Facile One‐Pot Synthesis of [1, 2, 3]Triazolo[1, 5‐a]Pyridines from 2‐Acylpyridines by Copper(II)‐Catalyzed Oxidative NN Bond Formation

An efficient and simple method for the synthesis of various [1, 2, 3]triazolo[1, 5‐a]pyridines has been established. The method involves a copper(II)‐catalyzed oxidative N?N bond formation that uses atmospheric oxygen as the terminal oxidant following hydrazonation in one pot. The use of ethyl acetate as the solvent dramatically promotes the oxidative N?N bond‐formation reaction and enables the application of oxidative cyclization in the efficient one‐pot reaction. A mechanism for the reaction was proposed on the basis of the results of a spectroscopic study.     

Temperature-responsive stationary phase utilizing a polymer of proline derivative for hydrophobic interaction chromatography using an aqueous mobile phase

A new method of chromatography is proposed, utilizing a thermo-responsive polymer carrying an amino acid ester residue for the stationary phase of high-performance liquid chromatography (HPLC). We have been investigating the new concept of chromatography, a temperature-responsive chromatography, using temperature-responsive poly(N-isopropylacrylamide) (PNIPAAm)-modified surface for HPLC with a constant aqueous media as the mobile phase. In this study, we designed and synthesized thermo-responsive poly(acryloyl-L-proline methyl ester) and its copolymer with N-isopropylacrylamide (NIPAAm). Homopolymers of acryloyl-L-proline methyl ester and copolymer were prepared by the reaction of radical telomerization. These polymers underwent a reversible phase transition from water-soluble forms into aggregates by changing the temperature, similar to PNIPAAm. The surface properties and functions of stationary phases modified with poly(acryloyl-L-proline methyl ester) were controlled by the external temperature. In the chromatographic system, we separated steroids and amino acids with a variety of hydrophobicities using a sole aqueous mobile phase. In contrast to a PNIPAAm-modified surface, a poly(acryloyl-L-proline methyl ester)-modified surface showed a greater affinity for hydrophobic amino acids.     

An efficient preparation and spectroscopic and electrochemical properties of quinodimethane derivatives with four 3-(methoxycarbonyl)azulen-1-yl groups

Reaction of methyl 1-azulenecarboxylate (8) with terephthalaldehyde (9) in acetic acid in the presence of hydrochloric acid at 25 °C for 2 h gives 1,4-bis[bis(3-methoxycarbonyl-1-azulenyl)methyl]benzene (12), in 93% yield, which upon oxidation with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in dichloromethane in the presence of hexafluorophosphoric acid at 25 °C for 1 h affords the dicarbenium-ion compound 15 in 94% yield. Furthermore, reduction of 15 with zinc powder in a mixed solvent of acetonitrile and chloroform at 25 °C for 1 h yields the target quinodimethane 18 in 90% yield. Similarly, as in the case of 18, the quinoid compounds 19 and 20 can be derived from the dicarbenium-ion compounds 16 and 17, quantitatively. A facile preparation as well as spectroscopic and electrochemical properties of 15-20 is reported.     

Protein modification by arginylation

The modification of protein by arginine catalyzed by arginyltransferases (ATE1) described by the Kashina group in this issue shows that arginylation of protein occurs widely in biology and is being recognized as a key regulatory reaction such as phosphorylation of proteins (Wang et?al., 2011).     

Thermo-responsive polymer brush-grafted porous polystyrene beads for all-aqueous chromatography

Poly(N-isopropylacrylamide) (PIPAAm) brush-grafted porous polystyrene beads with variable grafted polymer densities were prepared using surface-initiated atom transfer radical polymerization (ATRP) for applications in thermo-responsive chromatography. Utilization of these grafted beads as a stationary phase in aqueous chromatographic analysis of insulin provides a graft density-dependent analyte retention behavior. The separations calibration curve on PIPAAm-grafted polystyrene was obtained using pullulan standards and exhibited inflection points attributed to analyte diffusion into bead pores and partitioning into grafted PIPAAm brush surfaces. Presence of these inflection points supports a separation mechanism where insulin penetrates pores in polystyrene beads and hydrophobically interacts with PIPAAm brushes grafted within the pores. Control of PIPAAm brush graft density on polystyrene facilitates effective aqueous phase separation of peptides based on thermally modulated hydrophobic interactions with grafted PIPAAm within stationary phase pores. These results indicated that PIPAAm brush-grafted porous polystyrene beads prepared by surface-initiated ATRP was effective stationary phase of thermo-responsive chromatography for aqueous phase peptide separations.     

