Selectivity and recovery performance of phosphate-selective molecularly imprinted polymer

A phosphate-selective molecularly imprinted polymer was prepared using 1-allyl-2-thiourea as a functional monomer, and the binding ability and selectivity of the polymer were evaluated. The imprinted polymer showed high binding ability to and selectivity for phosphate in aqueous media. The recoverability of phosphate from the imprinted polymer was also examined, and nearly 70% of highly concentrated phosphate could be recovered.     

PRODAN-conjugated DNA: synthesis and photochemical properties

A solvatochromic fluorophore, PRODAN, has been used as a microenvironment-sensitive reporter. Based on the chemistry of PRODAN, we designed and synthesized four novel fluorescent nucleosides, PDNX (X = U, C, A, and G), to which a PRODAN fluorophore was attached at pyrimidine C5 or purine C8. The fluorescent nucleosides sensitively varied the Stokes shift values depending on the orientational polarizability of the solvent. The PDNX incorporated into DNA also changed the Stokes shift values depending on the DNA structure. In particular, the excitation spectrum of the PDNX-containing duplex shifted to a longer wavelength and gave a smaller Stokes shift value when the base opposite PDNX could form a Watson-Crick base pair with PDNX. A lower energy excitation of PDNX-containing DNA resulted in a strong fluorescence emission selective to the Watson-Crick pairing base. This unique photochemical character was applicable to the efficient typing of single-nucleotide polymorphisms of genes.     

氟催化废弃硅基还原剂与CO2还原转化反应

CO2是最重要的可再生碳源之一.为了将CO2转化为有用的有机化合物,我们研究了二种模型硅基"废"材料—乙硅烷和硅粉的反应活性.在这些反应中,氟盐的催化活性最高,在常压、在质子源水和硅基还原剂的存在下,CO2可转化为甲酸.原位NMR和动力学分析表明,含氢硅烷和五配位的硅物种分别是反应中间物和活性物种.     

Oligophenyls with Multiple Disulfide Bridges as Higher Homologues of Dibenzo[c,e][1,2]dithiin: Synthesis and Application in Lithium-Ion Batteries

Higher homologues of dibenzo[c,e][1,2]dithiin were synthesized from oligophenyls bearing multiple methylthio groups. Single-crystal X-ray analyses revealed their nonplanar structures and helical enantiomers of higher meta-congener 6 . Such dibenzo[1,2]dithiin homologues are demonstrated to be applicable to lithium-ion batteries as cathode, displaying a high capacity of 118 mAh g⁻¹ at a current density of 50 mA g⁻¹.     

Aerobic Oxidations Catalyzed by Colloidal Nanogold

Recently, dispersions of gold nanoclusters in liquid media (colloidal nanogold) have been extensively used as quasi‐homogeneous catalysts for various aerobic oxidation reactions. This review describes recent progress in such reactions, with a focus on our comprehensive studies on gold clusters (<2 nm) stabilized by poly(N‐vinyl‐2‐pyrrolidone) and their participation in oxidation reactions of alcohols, α‐hydroxylation reactions of benzylic ketones, and homocoupling reactions of organoboronates, as well as formal Lewis acidic reactions, such as intramolecular hydroalkoxylation and hydroamination reactions of nonactivated alkenes. Mechanistic studies have shown that a partial electron transfer from the gold clusters to O₂ generates superoxide‐ or peroxide‐like species and Lewis acidic centers, both of which play essential roles in the catalytic reactions.     

Platonic hexahedron composed of six organic faces with an inscribed Au cluster

The structures of nanomaterials determine their individual properties and the suprastructures they can form. Introducing anisotropic shapes and/or interaction sites to isotropic nanoparticles has been proposed to extend the functionality and possible suprastructure motifs. Because of symmetric anisotropy, Platonic solids with regular polygon faces are one of the most promising nanoscale structures. Introduction of Platonic solid anisotropy to isotropic nanomaterials would expand the functionality and range of possible suprastructure motifs. Here, we demonstrate a novel strategy to obtain nano-Platonic solids through the face coordination of square porphyrins on an inscribed Au sphere with adequate size. The face coordination of the multidentate porphyrin derivatives, with four acetylthio groups facing the same direction, on the Au cluster encased the Au cluster in a Platonic hexahedron with six porphyrin faces. Transmission electron microscopy, mass spectrometry, elemental analysis, and scanning tunnelling microscopy were used to confirm the formation of the nano-Platonic hexahedron.     

A new binding motif of sterically demanding thiolates on a gold cluster

A gold cluster, Au(41)(S-Eind)(12), was synthesized by ligating the bulky arenethiol 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacene-4-thiol (Eind-SH) to preformed Au clusters. Extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, and the fragmentation pattern in the mass spectrometry analysis indicated that formation of gold-thiolate oligomers at the interface was suppressed, in sharp contrast to conventional thiolate-protected Au clusters.     

Chiral magnetic soliton lattice on a chiral helimagnet

Using Lorenz microscopy and small-angle electron diffraction, we directly present that the chiral magnetic soliton lattice (CSL) continuously evolves from a chiral helimagnetic structure in small magnetic fields in Cr(1/3)NbS2. An incommensurate CSL undergoes a phase transition to a commensurate ferromagnetic state at the critical field strength. The period of a CSL, which exerts an effective potential for itinerant spins, is tuned by simply changing the field strength. Chiral magnetic orders observed do not exhibit any structural dislocation, indicating their high stability and robustness in Cr(1/3)NbS2.     

Controlled Synthesis of Diphosphine-Protected Gold Cluster Cations Using Magnetron Sputtering Method

We demonstrated, for the first time, atomically precise synthesis of gold cluster cations by magnetron sputtering of a gold target onto a polyethylene glycol (PEG) solution of 1,3-bis(diphenylphosphino)propane (Ph₂PCH₂CH₂CH₂PPh₂, dppp). UV-vis absorption spectroscopy and electrospray ionization mass spectrometry revealed the formation of cationic species, such as [Au(dppp)_n]⁺ (n = 1, 2), [Au₂(dppp)_n]²⁺ (n = 3, 4), [Au₆(dppp)_n]²⁺ (n = 3, 4), and [Au₁₁(dppp)₅]³⁺. The formation of [Au(dppp)₂]⁺ was ascribed to ionization of Au(dppp)₂ by the reaction with PEG, based on its low ionization energy, theoretically predicted, mass spectrometric detection of deprotonated anions of PEG. We proposed that [Au(dppp)₂]⁺ cations thus formed are involved as key components in the formation of the cluster cations.