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1.
Summary The oxidative coupling polymerization of racemic 3,3’-dihydroxy-2,2’-dimethoxy-1,1’-binaphthalene with copper(II) chloride-(-)-sparteine [(-)Sp] in methanol at room temperature was carried out and the enantiomer-selectivity during the polymerization was examined. The (R)-monomer preferentially reacted, and the purity of the unreacted monomer reached 80%ee (S) after 15 h, while that of the polymerized monomer gradually decreased from 26%ee (R) as a function of the polymerization. The ratio of the rate constants of both enantiomers, s=kR/kS, was determined to be 2.3. The model coupling reaction of the mono-benzylated (R)-monomer with CuCl2-(-)Sp showed that the R-configuration with respect to the carbon-carbon bonds between the monomer units was selectively constructed during the polymerization. 相似文献
2.
Asperamides A (1) and B (2), a sphingolipid and their corresponding glycosphingolipid possessing a hitherto unreported 9-methyl-C20-sphingosine moiety, were characterized from the culture extract of Aspergillus niger EN-13, an endophytic fungus isolated from marine brown alga Colpomenia sinuosa. The structures were elucidated by spectroscopic and chemical methods as (2S,2′R,3R,3′E,4E,8E)-N-(2′-hydroxy-3′-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (1) and 1-O-β-d-glucopyranosyl-(2S,2′R,3R,3′E,4E,8E)-N-(2′-hydroxy-3′-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (2). In the antifungal assay, asperamide A (1) displayed moderate activity against Candida albicans. 相似文献
3.
Summary The radical polymerization of a series of fumaramides and fumaramates, prepared from the reaction of various amines with fumaroyl
dichloride and fumaric chloride isopropyl ester, respectively, was investigated. Although the polymerization reactivity of
the N,N,N’,N’-tetrasubstituted fumaramides and N,N-disubstituted fumaramates was low, N-isopropyl fumaramate readily furnished the corresponding high molecular weight polymer. The highest number average molecular
weight (Mn) of 15,400 was obtained from the emulsifier-free emulsion polymerization in the presence of VA-086 as the initiator. The
decomposition temperature of the obtained polymer was determined to be 299 °C. The π-A isotherm of the polymer indicated the
formation of stable Langmuir monolayers with a limiting molecular area (per macromolecular repeating unit) of ca. 26 ?2. 相似文献
4.
The oxidative coupling polymerization of racemic-, (R)-, and (S)-2,2′,3,3′-tetrahydroxy-1,1′-binaphthyl derivatives bearing a crown ether moiety was carried out in the presence of a Cu(I) or Cu(II) catalyst with various ligands, such as N,N,N′,N′-tetramethylethylenediamine, (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine, (−)-sparteine [(−)Sp], and (S)-(−)-2,2′-isopropylidenebis(4-phenyl-2-oxazoline). Methanol-insoluble poly(binaphthyl crown ether) with a molecular weight up to Mn=4.1×103 was synthesized in moderate yields. Polymerization using (−)Sp proceeded in an S-selective manner; the polymer with the highest negative specific rotation was obtained with the (S)-monomer. The obtained polymers exhibited characteristic abilities for chiral recognition toward amino acids, such as 2-phenylglycine hydrochloride and 2-phenylglycine methyl ester hydrochloride. 相似文献
5.
The polymerization (polymer deposition) rate of styrene in an electrodeless glow discharge from styrene vapor and a mixture of styrene vapor and gas (H2, He, A, and N2) was investigated. The rate of polymerization, R, was found to be independent of the discharge power. The rate of polymerization of the pure monomer was found to be proportional to the square of monomer pressure pM. The addition of gas increased the rate of polymerization depending upon the partial pressure of the gas, px, and R can be generally expressed by R = a[pM]2{1 + b[px]}. The value of b is dependent of the type of gas and follows the order of N2, > A > He > H2. The distribution of polymer deposition was found to be nearly independent of the partial pressure of the gas and of the discharge power with N2 and H2 as plasma gas; however, with He and A, the distribution is highly dependent on the partial pressure of the gas and on the discharge power. The study strongly suggests that polymerization occurs in the vapor phase and that the growing polymer radicals deposit on the surface of the discharge vessel, yielding highly crosslinked polymer deposition. 相似文献
6.
