Infrared spectroscopic analyses of transformations of chemical species on the silica highly-reacted with gaseous BF3.

Transformations of chemical species formed by the reaction of gaseous BF3 with high pressure and silica preheated at 473 and 1093 K were studied with the use of infrared absorption spectrometry. The species containing -BF2 and the species containing >BF were transformed to each other on the highly-reacted silica depending on the pressure of BF3 in cell, and some of the species containing -BF2 were also desorbed without their transformations to the species containing >BF. H2O played important roles in these transformations.     

Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate

The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO₄ (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO₄, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006     

Synthesis of well‐defined syndiotactic poly(methyl methacrylate) with low‐temperature atom transfer radical polymerization in fluoroalcohol

The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (M_n) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured M_n's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr₂) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]₀/[methyl α‐bromoisobutyrate]₀/[CuBr]₀/[CuBr₂]₀/[Me₆TREN]₀ = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of Cu^IBr/Me₆TREN in HFIP, there were [Cu(Me₆TREN)Br]⁺ and [Cu(Me₆TREN)OCH(CF₃)₂]⁺, indicating that HFIP should coordinate to the Cu^I/Me₆TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006     

Signaling molecularly imprinted polymers: molecular recognition-based sensing materials

Molecular imprinting is a template polymerization technique that can easily provide synthetic polymers capable of molecular recognition for given target molecules. In addition to their highly specific recognition ability, we are attempting to introduce signaling functions to molecularly imprinted polymers, enabling them to respond according to specific binding events. Some of our work regarding such signaling molecularly imprinted polymers is presented here, including molecularly imprinted polymers that induce spectral shifts of target compounds because of binding. Such compounds include hydrogen-bonding-based fluorescent imprinted polymers and metalloporphyrin-based signaling molecularly imprinted polymers.     

Selective flow-injection determination of methanol in the presence of ethanol based on a multi-enzyme system with chemiluminescence detection

A highly selective flow-injection system was developed for the determination of methanol. The system consisted of three immobilized enzymes with luminol chemiluminescence detection. First, methanol was oxidized in the presence of alcohol oxidase to yield formaldehyde and hydrogen peroxide. The hydrogen peroxide produced was then destroyed by catalase. The formaldehyde formed in the first stage was further oxidized by NAD⁺-formaldehyde dehydrogenase. The NADH formed was oxidized by 1-methoxy-5-methylphenazinium methylsulphate (1-MPMS), and finally the reduced 1-MPMS was spontaneously oxidized and hydrogen peroxide was produced. The concentration of the hydrogen peroxide produced, which was proportional to the initial concentration of methanol, was determined by luminol chemiluminescence. The determination range was from 0.1 to 100 mg l⁻¹ and the response time was less than 2 min per sample with a relative standard deviation of less than 3%. The system showed good selectivity for methanol; the response was ca. 50 times higher than for ethanol.     

Specific heat on Sr<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> and Sr<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Specific heats on the single crystals of Sr₂Nb₂O₇, Sr₂Ta₂O₇ and (Sr_1-xBa_x)₂Nb₂O₇ were measured in a wide temperature range of 2-600 K. Heat anomalies of a λ-type were observed at the incommensurate phase transition of T_INC (=495 K) on Sr₂Nb₂O₇ and at the super-lattice phase transition of T_SL (=443 K) on Sr₂Ta₂O₇; the transition enthalpies and the transition entropies were estimated. Furthermore, a small heat anomaly was observed at the low temperature ferroelectric phase transition of T_LOW (=95 K) on Sr₂Nb₂O₇. The transition temperature T_LOW decreases with increasing Ba content x and it vanishes for samples of x>2%.     

Output and picosecond amplification characteristics of an efficient and high-power discharge excimer laser

Improvements in output pulse energy and efficiency of a conventional capacitor-transfer-type discharge excimer laser with automatic preionization have been achieved by extending the discharge volume and resulting moderate pumping of the active medium. The discharge laser produces a pulse energy of more than 1 J for XeCl, KrF, and ArF lasers in square beams of about 2×2 cm², and the maximum overall efficiency observed is 2.9% for XeCl, 3.2% for KrF and 1.8% for ArF. The laser device has been involved in a picosecond ( 32 ps) XeCl laser amplification system, and was operated as an amplifier at a repetitive frequency of 10 Hz. Saturation fluence for XeCl laser was measured to be 1.4 mJ/cm², and the picosecond pulse energy of 40 mJ was extracted from the amplifier.On leave from Ebara Corp., 6-6-7, Ginza, Chuo-ku, Tokyo 104, JapanOn leave from Mitsubishi Heavy Industries, LTD., 4-6-22, Kan-on shinmachi, Nishi-ku, Hiroshima 733, Japan     

Biosynthesis of a lactate (LA)-based polyester with a 96 mol% LA fraction and its application to stereocomplex formation

A poly(lactic acid) (PLA)-like terpolyester consisting of 96 mol% lactate (LA), 1 mol% 3-hydroxybutyrate and 3 mol% 3-hydroxyvalerate was produced in recombinant Escherichia coli LS5218 expressing LA-polymerizing enzyme (LPE). The strain was grown on glucose with a feeding of valerate as the monomer precursor. The glass transition and melting temperatures of the terpolyester were close to those of chemically synthesized poly(L-LA)s (PLLAs) having similar molecular weights. Additionally, a blend of the terpolyester, which was composed entirely of (R)-LA (D-LA) due to the strict enantiospecificity of LPE, with PLLA formed a stereocomplex with higher melting temperature (201.9 °C). These results indicate that the biological PLA-like polyester produced via this one-step microbial process has comparable thermal properties to chemically synthesized PLAs.     

Synthesis and Cation-Binding Properties of (1→6)-2,5-Anhydro-D-glucitol with 3,4-Di-O-Pentyl and Decyl Groups by Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols

Abstract

The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF₃OEt₂ and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF₃O-decyl₂ comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl₃, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs⁺ > Rb⁺ > K⁺ ? Na⁺ > Li⁺. The ratio of K⁺ and Na⁺, K⁺/Na⁺, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c.     

Diastereo‐ and Regioselective Addition of Thioamide Dianions to Imines and Aziridines: Synthesis of N‐Thioacyl‐1,2‐diamines and N‐Thioacyl‐1,3‐diamines

Addition reactions of thioamide dianions that were derived from N‐arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N‐thioacyl‐1,2‐diamines in a highly diastereoselective manner in good‐to‐excellent yields. The diastereomeric purity of these N‐thioacyl‐1,2‐diamines could be enriched by simple recrystallization. The reduction of N‐thioacyl‐1,2‐diamines with LiAlH₄ gave their corresponding 1,2‐diamines in moderate‐to‐good yields with retention of their stereochemistry. The oxidative‐desulfurization/cyclization of an N‐thioacyl‐1,2‐diamine in CuCl₂/O₂ and I₂/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N‐tosylaziridines gave the addition products of N‐thioacyl‐1,3‐diamines with low diastereoselectivity but high regioselectivity and in good‐to‐excellent yields. The use of AlMe₃ as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X‐ray diffraction.