Effect of substituent distribution on water solubility of O-methylcellulose

The effect of substituent distribution on the water solubility of O-methylcellulose (MC) was re-examined to elucidate the lower limit of the degree of substitution (DS) in water-soluble MC. To this end, a series of 2,3-MCs which are regioselectively substituted at the C-2 and C-3 hydroxyl groups were prepared by homogeneous methylation. It was found that the lower limit for the DS value of water-soluble 2,3-MC was almost the same as that for MCs having even distributions of substituents along the cellulose chain as well as in the anhydroglucose units. This revised version was published online in August 2006 with corrections to the Cover Date.     

NMR analysis of cellulose dissolved in aqueous NaOH solutions

Low molecular weight cellulose (degree of polymerization = ca 15) was dissolved in 4-- 30% NaOD/D2O, and relationships between 1H- and 13C-chemical shifts of the cellulose and NaOD concentrations were studied in terms of the dissociation of three hydroxyl groups of cellulose in aqueous NaOH solutions. All C---H proton resonances were shifted upfield linearly with an increase in the NaOD concentration, indicating that all C---H protons of cellulose undergo the electron-shielding effect by NaOH. On the other hand, the shifting patterns of carbon resonances varied among the six carbons: C1 and C4 carbons undergo the electron-shielding effect, whereas C2, C3, C5, and C6 carbons experience the electron-deshielding effect by NaOH. Changes in 13C-chemical shifts of cellulose carbons in 4--30% NaOD/D2O indicate that C3---OH has the highest resistance to dissociation in aqueous NaOH of the three hydroxyl groups of an anhydroglucose residue. It is plausible, at least from the aspects of 13C-chemical shifts, that cellulose molecules dissolving in 20--30% NaOH behave differently from those swollen in 20--30% NaOH as alkali- cellulose     

多乙酰氧基烷基(艹卓)酮和多羟基烷基(艹卓)酮的合成

各种溴代的烷基酚酮的乙酸酯用乙酸酐/三氟乙酸酐/乙酸(以下简称ATA)醋解可得高收率的相应的多乙酰氧基烷基酮,后者经稀酸水解几乎定量地得多羟基烷基酮。部分多乙酰氧基酮对肺癌A_(549)和上皮细胞癌显出抑制活性。     

ULTRAVIOLET RESONANCE RAMAN SPECTRA OF PHYTOCHROME: A COMPARISON OF THE ENVIRONMENTS OF TRYPTOPHAN SIDE CHAINS BETWEEN RED LIGHT-ABSORBING AND FAR-RED LIGHT-ABSORBING FORMS

Ultraviolet resonance Raman spectra of phytochrome in the red light-absorbing form (Pr) and the far-red light-absorbing form (Pfr) are reported. The spectra excited at 240-nm provide structural information about the protein part of phytochrome. The protein contains only a very small amount of β-sheet structure and most of the tyrosine side chains are located in hydrophobic environments. Indole rings of tryptophan (Trp) interact with neighboring groups in the Pr form and these interactions become weaker with the conversion from Pr to Pfr. Some Trp side chains of Pfr are surrounded by aliphatic groups but such is not the case in Pr. These changes in the environment occur at the same time as changes in orientation of Trp side chains. Our observations suggest that interactions between Trp residues and the tetrapyrrolic chromophore occur in the Pr form and that the strength of these interactions diminishes in the Pfr form.     

Three Dimensional Numerical Flow Simulation Around Parallel Rectangular Cylinders

Noises of flow around parallel rectangular cylinders are likely to be caused by wind flow. According to the wind tunnel experiment, it is known that there are three kinds of special noises. Two kinds of noises occur when the wind comes from a perpendicular direction to the cylinders. These noises are caused by the vortex excited oscillation. Another noise occurs when the wind comes from an inclined direction to the cylinders. This noise is very high frequency, and its mechanism is not clear. Therefore in this study, the three dimensional numerical flow simulation is performed to clarify the high frequency noise of flow around parallel rectangular cylinders.     

Application of the elongation method to nonlinear optical properties: finite field approach for calculating static electric (hyper)polarizabilities

A novel finite-field approach for calculating electric (hyper)polarizabilities based on the elongation method is developed. The method was tested at the semi-empirical PM3 level by using three model systems: the hydrogen chain, the water chain and polyacetylene. The results satisfactorily reproduce the ‘exact’ MOPAC values. The most important advantage of this approach is the large saving of computer time since the dimension of the SCF equation remains the same regardless of the number of atoms in the system. Thus, it is a very useful tool to treat large systems. The method can also be applied to building up a chain containing an arbitrary sequence of monomers.     

Complex Formation of Cyclodextrins with Various Thiophenes and their Polymerization in Water: Preparation of Poly-pseudo-rotaxanes containing Poly(thiophene)s

Cyclodextrins (α-CD, β-CD and 2,6-di-O-dimethyl-β-CD (DM-β-CD)) were found to form inclusion compounds with thiophenes (thiophene (T), bithiophene (2T)) in water and in crystalline states. The structures of α-CD–T, β-CD–2T, and DM-β-CD–2T inclusion complexes were determined by X-ray crystallography. DM-β-CD forms a 1:1 cage type complex with 2T. In contrast, β-CD formed 2:3 (CD:guest) complexes with thiophene and α-CD formed 2:3 complexes, both of the channel type. These inclusion complexes were found to polymerize by FeCl₃ in the inclusion compounds in water. The products were formed poly-pseudo-rotaxane between cyclodextrins and poly(thiophene) characterized by IR, ¹H-NMR and ¹³C CP/MAS NMR. The molecular weights of the poly-pseudo-rotaxanes with poly(thiophene) were determined by the MALDI-TOF mass spectra to be 3000–5000. In comparison between poly-pseudo-rotaxane (DM-β-CD–poly(thiophene)), authentic poly(thiophene) and the washed DM-β-CD–poly(thiophene) which was washed with DMF to dethread DM-β-CD, these poly-pseudo-rotaxane was characterized by Raman, UV–vis and fluorescence spectra. The maximum emission band of DM-β-CD–poly(thiophene) shifted to a shorter wavelength. The hypsochromic shift was derived from poly-pseudo-rotaxane with DM-β-CD.     

MoS2在菜籽油中的高温摩擦磨损性能研究

采用多功能SRV摩擦磨损试验机考察了含质量分数5%MoS2的菜籽油的高温摩擦磨损性能.结果表明:在点接触条件下,MoS2在200～400 ℃范围内表现出非常低的摩擦系数(约0.06),但在100 ℃和500 ℃时,其摩擦系数与菜籽油相当;在线接触条件下,MoS2在不同温度下的摩擦系数变化趋势与点接触条件下的相似;无论在点接触还是线接触条件下,MoS2在不同试验温度下的抗磨性能均比菜籽油好,尤其在300 ℃时MoS2显示出优异的抗磨性能,含5%MoS2的菜籽油在300 ℃时显示出非常优异的减摩抗磨性能.这是因为MoS2主要以吸附形式存在于摩擦表面.