The effect of pulegone chiral center configuration on its antifeedant activity to Myzus persicae was examined. Biological consequences of structural modifications of (R)-(+)- and (S)-(−)-pulegone, the lactonization, iodolactonization, and incorporation of hydroxyl and carbonyl groups were studied, as well.
The most active compounds were (R)-(+)-pulegone (1a) and δ-hydroxy-γ-spirolactones (5S,6R,8S)-(−)-6-hydroxy-4,4,8-trimethyl-1-oxaspiro[4.5]decan-2-one (5b) and (5R,6S,8S)-6-hydroxy-4,4,8-trimethyl-1-oxaspiro[4.5]decan-2-one (6b) derived from (S)-(−)-pulegone (1b). The compounds deterred aphid probing and feeding at preingestional, ingestional, and postingestional phases of feeding.
The preingestional effect of (R)-(+)-pulegone (1a) was manifested as difficulty in finding and reaching the phloem (i.e., prolonged time preceding the first contact with phloem
vessels), a high proportion of probes not reaching beyond the mesophyll layer before first phloem phase, and/or failure to
find sieve elements by 20% of aphids during the 8-hr experiment. The ingestional activity of (R)-(+)-pulegone (1a) and hydroxylactones 5b and 6b resulted in a decrease in duration of phloem sap ingestion, a decrease in the proportion of aphids with sustained sap ingestion,
and an increase in the proportion of aphid salivation in phloem. δ-Keto-γ-spirolactone (5R,8S)-(−)-4,4,8-trimethyl-1-oxaspiro[4.5]decan-2,6-dione (8b) produced a weak ingestional effect (shortened phloem phase). The postingestional deterrence of (R)-(+)-pulegone (1a) and δ-hydroxy-γ-spirolactones (5R,6S,8R)-(+)-6-hydroxy-4,4,8-trimethyl-1-oxaspiro[4.5]-decan-2-one (5a), 5b, (5S,6R,8R)-6-hydroxy-4,4,8-trimethyl-1-oxaspiro[4.5]decan-2-one (6a), 6b, and δ-keto-γ-spirolactone 8b prevented aphids from settling on treated leaves. The trans position of methyl group CH3–8 and the bond C5–O1 in lactone 6b appeared to weaken the deterrent activity in relation to the cis diastereoisomer (5b). 相似文献
7.
Two antibacterial and xanthine oxidase inhibitory cerebrosides, one of which is chemically new, were characterized from the
chloroform-methanol (1∶1) extract of Fusarium sp. IFB-121, an endophytic fungus in Quercus variabilis. By means of chemical and spectral methods [IR, electrospray ionization MS (ESI-MS), tandem ESI-MS, 1H and 13C NMR, distortionless enhancement by polarization transfer, COSY, heteronuclear multiple-quantum coherence, heteronuclear
multiple-bond correlation, and 2-D nuclear Overhauser effect correlation spectroscopy], the structure of the new metabolite
named fusaruside was established as (2S,2′R,3R,3′E,4E,8E,10E)-1-O-β-d-glucopyranosyl-2-N-(2′-hydroxy-3′-octadecenoyl)-3-hydroxy-9-methyl-4,8,10-sphingatrienine, and the structure of the other was identified as
(2S,2′R,3R,3′E,4E,8E)-1-O-β-d-glucopyranosyl-2-N-(2′-hydroxy-3′-octadecenoyl)-3-hydroxy-9-methyl-4,8-sphingadienine. Both new and known cerebrosides, although inactive to
Trichophyton rubrum and Candida albicans, showed strong antibacterial activities against Bacillus subtilis, Escherichia coli, and Pseudomonas fluorescens, with their minimum inhibitory concentrations being 3.9, 3.9, and 1.9 μg/mL, and 7.8, 3.9, and 7.8 μg/mL, respectively. Furthermore,
both metabolites were inhibitory to xanthine oxidase, with the IC50 value of fusaruside being 43.8±3.6 μM and the known cerebroside being 55.5±1.8 μM. 相似文献
8.
