PREPARATION AND STRUCTURE OFFIVE DERIVATIVES OFβ-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM*

A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β-(1→3)-D-glucan, sample PCS3-Ⅱ, isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me2SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3-Ⅱ, C-PCS3-Ⅱ, M-PCS3-Ⅱ, HE-PCS3-Ⅱand HP-PCS3-Ⅱ. Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), ^1H-NMR, ^13C-NMR, 2D-COSY, 2D-TOCSY and 2D-^1H-detected ^1H ^13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β(1→3)-D-glucan is in the order C-6 ＞ C-4 ＞ C-2 on the whole. The substitution of the samples S-PCS3-Ⅱ, C-PCS3-Ⅱ and M-PCS3-Ⅱ occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3-Ⅱ occurred at C-6 and C-4 positions and of HP-PCS3-Ⅱ almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from ^13C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3-Ⅱ ＞ C-PCS3-Ⅱ ＞ M-PCS3-Ⅱ ＞ HE-PCS3-Ⅱ ＞ HP-PCS3-Ⅱ. This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β-(1→3)-D-glucan.     

SOLUTION PROPERTIES OF ANTITUMOR CARBOXYMETHYLATED DERIVATIVES OF α-(1→3)-D-GLUCAN FROM GANODERMA LUCIDUM

Fractions of a water insoluble α-(1→3)-D-glucan (GL) extracted from Ganoderma lucidum were carboxy-methylated (CM) to obtain water-soluble carboxymethylated derivatives (CM-GL) having a degree of substitution (DS) of0.38～0.51. Weight-average molecular weight M_w and intrinsic viscosity [η] of the samples CM-GL were measured by gelpermeation chromatography combined with laser light scattering (GPC-LLS) and viscometry. The CM-GL exhibits a stifferchain in aqueous solution at 25℃ than the original glucan, The antitumor activities against Ehrlich ascites carcinoma (EAC,5×10~6) of the carboxymethylated derivatives from the α-glucan and curdlan, a β-glucan, are significantly higher than thoseof the original glucans. The effects of the relatively low molecular weight, expanded chains and better water-solubility of theCM-GL on the enhancement of antitumor activity could not be neglected. The chain stiffness decreased speedily withincrease of temperature from 40 to 60℃ or NaOH concentration from 0.1 to 0.4 in the solution, respectively, and the changeof the chain stiffness is reversible.     

EFFECT OF THE COMPOSITION OF m-CRESOL/H2O SOLVENT ON HYDRODYNAMIC PROPERTIES OF NYLON 6

The intrinsic viscosity [ η], Huggins constant (KH), [ η]0, α3 and flow activation energy values of nylon 6 have been measured in water/m-cresol (0/100-20/80) systems at different temperatures (20-60℃). It has been found that the intrinsic viscosity, [η]0 and α3 increase with the increase in water contents in m-cresol up to 15% and then decrease. They increase with the increase in temperature irrespective of solvent composition. It has been noted that the percent increase of α3 is the highest at 60℃ and the lowest at 20℃ for a particular solvent system. The intrinsic viscosity data obey Arrhenius equation over the considered conditions. The activation energy and the KH values decrease very sharply with the addition of water,giving a minimum value at 15% of water and then increase slowly. The variation of all the parameters has been explained in terms of variation in thermodynamic quality of solvent with the addition of water to m-cresol and change in temperature,resulting in the change of conformational and orientational properties of polymer molecules. This change of solvent quality also results in variation of selective sorption of solvent over the polymer, such as hydrogen bonding, etc.     

STRUCTURE, MOLECULAR WEIGHT AND BIOACTIVITIES OF （1→3）-β-D-GLUCANS AND ITS SULFATED DERIVATIVES FROM FOUR KINDS OF LENTINUS EDODES

