Stereoregulation in cationic polymerization. III. High isospecificity with the bulky phosphoric acid [(RO)2PO2H]/SnCl4 initiating systems: Design of counteranions via initiators

In the cationic polymerization of isobutyl vinyl ether (IBVE) with binary initiating systems consisting of a protonic acid as an initiator and a Lewis acid as an activator/catalyst, phosphoric acid derivatives [(RO)₂POOH] coupled with SnCl₄ gave highly isotactic poly(IBVE)s, whereas those with a bulky substituent (R), [C₄H₉CH(C₂H₅)CH₂O]₂POOH ( 7 ) and (n‐C₁₀H₂₁)₂POOH ( 8 ), led to the highest isotacticity [meso dyad (m) = 86%]. In contrast, isospecificity was lower with IBVE–HCl and CF₃COOH under the same conditions. From the effects of the polymerization temperature (−78 to 0 °C), it was concluded that the high isospecificity with 7 and 8 was due to an enthalpic factor. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1067–1074, 2001     

Pretreatment with ammonia water for enzymatic hydrolysis of corn husk, bagasse, and switchgrass

Bagasse, corn husk, and switchgrass were pretreated with ammonia water to enhance enzymatic hydrolysis. The sample (2 g) was mixed with 1–6 mL ammonia water (25–28% ammonia) and autoclaved at 120°C for 20 min. After treatment, the product was vacuum-dried to remove ammonia gas. The dried solid could be used immediately in the enzymatic hydrolysis without washing. The enzymatic hydrolysis was effectively improved with more than 0.5 and 1 mL ammonia water/g for corn husk and bagasse, respectively. In bagasse, glucose, xylose, and xylobiose were the main products. The adsorption of CMCase and xylanase was related to the initial rate of enzymatic hydrolysis. In corn husks, arabinoxylan extracted by pretreatment was substantially unhydrolyzed because of the high ratio of arabinose to xylose (0.6). The carbohydrate yields from cellulose and hemicellulose were 72.9% and 82.4% in bagasse, and 86.2% and 91.9% in corn husk, respectively. The ammonia/water pretreatment also benefited from switchgrass (Miscanthus sinensis and Solidago altissima L.) hydrolysis.     

A C4N4 Diaminopyrimidine Fluorophore

A new scaffold for producing efficient organic fluorescent materials was identified: 2,5-diamino-4,6-diarylpyrimidine featuring a C4N4 elemental composition. Single-step installation of two aryl groups at the 4,6-positions of the pyrimidine core delivered fluorescent organic materials in a modular fashion. A range of fluorescent compounds with distinct absorption/emission properties was readily accessed by changing the aromatic attachments. A generally high absorption coefficient and quantum yield were observed, including C4N4 derivatives that could fluoresce even in the solid state. The two amino groups at the 2,5-positions of the pyrimidine were essential for intense fluorescence with a large Stokes shift, which was corroborated by structural relaxation to a p-iminoquinone-like structure in the excited state. Besides live-cell imaging capabilities, fluorescent labeling of a protein involved in autophagy elucidated a new protein–protein interaction, supporting potential utility in bioimaging applications.     

Synthesis of 1,2:5,6-Di-O-isopropylidene-3-O-[3-(uracil-1-yl)propionoyl]-α-D-glucofuranose and 1,2-Mono-O-isopropylidene-6-O-[3-(uracil-1-yl)propionoyl]-α-D-glucofuranose

1,2:5,6-Di-O-isopropylidene-3-O-[3-(uracil-1-yl)propionoyl]-α-D-glucofuranose and 1,2-mono-O-isopropylidene-6-O-[3-(uracil-1-yl)propionoyl]-α-D-glucofuranose were synthesized.     

Protic N‐Heterocyclic Carbene Versus Pyrazole: Rigorous Comparison of Proton‐ and Electron‐Donating Abilities in a Pincer‐Type Framework

Evaluation of the acidity of proton‐responsive ligands such as protic N‐heterocyclic carbenes (NHCs) bearing an NH‐wingtip provides a key to understanding the metal–ligand cooperation in enzymatic and artificial catalysis. Here, we design a CNN pincer‐type ruthenium complex 2 bearing protic NHC and isoelectronic pyrazole units in a symmetrical skeleton, to compare their acidities and electron‐donating abilities. The synthesis is achieved by direct C?H metalation of 2‐(imidazol‐1‐yl)‐6‐(pyrazol‐3‐yl)pyridine with [RuCl₂(PPh₃)₃]. ¹⁵N‐Labeling experiments confirm that deprotonation of 2 occurs first at the pyrazole side, indicating clearly that the protic pyrazole is more acidic than the NHC group. The electrochemical measurements as well as derivatization to carbonyl complexes demonstrate that the protic NHC is more electron‐donating than pyrazole in both protonated and deprotonated forms.     