A new C18-ceramide congener named pecipamide (1), together with the known ergosta-4,6,8(14),22-tetraen-3-one (2), was isolated from the solid fermentations of the basidiomycetous fungus Polyporus picipes. The structure of the new metabolite was established as (2′R,2S,3R)-N-2′-hydroxyheptadecanoyl-2-amino-octadecane-1,3-diol on the basis of spectroscopic data, including 1D- and 2D- nuclear magnetic
resonance spectroscopy (NMR) experiments, as well as by means of mass spectrometric measurements (MS). 相似文献
9.
Qian ZHAO Shirong WANG Xianggao LI LiIi HE 《Frontiers of Chemical Engineering in China》2008,2(3):330-334
Six bisazo compounds were synthesized by coupling 2-(4′-aminophenyl)-6-aminobenzoxazole as diazo component with N-phenyl-N′-(2-hydroxy-3-naphthoyl)urea derivatives, and characterized by ultra-violet and visible spectroscopy (UV-Vis), Fourier transform
infrared spectroscopy (FT-IR) and elemental analysis (EA). Using these bisazo compounds as charge generation materials and
CT-191(2-methyl-4-(N,N-dibenzyl) aminobenzoaldehyde-1,1-diphenylhydrazone) as charge transportation material, organic photoconductive devices were
prepared. The result from photoconductivity measurement of the devices shows that the bisazo compound from N-(2-methylphenyl)-N′-(2-hydroxy-3-naphthoyl)urea has the best xerographic performance, V
0=600 V, V
R=30 V, R
d=15 V·s−1, E
1/2=3.5 lx·s.
__________
Translated from Journal of Tianjin University, 2007, 40(11): 1295–1299 [译自: 天津大学学报] 相似文献
10.
Jarosław Spychała 《Catalysis Letters》2006,109(1-2):55-60
The reacion of thioamides with the R1R2N–ZnCl ammoniates leads to N-mono-, N,N′-di-, N,N-disubstituted, and unsubstituted amidines with high concentrations of amines in absolute ethanol. The efficient direct formation
of the N,N′-dimethylamidine can be explained by a greater reactivity of methylamine compared with dimethylamine. Discovery of a new
zwitterion (induced by a carbonyl oxygen) suggests that the stabilization in the thymine N-methylamidine is too slight to prevent the subsequent reaction with methylamine. 相似文献
11.
60Co γ rays induced styrene emulsion polymerizations were carried out with sodium undec-10-enoate (UDNa) as emulsifier at room
temperature and the different kinetics was discussed. The influence of absorbed dose rate, monomer concentration and emulsifier
concentration on kinetics and latex particles was studied. The polymerization kinetics relation was found as R
P
∝ D
0.37
·
M
0.75
·
E
0.70 (R
P
, maximum polymerization rate; D, absorbed dose rate; M, monomer concentration; E, emulsifier concentration). The particles’ diameter increases and particle size distribution (PSD) becomes narrower with the decrease of absorbed dose rate and increase of monomer content. The effect of UDNa content on
particles’ diameter and particle size distribution is the same as that of emulsifier in conventional emulsion system. This
type of emulsion polymerization can easily form monodisperse particles. 相似文献
12.
Three different structures were synthesized via solution free radical polymerization. Polyacrylamides hydrophobically modified
with small amounts of two different N′N-dialkylacrylamides [N,N-dihexylacrylamide (DHAM) and N,N-dioctylacrylamide (DOAM)] and two different N-alkylacrylamides [N-dodecylacrylamide (DAM) and N-hexadecylacrylamide (HDAM)] have been synthesized using two linear hydrophobic initiators with 12 (ACVA12) and 16 (ACVA16) carbon atoms and two di-substituted hydrophobic initiator with two chains of 6 (ACVAdi6) and 8 (ACVAdi8) carbon atoms derived from 4′4-azobis(4-cyanopentanoic acid) (ACVA). The polymers obtained were telechelic, multisticker
and combined. The initiators, monomers and polymers synthesized were characterized by 1H NMR and light scattering (LS). The rheological properties of these three different associative polymers were investigated
using steady-state experiments. The effect of location and structure (linear or di-substituted) of the hydrophobic groups
upon the viscosity of the polymer in solution was studied. 相似文献
13.