Abstract Lentinan samples, (1→3)-β-D-glucans containing 4.6-15.2 wt% proteins, coded as L-I1. L-I2. L-I3 and L-I4 (L-I)were isolated from four kinds of Lentinus edodes. These glucans were treated with acetone to remove the protein in order to obtain free protein glucans coded as LNP-I1. LNP-I2, LNP-I3 and LNP-I4 (LNP-I). The free-protein polysaccharides were sulfated to give derivatives (S-LNP-I) with degree of substitution (DS) from 0.4-0.8. The structural features and weight- average molecular weight (Mw) of the samples were investigated by using infrared spectroscopy, elemental analysis,^13C-NMR, size exclusion chromatography combined with laser light scattering (SEC-LLS) and viscometry. The effects of structure and conformation of the polysaccharides on antitumor activities were assayed in vivo (Sarcoma 180 solid tumors)and in vitro (Sarcoma 180, HL-60, MCF-7 and Vero tumors). The results indicated that the predominant species of the samples L-I and LNP-I in 0.2 mol/L NaCl aqueous solution existed as triple-helical chains with high rigidity and in dimethyl sulfoxide (DMSO) as single-flexible chains. Interestingly, the antitumor activities of LNP-I are lower than those of the native glucans (L-I), whereas their sulfated derivatives have higher inhibition ratio against Sarcoma 180 than LNP-I. The results reveal that the binding of protein, sulfated modification and the triple helix conformation are important factors in the enhancement of the antitumor activities of polysaccharides on the whole.     

Synthesis and MALDI-TOF Characterization of β-CD Core ATRP Initiators and RAFT Chain Transfers with Different Degrees of Substitution

In this paper, three different kinds of β-CD derivatives were synthesized as atom transfer radical polymerization(ATRP) initiator or reversible addition-fragmentation chain transfer polymerization(RAFT) chain transfers. The degree of substitution for each derivative was carefully characterized through 1H-NMR, 13C-NMR spectroscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry(MALDI-TOF-MS). The factors influencing the degree of substitution were discussed. Moreover, the comparison between ATRP and RAFT was shown in the polymerization of Nisopropyl acrylamide(NIPAM).     

GRAFT COPOLYMERIZATION OF DENTAL COLLAGEN WITH METHYL METHACRYLATE

The graft copolymerization of MMA onto human dentin was studied with the redox system usingK_2S_2O_8+NaHSO_3 as initiator. The IR spectrum of the copolymer showed the presence of C=Oband at 1720 cm~(-1),C--O at 1260~(-1), CH_3, at 2850 cm~(-1). indicating the presence of polymerized me-thacrylate on the detin. The ppt. of the acid hydrolysis of the graft copolymer showed an -NH_3~+band of amino acid at 3200 cm~(-1). Most marked percent decreases in contents of amino acids inthe acid hydrolysate were observed in serine, tyrosine and methionine. The absolute amounts ofglycine, alanine and proline have also decreased markedly. This suggests that it was most proba-ble that the graft copolymerization occurred at these residues. The tubular stripes and cross sectioncavities of dentin tublets were covered with a high polymer graft which could be seen from the SEMpictures. The mol. wt. of this grafted high polymer, as determined by GPC, was higher than thatof the homopolymer and the former had a broader mol. wt. distribution. All these facts suggest-ed that a genuine graft copolymerization of MMA onto human dentin occurred.     

Theoretical Calculation about the High Energy Density Molecules of Nitrate Ester Substitution Derivatives of Prismane

The nitrate ester substitution derivatives of prismane were studied at the B3LYP/6-311G** level. The sublimation enthalpies and heats of formation in gas phase and solid state were calculated. The detonation performances were also predicted by using the famous Kamlet-Jacbos equation. Our calculated results show that introducing nitrate ester group into prismane is helpful to enhance its detonation properties. Stabilities were evaluated through the bond dissociation energies, bond order, characteristic heights(H50) and band gap calculations. The trigger bonds in the pyrolysis process of prismane derivatives were confirmed as O–ON_2 bond. The BDEs of all compounds were large, so these prismane derivatives have excellent stability consistent with the results of H50 and band gap.     

PREPARATION OF POLYETHERSULFONE ULTRAFILTRATION MEMBRANES FOR MILK CONCENTRATION AND EFFECTS OF ADDITIVES ON THEIR MORPHOLOGY AND PERFORMANCE

Polyethersulfone membranes were prepared from quaternary systems containing N,N-dimethylacetamide （DMAc） as solvent, polyvinylpyrrolidone （PVP） as constant additive and acetic acid, acetone and water as variable additives. Phase inversion via immersion precipitation was employed for manufacturing of membranes. The prepared films were immersed in the mixture of pure water and 2-propanol （30/70 vol%） as the non-solvent. Acetic acid caused an increment in the flux at high polymer concentration （16 wt%） and a decline in the flux at low polymer concentrations （10 wt% and 13 wt%）. Acetone and water as the solvent in the casting solution declined the flux at any polymer concentration tested. The morphology and performance of the prepared membranes were investigated by scanning electron microscopy and separation experiments using milk as the feed.     

