexafluoroacetylacetonate, dpedot: 2,5-bis(diphenylphosphoryl)-3,4-ethylenedioxythiophene) in our previous study, a dithiane hexyl ring was introduced instead of a dioxane ring. The prepared [Eu(hfa)₃(dpedtt)]_n (dpedtt: 2,5-bis(diphenylphosphoryl)-3,4-ethylenedithiothiophene) exhibited thermal stability by suppressing side group decomposition. The dpedtt ligand showed a smaller dipole moment than that of dpedot, and [Eu(hfa)₃(dpedtt)]_n formed less twisted and densely packed polymer chains, resulting in excellent photophysical properties (quantum yield > 60%).

To solve the critical issue of the poor cycling stability caused by large volume expansion of Si-based anodes during Li lithiation/delithiation processes, spherical Si hollow nanostructures are prepared based on Kirkendall effect via a simple molten salt-assisted magnesiothermic reduction technique. The hollow structure of silicon provides additional internal space for the volume expansion of silicon. The novel hollow Si nanostructure shows good electrochemical performance as Li-ion battery anodes. After 50 cycles, it can provide 1302 mAh·g⁻¹ capacity with current density of 0.2 A·g⁻¹. The material has a unique hollow structure that allows the expansion of silicon during the lithium process, providing better cycle life and rate capability than direct reduction of bulk silicon.

We focused on introducing inclusion capability of β-cyclodextrin (β-CD) in an aqueous two-phase system (ATPS). A phase separation between two aqueous solutions of poly(ethylene glycol) (PEG) and dextran was prepared with a β-CD-modified PEG. Inclusion complexation between the β-CD-modified PEG and an adamantine-modified protein contributed to an increase in the distribution to the upper phase (PEG phase). Furthermore, by adding a competitive molecule, the inclusion complex was dissociated, suggesting the modulation of protein partition by the host-guest system.

Catalytic chemistry of glucose oxidase has been proved as an efficient cancer therapeutic strategy. Herein we constructed an excellent enzyme delivery nanocarrier based on the host-guest interaction between a β-cyclodextrin (β-CD) dimer and a tripod molecule bearing three adamantine units. A series of experiments were carried out to explore the therapeutic effect, in order to demonstrate the supramolecular vesicles more promising for cancer therapy.