A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters by use of solid-phase extraction, and its applications to brackish lake waters

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters has been developed for field analysis. This method is based on solid-phase extraction on a zirconium-loaded Sep-Pack Accell CM cartridge (Zr-SP) and is applicable to studies in which sampling is performed by use of a graduated syringe to prevent contamination and to ensure easy operation at sampling sites. The Zr-SP cartridge was prepared by passing 0.1 mol L^–1 zirconium solution through a Sep-Pak Accell CM cartridge, packed with cation exchange sorbent based on a silica matrix. The adsorption of phosphate and its desorption depend only on the pH of the solution. A water sample containing phosphate was adjusted to pH 2 and passed through the Zr-SP cartridge to collect it. The retained phosphate was quantitatively eluted with 0.5 mol L^–1 sodium hydroxide solution. The phosphate retained in the Zr-SP cartridge was stable for at least one month. The established preconcentration method was successfully applied to brackish lake waters to investigate seasonal changes in the distribution and behavior of phosphate in a brackish lake.     

The scalar curvature of CR submanifolds of maximal CR dimension of complex projective space

We treat n-dimensional compact minimal submanifolds of complex projective space when the maximal holomorphic tangent subspace is (n − 1)-dimensional and we give a sufficient condition for such submanifolds to be tubes over totally geodesic complex subspaces. Authors’ addresses: Mirjana Djorić, Faculty of Mathematics, University of Belgrade, Studentski trg 16, pb. 550, 11000 Belgrade, Serbia; Masafumi Okumura, 5-25-25 Minami Ikuta, Tama-ku, Kawasaki, Japan     

Theoretical studies on magnetic interactions between Cu(II) ions in hydroxypyridone nucleobases

The origin of a ferromagnetic interaction between Cu²⁺ ions in the Cu²⁺–DNA system which reported by Tanaka et al. is examined by using DFT calculations. In order to consider effects of an entanglement and a dis-entanglement of the double helix chain, three types of structural disorders i.e. distance, rotation angle and discrepancy in XY-plane, are considered in the model dimer structure. All calculated results show that J_ab values are weak anti-ferromagnetic couplings. Boltzmann distribution simulation indicates that the high spin (HS) species exist 21% at 1.5 K by thermal excitation within the model structure.     

Biosensor for peptide determination constructed by immobilizing proteolytic enzymes on coated-wire electrodes

A biosensor for peptide determination was constructed with trypsin or α-chymotrypsin immobilized on hydrogen ion-selective coated-wire electrode and its fundamental properties were investigated with two artificial peptides. The substrates could be determined in the range 0.1–40 mM with response times of 5–10 min. The effects of pH and concentration of buffer solution on the determination were investigated.     

A novel anthracene-based fluorescent colorimetric sensor for the simple naked-eye diagnosis of methylmalonic aciduria

A novel molecular sensor using anthracene bearing two amidopyridines emits blue fluorescence in the presence of succinic acid and green fluorescence in the presence of malonic acid, and its fluorescence intensity increased upon binding. Using this molecular sensor, we succeeded in detecting the difference of one carbon atom between succinic acid and malonic acid with the naked-eye. Furthermore, when methylmalonic acid was dissolved in urine to provide a model system for methylmalonic aciduria, the fluorescence changed from blue to green, and methylmalonic acid was successfully detected with the naked-eye.     

Platinum Nanoflowers on Scratched Silicon by Galvanic Displacement for an Effective SALDI Substrate

We report a new and facile method for synthesizing 3D platinum nanoflowers (Pt Nfs) on a scratched silicon substrate by electroless galvanic displacement and discuss the applications of the Pt Nfs in surface‐assisted laser desorption/ionization‐mass spectrometry (SALDI‐MS). Surface scratching of n‐type silicon is essential to induce Pt Nf growth on a silicon substrate (to obtain a Pt Nf silicon hybrid plate) by the galvanic displacement reaction. The Pt Nf silicon hybrid plate showed excellent SALDI activity in terms of the efficient generation of protonated molecular ions in the absence of a citrate buffer. We propose that the acidity of the Si? OH moieties on silicon increases because of the electron‐withdrawing nature of the Pt Nfs; hence, proton transfer from the Si? OH groups to the analyte molecules is enhanced, and finally, thermal desorption of the analyte ions from the surface occurs. Signal enhancement was observed for protonated molecular ions produced from a titania nanotube array (TNA) substrate on which Pt nanoparticles had been photochemically deposited. Moreover, surface modification of the Pt Nf silicon hybrid plate by perfluorodecyltrichlorosilane (FDTS) (to obtain an FDTS‐Pt Nf silicon hybrid plate) was found to facilitate soft SALDI of labile compounds. More interestingly, the FDTS‐Pt Nf silicon hybrid plate acts 1) as a high‐affinity substrate for phosphopeptides and 2) as a SALDI substrate. The feasibility of using the FDTS‐Pt Nf silicon hybrid plate for SALDI‐MS has been demonstrated by using a β‐casein digest and various analytes, including small molecules, peptides, phosphopeptides, phospholipids, carbohydrates, and synthetic polymers. The hybridization of Pt Nfs with a scratched silicon substrate has been found to be important for achieving excellent SALDI activity.     

Air-stable, room-temperature emissive disilenes with π-extended aromatic groups

π-Conjugated disilenes with 2-naphthyl or 2-fluorenyl groups on the silicon atoms have been synthesized as air-stable emissive red solids using the bulky 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl (Eind) groups. The strong π-π* absorptions and distinct emission at room temperature, both in solution and in the solid state, have been observed due to the substantial contribution of the 3p(π)*(Si-Si)-2p(π)*(carbon π-electron system) conjugation.     

Fully and partially fluorinated flavone derivatives

In the crystal structures of the fully and partially fluorinated flavone derivatives 5,6,7,8‐tetrafluoro‐2‐(2,3,4,5,6‐pentafluorophenyl)‐4H‐1‐benzopyran‐4‐one, C₁₅HF₉O₂, (I), and 5,6,7,8‐tetrafluoro‐2‐phenyl‐4H‐1‐benzopyran‐4‐one, C₁₅H₆F₄O₂, (II), the pentafluorophenyl group and the pyranone moiety in (I) are twisted due to repulsion of the F substituents, and a CO(δ⁻)...π(δ⁺) intermolecular interaction is observed between the carbonyl O atom and the pentafluorophenyl group. In (II), on the other hand, the phenyl group and the pyranone moiety are almost coplanar, and arene–perfluoroarene interactions are observed in the head‐to‐tail intermolecular columnar stacking between the phenyl group and the tetrafluorophenylene moiety.