SYNTHESIS AND CATIONIC RING-OPENING POLYMERIZATION OF 1, 4-ANHYDRO-2, 3-DI-O-(P-AZIDOBENZYL)-α-D-RIBOPYRANOSE

New highly stereoregular 2, 3 -di- O-(p-azidobenzyl )-(1 →5 ) - α-D -ribofuranan was synthesized byselective ring-opening polymerization of 1, 4-anhydro-2, 3 - di-O -(p-azidobenzyl )-α-D -ribopyranose(ADABR) using phosphorus pentafluoride or tin tetrachloride as catalyst at low temperature indichloromethane. The monomer was obtained by the reaction of p - bromomethyl -phenyleneazide with 1, 4 -anhydro-α-D-ribose in DMF. The structure of poly(ADANR) was identified by specific rotation and ~(13)C-NMR spectroscopy. Acid chloride-AgCl_4 complex catalyst such as CH_2=C(CH_3)C~+OClO_4~- used in thepolymerization resulted in polymers with mixed structures, i.e. (1→5)-α-D-ribofuranosidic and (1→4)-β-D-ribopyranosidic units. However, with C_6H_5C~+OClO_4~- as catalyst, pure (1→5)-α-D-ribofuranan was obtained.The effects of catalyst, polymerization temperature and time on polymer stereoregularity were examined, andthe mechanism of the ring-opening polymerization was discussed.     

ESR SPECTRA STUDY OF COPPER(Ⅱ) COORDINATION COMPLEXES OF PYRIDI

The ESR spectra of powdered samples of Cu(Ⅱ) complexes with pyridine and its sixhomologues and pyrrol, aniline, as well as their solutions are measured at 77K in this paper.The electronic levels of these complexes are calculated from the ESR spectral parameters.It is found that the non-pyridine ligands of complexes which can be substituted by pyridinemolecules of solvent in solution of pyridine/chloroform form Py_4Cu~(2 ). A molecular configura-tion is proposed. for Py_4Cu~(2 ) in solution. It is shown that the treatment with D_(2h) symmetryinstead of D_(4h) symmetry leads to a more satisfactory explanation of the ESR spectra.     

CRITICAL CONCENTRATIONS OF α(1→3)-D-GLUCAN FROM LENTINUS EDODES IN NaOH AQUEOUS SOLUTION

Critical concentrations of α-(1→3)-D-glucan L-FV-Ⅱ from Lentinus edodes were studied by viscometry andfluorescence probe techniques. The dependence of the reduced viscosity on concentration of the glucan in 0.5 mol/L NaOHaqueous solutions with or without urea showed two turning points corresponding to the dynamic contact concentration c_s andthe overlap concentration c~* of the polymer. The values of c_s and c~* were found to be 1×10~(-3) g cm~(-3) and 1.1×10~(-2) g cm~(-3),respectively, for L-FV-Ⅱ in 0.5 mol/L NaOH aqueous solutions. The two critical concentrations of L-FV-Ⅱ in 0.5 mol/LNaOH aqueous solutions were also found to be 1.2×10~(-3) g cm~(-3) fbr c_s and 9.2×10~(-3) g cm~(-3) for c~* from the concentrationdependence of phenanthrene fluorescence intensities. The overlap concentration c~* of L-FV-Ⅱ in 0.5 mol/L NaOH aqueoussolutions was lower than that of polystyrene with same molecular weight in benzene, owing to the fact that polysaccharidetends to undergo aggregation caused by intermolecular hydrogen bonding. A normal viscosity behavior of L-FV-Ⅱ in 0.5 mol/L urea/0.5 mol/L NaOH aqueous solutions can still be observed in an extremely low concentration range at 25℃.     

