Hybrid dendritic–linear graft copolymers: Steric considerations in “coupling to” approach

A “coupling to” approach was developed for the synthesis of hybrid dendritic–linear block copolymers. Fréchet‐type polyether dendrons were prepared by the convergent growth approach and coupled with well‐defined functionalized polystyrene backbones prepared by living free radical procedures. The subtle interplay between the degree of functionalization present in the backbone and the size of the dendritic fragment led to incomplete reactions as steric crowding along the backbone increased. This resulted in globular hybrid macromolecules instead of the extended rods typically formed from the polymerization of dendritic macromonomers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1033–1044, 2000     

Thin Layer Chromatography of Purines on Silica Gel G Impregnated with Transition Metal Ions; Assay of Caffeine and Theophylline in Pharmaceutical Formulations

This study was undertaken to develop thin layers of silica gel G impregnated with transition metal ions for separation, identification and estimation of purines. The influence of transition metal ions and eluting solvents on chromatographic behaviour (hR_f) has been studied. The method was applied for qualitative analysis of purines in the mixtures and quantitative analysis of purine bases in the mixture as well as in pharmaceutical formulations. The results were compared statistically with those obtained by official methods. The method is simple, reproducible, and accurate within 1.3 ± 0.6%.     

Revisiting parallel car parking problem

Among many physical and mechanical engineering problems, parallel car parking has drawn the attention of many researchers as it shows how methods of Lie algebra and differential geometry can be applied elegantly to explain the behavior of such a system. In this paper we have reviewed some aspects of this problem in this context and analyse the stability and controllability of such a system by some unconventional integrators like Kahan and Lie trotter integrator. At the same time we have also given the results obtained through conventional Runge Kutta integrator to see a comparison.     

Effect of metamaterial layer on optical surface plasmon resonance sensor

In this paper an optical surface plasmon resonance (SPR) sensor with metamaterial for four and five layered structure is studied. The numerical results presented in this paper leads to a significant properties of metamaterials in sensing field. Computed results of SPR sensors using metamaterial are compared with conventional optical SPR sensors for four and five layered structure. It is seen that wider dynamic range or effective range of measurable refractive index increases when metamaterial layer is used. It is also verified that SPR sensor with metamaterial layer can dramatically enhance the resolution and reduce the reflectivity compared with conventional SPR. Validity of the magnetic field results is proved on the basis of smooth match of the fields in the different layers of the proposed optical SPR sensor.     

First principles electronic structure investigation of order of singlet and triplet states of oxyhemoglobin and analysis of possible influence of muon trapping

Interest in the possibility of magnetic character for oxyhemoglobin (OxyHb) has been recently stimulated by the observations of muon spin-lattice relaxation effects studied (Nagamine et al., Proc Jpn Acad Ser B Phys Biol Sci 83:120–126, 2007) with the muon-spin rotation (μSR) technique. In view of this, we have carried out first-principles electronic structure investigations involving Hartree–Fock theory combined with many body perturbation effects for the singlet and triplet states of OxyHb. Our results indicate that using two recent x-ray structural data (Paoli et al., J Mol Biol 256:775, 1996; Park et al., J Mol Biol 360:690, 2006) for OxyHb, for only Hartree–Fock theory without many-body effects included, the singlet state lies above the triplet state by energies of about 0.08 and 0.13 a.u. for the two structures in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). Incorporation of many-body effects by the perturbation method reverses the order, with the triplet state located 0.18 and 0.14 a.u. above the singlet state for the structures in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). Physical reasons for these relative orderings of the singlet and triplet states will be discussed. It is clear that OxyHb by itself would be in a singlet state at room temperature or below, since from our calculation, the triplet state lies about KT above the singlet state with T having the value of 44,098 K and 56,449 K for the two structural data in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). As regards the muon spin-lattice relaxation effects obtained by recent μSR measurements (by Nagamine et al., Proc Jpn Acad Ser B Phys Biol Sci 83:120–126, 2007) at room temperature, the sensitive dependence of the singlet-triplet separation on many-body effects in our investigation suggests that it is possible that the singlet-triplet separation could be reversed or reduced significantly when a muon is trapped near an oxygen atom of the oxygen molecule, allowing the triplet to be occupied at room temperature and lead to significant muon spin-lattice relaxation.     