Multimetal‐Substituted Epsilon‐Iron Oxide ϵ‐Ga0.31Ti0.05Co0.05Fe1.59O3 for Next‐Generation Magnetic Recording Tape in the Big‐Data Era

From the viewpoints of large capacity, long‐term guarantee, and low cost, interest in magnetic recording tapes has undergone a revival as an archive storage media for big data. Herein, we prepared a new series of metal‐substituted ?‐Fe₂O₃, ?‐Ga^III_0.31Ti^IV_0.05Co^II_0.05Fe^III_1.59O₃, nanoparticles with an average size of 18 nm. Ga, Ti, and Co cations tune the magnetic properties of ?‐Fe₂O₃ to the specifications demanded for a magnetic recording tape. The coercive field was tuned to 2.7 kOe by introduction of single‐ion anisotropy on Co^II (S=3/2) along the c‐axis. The saturation magnetization was increased by 44 % with Ga^III (S=0) and Ti^IV (S=0) substitution through the enhancement of positive sublattice magnetizations. The magnetic tape media was fabricated using an actual production line and showed a very sharp signal response and a remarkably high signal‐to‐noise ratio compared to the currently used magnetic tape.     

Conductance Study of 1 : 1 19-Crown-6 Complexes with Various Mono- and Bivalent Metal Ions in Water

Formation constants (ML) of 1 : 1 19-crown-6 (19C6) complexes with mono- (M+) and bivalent metal ions (M2+) were determined in water at 25 °C by conductometry. The KML value of 19C6 for M+ and M2+ decreases in the order Rb+ K+ > Tl+ > Na+ = Ag+ > Li+ Cs+ and Pb2+ > Ba2+ > Sr2+ > Cd2+ > Ca2+, respectively. The selectivity for the neighboring alkali metal ions in the periodic table is lower for 19C6 than for 18-crown-6 (18C6) except for the case of Rb+ and Cs+. The same is true for the alkaline earth metal ions. Generally, the KML values of 19C6 with M2+ are greater than those with M+. For Na+ and the ions which are smaller in size than Na+ (Li+, Ca2+, Cd2+), the KML value is larger for 19C6 than for 18C6, but the contrary holds for all the other ions of larger sizes than Na+. The limiting ionic molar conductivity (°) of the 19C6–K+ complex in water at 25 °C was determined to be 43. Although 19C6 is larger than 18C6, the 19C6–K+ complex is much more mobile in water than the 18C6–K+ complex.     

Enantioseparation of 3-Hydroxycarboxylic Acids via Diastereomeric Salt Formation by 2-Amino-1,2-diphenylethanol (ADPE) and Cinchonidine

Enantioseparation of 3-hydroxycarboxylic acids via diastereomeric salt formation was demonstrated using 2-amino-1,2-diphenylethanol (ADPE) and cinchonidine as the resolving agents. Racemic 3-hydroxy-4-phenylbutanoic acid (rac-1), 3-hydroxy-4-(4-chlorophenyl)butanoic acid (rac-2), and 3-hydroxy-5-phenylpentanoic acid (rac-3) were efficiently resolved using these resolving agents. Moreover, the successive crystallization of the less-soluble diastereomeric salt of 1 and cinchonidine using EtOH yielded pure (R)-1 · cinchonidine salt in a high yield. The crystal structures of less-soluble diastereomeric salts were elucidated and it was revealed that hydrogen bonding and CH/π interactions play an important role in reinforcing the structure of the less-soluble diastereomeric salts.     

Improvement of magnetic intergranular isolation and evaluation of read/write characteristics on SmCo5 perpendicular magnetic thin films

SmCo₅ alloy is a promising candidate for ultra-high-density perpendicular magnetic recording (PMR) media because of its high uniaxial magnetocrystalline anisotropy K_u of more than 1.1×10⁸ erg/cm³. Previously, we successfully achieved high K_u in a sputter-deposited SmCo₅ thin film by introducing a Cu/Ti dual underlayer. However, in order to apply the SmCo₅ films to practical PMR media, it is necessary to decrease medium noise. A granulated magnetic film comprising of small and magnetically decoupled grains is effective in reducing the medium noise. In this paper, we have proposed a new granular film that is fabricated by partial thermodiffusion of Cu between the Sm-Co continuous layer and the Cu underlayer, which is granulated using compositional segregation caused by the addition of Ta₂O₅. We have analyzed the magnetic properties, magnetic domain size, and magnetization reversal process of the proposed SmCo₅ film. The magnetic domain size decreased and the magnetization reversal process changed from the magnetic-wall-motion mode to a coherent rotation mode to some extent on isolation of magnetic grains. The read/write characteristics of granulated SmCo₅ double-layered media were also evaluated. The medium noise decreased and the signal-to-noise ratio increased for the granulated double-layered (PMR) medium.     

A photoluminescent six-coordinated zinc(II) complex with hydroxides as axial ligands, [Zn(Hhpa)2(OH)2] (Hhpa = 3-hydroxypicolinamide)

A highly luminescent zinc(II) complex has been prepared using 3-hydroxypicolinamide; it has a six-coordinated octahedral structure with hydroxides as axial ligands in solution.