Effect and Mechanism Analysis of Solvent on the Electron Transition of Fluoroquinolones Based on Quantum Chemical Calculation

Ciprofloxacin(CIP), moxifoxacin(MOX) and enrofloxacin(ENR) were selected as typical fluoroquinolones(FQs) to analyze the excitation-enhancing effect and mechanism of solvents on FQs' electron transition based on quantum chemical calculations. The UV spectra of three FQs in gas and five different solvents(water, cyclohexane, dimethylsulfoxide, methanol, acetone) were calculated using Gaussian 09 software. The transition mechanisms of FQs' main electron transitions were analyzed by natural bond orbital(NBO) theory, and the solvent effect on each electron transition was assessed qualitatively and quantitatively by sensitivity analysis and an established index system. The excitation enhancing mechanism of solvent on electron transitions of FQs was analyzed from the view of photo-induced reactions between solvent and FQs molecules. The results show that there are two main transitions located in the spectrum ranges of 300~380 and 240~300 nm for each FQ in any medium, which are assigned as n →π* and π→π* electron transitions, respectively. By comparison, the n →π* transition is more sensitive to solvent because of the energy transfer between solvent molecules and FQs, but the solvent effect on the π→π* transition is stronger than on the n →π* transition. The sequence of affected extent of solvent effect on electron transition was CIP MOX ENR, and the sequence of solvent effect was water DMSO methanol acetone cyclohexane(stronger solvent effect with increasing the dielectric constant of solvent). From the view of photo-induced reactions, the reaction between FQs*T1 and solvent*T1 has the decisive regulatory effect on the n →π* transition of FQs in solvent, and the reaction between FQsS0 and solvent*TI has an enhancing effect on the π→π* transition.     

STRUCTURE AND CATALYTIC ACTIVITY OF RHODIUM COMPLEX COORDINATED ON 2-VINYLPYRIDINE-METHYL ACRYLATE COPOLYMER FOR THE CARBONYLATION OF METHANOL

A series of rhodium complexes coordinated on the hybrid ligand. 2-vinylpyridine-methyl acrylate copolymers, as catalyst for the carbonylation of methanol were synthesized by the reaction of the copolymers with tetracarbonyldichlorodirhodium. These complexes were in general very reactive in carbonylation of methanol to form acetic acid and methyl acetate without other by-product. The XPS studies of the complexes showed that the binding energies of Nls(399.1-399.4 eV) and that of Ols(532.5-532.9 eV) were higher than that of the copolymer ligand (Nls 398.1-398.3 eV and Ols 532.2-532.3 eV), indicating the fromation of N→Rh and O→Rh coordination bonds. The IR spectra of complexes showed that the appearance of two absorption peaks of terminal carbonyl at 1990-2100 cm~(-1), characteristic of the cis-dicarbonyl rhodium moiety. These XPS and IR studies confirm the formation of cis-dicarbonylrhodium complex with the active centers(A) and (B) as shown in the text. The increase of activity of the complex in the c     

Solvent-induced molecular gel formation at room temperature and the preparation of related gel-emulsions

The gelation behaviors of four recently reported amphiphilic cholesteryl derivatives (1, 2, 3 and 4) have been evaluated. It was found that the gel formation process can be controlled by introduction of water at room temperature. Addition of water to an acetone solution of 4 immediately results in the system becoming turbid, and a gel subsequently forms within a few minutes. Interestingly, 4 is a super-gelator for a mixed solvent of acetone and water at room temperature, in particular when their volume ratio is close to 1:1 at which the critical gelation concentration (CGC) is 0.06% (w/v). It was found that the introduction of water favors the formation of gel networks, and the gel possesses smart and reversible thixotropic properties. FTIR and 1H NMR spectroscopy confirmed that hydrogen bonding is one of the main driving forces for the gelation of the solvents. XRD demonstrated that 4 self-assembled into a layered structure within the acetone-water mixed solvent gel. Furthermore, 1 and 2 can be used as excellent stabilizers for gel emulsions of alkanes and water. The maximum of the dispersed phase, water, in one of the gel-emulsions can be as high as 97% (v/v).     