Characteristics of a High Maltose-Forming, Acid-Stable, and Ca2+-Independent α-amylase of the Acidophilic Bacillus acidicola

The purified acidic α-amylase of Bacillus acidicola is a monomer of 66.0 kDa, optimally active at pH 4.0 and 60 °C. The enzyme is Ca²⁺ independent with T _1/2 for 18 min at 80 °C. The K _m, V _max, and catalytic efficiency (k _cat/K _m) of the enzyme are 1.6 mg mL^?1, 23.8 μmol mg^?1 min^?1, and 981 μmol s^?1, respectively. Among detergents, Tween 20, 40, and 80 stimulated enzyme activity, whereas sodium dodecyl sulfate and Triton X-100 inhibited even at low concentration. EGTA has not affected the activity, whereas EDTA β-mercaptoethanol, iodoacetic acid, and Dithiothreitol exhibited a slight inhibitory action. Phenylmethanesulfonyl fluoride, N-bromosuccinimide, and Hg²⁺ strongly inhibited enzyme activity. The experimental activation energy and temperature quotient are 50.12 kJ mol^?1 and 1.37. When thermodynamic parameters (ΔH and ΔS) of the enzyme have been determined at different temperatures, ΔG is positive suggesting that the enzyme is thermostable. The enzyme hydrolyzes raw starches, and therefore, the enzyme finds application in raw starch saccharification at sub-gelatinization temperatures that saves energy needed for gelatinization of raw starch at 105 °C.     

Non-aqueous synthesis of nano-sized aluminium(III) isopropoxide derivatives with 8-hydroxyquinoline and their sol–gel transformation to nano-sized δ-alumina

Non-aqueous reactions of aluminum isopropoxide with 8-hydroxyquinoline (Hq = HONH₆C₉) in 1:1, 1:2 and 1:3 molar ratios in anhydrous benzene yield complexes of the type [q_nAl(OPrⁱ)_3?n] {where n = 1 (1), n = 2 (2), n = 3 (3)}. Progress of the reactions were monitored by estimating liberated 2-propanol in benzene-2-propanol azeotrope by oxidimetric method. All the products were fluorescent green powders, sparingly soluble in CHCl₃. They were characterized by elemental analysis, FT-IR and (¹H, ¹³C and ²⁷Al) NMR studies. The ESI mass spectral studies indicate dimeric nature for (1) and (2) and monomeric nature for the compound (3). The XRD spectra of (1–3) showed crystalline nature with the average particle size of 45, 32 and 27 nm respectively, as evaluated from Debye–Scherrer equation. The XRD spectrum of (3) also suggests the formation of β-crystalline polymorphs of Alq₃. The SEM images appear to indicate granular morphology for (1) and formation of cylindrical shaped rods for (2) and (3). Sol–gel hydrolysis of (1), (2) or (3) in presence of a strong acid as well as of the precursor, Al(OPrⁱ)₃,without acid or base catalyst, followed by sintering at 950 °C yielded tetragonal primitive phase of nano-sized δ-alumina in all the cases, as reflected by their powder X-ray diffraction pattern. The IR, SEM and EDX studies also support the formation of transition alumina.     

A Convenient Synthesis of Novel Glycosyl Azetidines Under Mitsunobu Reaction Conditions

Abstract

A facile, simple, and high-yielding protocol for synthesis of novel glycosyl azetidines was developed from glycosyl β-amino alcohols via intramolecular cyclization under Mitsunobu reaction conditions.     

Microwave‐Assisted Synthesis of 10‐(Phthalimidoalkyl)‐halosubstitutedpyrido [3,2‐b][1,4]‐benzothiazine in Dry Media

N‐Alkylation of 10H‐9‐fluoropyrido[3,2‐b][1,4]‐benzothiazine 5a, 10H‐7‐fluoropyrido[3,2‐b][1,4]‐benzothiazine 5b, and 10H‐7‐chloropyrido[3,2‐b][1,4]‐benzothiazine 5c with different N‐(bromoalkyl)phthalimides using anhydrous K₂CO₃ and tetrabutylammonium bromide (TBAB) under dry conditions with microwave irradiation leads to the formation of 10‐(phthalimidoalkyl)‐halosubstitutedpyrido[3,2‐b][1,4]‐benzothiazine (6a–f) along with some unidentified product. Compound 5a is a new azaphenothiazine derivative and was obtained from hitherto unknown 2‐acetylamino‐3‐fluorophenyl‐3′‐nitro‐2′‐pyridylsulfide 4a via Smiles rearrangement. Compound 4a is required for the synthesis and has been prepared starting from 2‐amino‐3‐fluorobenzenethiol 1a in three steps.