Phosphorylation of D-glucose derivatives with inorganic monoimido-cyclo-triphosphate

Phosphorylation of several D-glucose derivatives has been achieved using inorganic monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the phosphorylation of D-glucose, D-glucuronic acid, 2-deoxy-D-glucose and D-galactose, 1-O-diphosphoramidophosphono-beta-D-glucose, 1-O-diphosphoramidophosphono-beta-D-glucuronic acid, 1-O-diphosphoramidophosphono-2-deoxy-beta-D-glucose, and 1-O-diphosphoramidophosphono-beta-D-galactose were stereoselectively synthesized with yields of 54, 32, 37 and 46%, respectively. In the case of methyl alpha-D-glucoside, the phosphorylated products were methyl 3-O-diphosphoramidophosphono-alpha-D-glucoside and methyl 4-O-diphosphoramidophosphono-alpha-D-glucoside, and in the case of methyl beta-D-glucoside the products were methyl 2-O-diphosphoramidophosphono-beta-D-glucoside, methyl 3-O-diphosphoramidophosphono-beta-D-glucoside, and methyl 4-O-diphosphoramidophosphono-beta-D-glucoside. For D-mannose and D-allose, several phosphorylated products were obtained and the main products were 1-O-diphosphoramidophosphono-beta-D-aldoses.     

Extraction of tetrafluoroborate with crown ethers and its application to silicate rock analysis

Summary The extraction behaviour of tetrafluoroborate with crown ethers was studied. A high distribution ratio of tetrafluoroborate is obtained by extraction with dicyclohexano-18-crown-6 (DC18C6) in an organic solvent of high dielectric constant from potassium fluoride solution. The molar ratios of crown ether to KBF₄ in the extracted species are probably 1:1 for DC18C6, dibenzo-18-crown-6 and 18-crown-6, and 2:1 for benzo-15-crown-5 and 15-crown-5. The flow-injection extraction-spectrophotometric determination of tetrafluoroborate with Brilliant Green was worked out. Many rock reference samples were analyzed for boron (1–150 ppm).     

Thermally responsive chromatographic materials using functional polymers

Functional polymers that respond to small changes in environmental stimuli with large changes in their structure and properties are often called "intelligent" polymers. We have modified material surfaces with such polymers and used them in separation systems. Silica beads were modified with the temperature-responsive polymer poly(N-isopropylacrylamide) (PNIPAAm). PNIPAAm-grafted surfaces exhibited temperature-driven alterations of hydrophilic-hydrophobic surface-properties. Using this feature, PNIPAAm and related temperature-responsive polymers have been used to generate temperature-sensitive stationary phases for chromatographic separations. We attached several different functional polymers, including temperature- and pH-responsive polymers, to silica beads. These temperature-responsive stationary phases are useful in development of separation methods since adjusting the temperature represents an extra tool for optimizing the selectivity. Applications of thermally responsive columns for separations in the HPLC mode are demonstrated.     

Approaching over 10 000‐fold sensitivity increase in chiral capillary electrophoresis: Cation‐selective exhaustive injection and sweeping cyclodextrin‐modified micellar electrokinetic chromatography

A novel and simple method that combines an online concentration technique with an enantioseparation technique for capillary electrophoresis—namely, cation‐selective exhaustive injection and sweeping cyclodextrin‐modified micellar electrokinetic chromatography (CSEI‐sweeping CD‐modified MEKC)—realizes the effective enantioseparation of cationic analytes while keeping a significant increase of detection sensitivity. This technique consists of a slight modification of the basic CSEI‐sweeping MEKC. The main idea is to simply add an anionic CD as a chiral selector into the micellar buffer including sodium dodecyl sulfate, but not to change any other buffers in order to preserve the online concentration mechanism. When applied to analysis of the street drug, methamphetamine, the method achieved not only a baseline enantioseparation but also limits of detection (LODs; S/N = 3) of 70–90 pg/mL (ppt) for each isomer. This translates to a more than 10 000‐fold improvement compared to the LODs by the usual injection method. The present technique, which was made from a slight modification of CSEI‐sweeping MEKC, would give an attractive approach that is applicable to almost any analytes for which CSEI‐sweeping MEKC is applicable; all that is required is the selection of an appropriate anionic CD to be added to the micellar buffer.     

Optical activity induced by helical arrangements of tryptamine and 4-chlorobenzoic acid in their cocrystal

Optical rotatory powers of chiral cocrystals formed from the achiral molecules tryptamine and 4-chlorobenzoic acid were determined by the HAUP (high accuracy universal polarimeter) method. These cocrystals belonged to space group P2(1)2(1)2(1), and their absolute configuration was confirmed by the Flack parameter. In the M-crystal, 2-fold helical arrangements are formed in a counterclockwise direction between the two components through the quaternary ammonium salt bridge, hydrogen bond, and the aromatic pi-piinteraction along the c axis, while clockwise helices alone exist in the P-crystal. Large rotatory powers rho(3)(M) = -355 and rho(3)(P) = +352 deg mm(-)(1) were obtained along the c axis in the M- and P-crystal, respectively, at 632.8 nm and 303 K. The magnitude was 10 to 100 times larger than those for ordinary organic crystals. Further, it was confirmed that the negative sign was induced by the counterclockwise helical structures and the positive sign by the clockwise helices. In contrast, the rotations along the a and b axis which are in perpendicular directions to the screw axis were rho(1)(M) = +138, rho(1)(P) = -140 deg mm(-)(1), and rho(2)(M) = -56, rho(2)(P) = +58 deg mm(-)(1), much smaller than rho(3)(M) and rho(3)(P) . The results revealed that the helically arranged aromatic pi electrons as well as the helical ionic and hydrogen bond networks in the crystal contributed to the enhancement of the magnitude of these rotations.