SYNTHESIS,PHOTOCHROMIC PROPERTIES OF PYRRYL SUBSTITUTED HETEROCYCLIC FULGIDES

Nine new 3-acetyl pyrrole derivatives and corresponding 3-pyrryl substitutedheterocyclic fulgides:3-pyrryl-ethylidene(isopropylidene)succinic anhydrides havebeen synthesized and characterized.Their photochromic behavour in several organicsolvents were investigated.The coloured form of fulgide Ⅱc,(E)-α-(1,2,4-trimethyl-3-pyrryl)-ethylidene(isopropylidene)succinic anhydride,shows absorption maxmium at715nm in acetonitrile.It is the longest absorption among the known photochromicfulgides     

SOLVENT QUALITY AND SOLUTION BEHAVIOR OF NYLON 12

The refractive index increment,dynamic and static laser light scattering,intrinsic viscosity[η]and Huggins constant(K_H)of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60℃.The intrinsic viscosity,R_H,R_g,A_2,and(~2)~(1/2)(calculated from viscosity data)and"a"values of nylon 12 are found to be higher in m-cresol than in sulphuric acid.All these parameters decrease with the increase in water contents in sulphuric acid.The refractive index increment,K_H and activation energy show an opposite trend to that of[η].The intrinsic viscosity,R_H,R_g,A_2, and(~2)~(1/2) have maximum values around 30-40℃in sulphuric acid/water system,whereas in m-cresol they fall at about 20℃.It has been concluded that the variation in size,interaction parameter(second virial coefficient),[η]and K_H of the polymer solutions with the alteration in solvent composition and temperature are the out come of change in thermodynamic quality of solvents,selective adsorption,hydrogen bonding and conformational transitions.It has also been concluded that the increase in temperature first enhances the quality of the solvent,encourages hydrogen bonding and specific adsorption, and then deteriorates,bringing conformational transitions in the polymer molecules.However,the addition of water to sulphuric acid continuously deteriorates the solvent quality.This characteristic of the solvent system brings conformational changes in the polymer especially at low temperatures.     

Synthesis of novel analogues of zanamivir as neuraminidase inhibitors

<正>A versatile synthesis of novel zanamivir analogues modified at C-4 and C-8 positions was described.The formation of amides from the acid with corresponding amines,followed by click chemistry generated the triazole substituted compounds as novel analogues of neuraminidase inhibitors in good yields.     

POTENTIOMETRIC BEHAVIOR OF CHELATING ION EXCHANGE RESIN IN WATER AND IN ETHANOL-WATER MIXTURES

The potentiometric behavior of the chelating ion exchange resin D751 containing iminodiacetic acid groups has been studied at 25℃ by batch titration with alkali and acid in water and in ethanol - water mixture solvent. The titrtion curves, the amount of chemically bound counter-ions and invasive electrolytes in the resin phase,and the solvent contents of the resin have been investigated.     

STUDIES OF ACTIVE DIACYLAMIDES OF BENZOTRIAZOLE Ⅰ. SYNTHESIS OF POLYAMIDES AND POLYESTERS*

Two new routes to polyamides and polyesters were established, based on the polycondensationof new typical active diacylamide of benzotriazole, such as 1, 1'-(isophthaloyl) bisbenzotriazole(IPBBT) and 1, 1'-(terephthaloyl)bisbenzotriazole (PBBT) with diamines, diols and diphenol underdifferent mild conditions. The N-acylation of polycondensation occurred at room temperaturewithout added catalyst, the O-acylation of polycondensation had to complete in the presence oftriethylamine as a catalyst at 60℃.     

COMPARATIVE OBSERVATION OF FIRST MITOSIS IN DIFFERENTIATION AND

On the basis of observing the continuous process of the first mitosis of normal differ-entiation in vivo and comparing this observed results with the process of the first mitosisof dedifferentiation in vitro in wheat pollen grains, the cytological differences between thetwo kinds of mitosis have been found. These differences are expressed chiefly by the posi-tions of nuclei and cytoplasm as well as the positions and shapes of spindles and new cellwalls. The author considers: (i) The differences exist as soon as cell division begins. Sothe critical moment causing cell dedifferentiation is at the interphase instead of the divisionstage. Therefore, the viewpoint that the cause of dedifferentiating initiation is the altera-tion of the direction of the spindle axis could not be agreed. (ii) The cause producing thesecytological differences can be related to the loss of polarity in the dedifferentiating process.