The aim of present study is to examine the photo-initiation efficiency of N,N-dimethylacrylamide-based allylic ammonium salt as one component addition-fragmentation agent (cationic photoinitiator cum
radical source) in free radical accelerated cationic polymerization. Novel addition-fragmentation agent (AFA), 2-(N,N-dimethylcarboxy-3-propenyl)(phenylcarbonyl-4-phenylene) dimethyl ammonium hexafluoroantimonate (DMPDA) was synthesized as
cationic photoinitiator and its initiation efficiency was examined in polymerization of cyclohexene oxide (CHO), isobutyl
vinyl ether (IBVE), and n-butyl vinyl ether (n-BVE) in CH2Cl2 solvent at wavelength λ > 290 nm. The rate of polymerization increases with the increase in initiator concentration and reaction
time. The results demonstrate that DMPDA acts as an efficient photoinitiator (AFA) without use of radical source in free radical
accelerated cationic polymerization. 相似文献
14.
A mixture of five new ceramides was isolated from the aerial parts of Rantherium suaveolens and characterized by spectroscopic and chemical methods. Their structures were elucidated by spectroscopic and chemical methods
as (2S, 3S, 4R, 2′R, 14E)-2-(2′-hydroxydocosanoylamino)-14-octadecene-1,3,4-triol (1), (2S,3S,4R,2′R, 14F)-2-(2′-hydroxytricosanoylamino)-14-octadecene-1,3,4-triol (2), (2S,3S,4R,2′R,14F)-2-(2′-hydroxytetracosanoylamino)-14-octadecene-1,3,4-triol (3), (2S,3S,4R,2′R,14E)-2-(2′-hydroxypentacosanoylamino)-14-octadecene-1,3,4-triol (4), and (2S,3S,4R,2′R,14E)-2-(2′-hydroxyhexacosanoylamino)-14-octadecene-1,3,4-triol (5). 相似文献
15.
Prof. Dr. Arun K. Ghosh Dr. Margherita Brindisi Dr. Yu-Chen Yen Emma K. Lendy Dr. Satish Kovela Emilio Leal Cárdenas Dr. Bhavanam Sekhara Reddy Dr. Kalapala Venketeswara Rao Deborah Downs Dr. Xiangping Huang Dr. Jordan Tang Prof. Dr. Andrew D. Mesecar 《ChemMedChem》2019,14(5):545-560
Herein we present the design, synthesis, and biological evaluation of potent and highly selective β-secretase 2 (memapsin 1, beta-site amyloid precursor protein cleaving enzyme 2, or BACE 2) inhibitors. BACE2 has been recognized as an exciting new target for type 2 diabetes. The X-ray structure of BACE1 bound to inhibitor 2 a {N3-[(1S,2R)-1-benzyl-2-hydroxy-3-[[(1S,2S)-2-hydroxy-1-(isobutylcarbamoyl)propyl]amino]propyl]-5-[methyl(methylsulfonyl)amino]-N1-[(1R)-1-phenylpropyl]benzene-1,3-dicarboxamide} containing a hydroxyethylamine isostere was determined. Based on this structure, a computational docking study was performed which led to inhibitor 2 a -bound BACE2 models. These were used to optimize the potency and selectivity of inhibitors. A systematic structure–activity relationship study led to the identification of determinants of the inhibitors’ potency and selectivity toward the BACE2 enzyme. Inhibitors 2 d [N3-[(1S,2R)-1-benzyl-2-hydroxy-3-[[(1S,2S)-2-hydroxy-1-(isobutylcarbamoyl)pentyl]amino]propyl]-N1-methyl-N1-[(1R)-1-phenylpropyl]benzene-1,3-dicarboxamide; Ki=0.031 nm , selectivity over BACE1: ≈174 000-fold] and 3 l [N1-((2S,3R)-3-hydroxy-1-phenyl-4-((3-(trifluoromethyl)benzyl)amino)butan-2-yl)-N3,5-dimethyl-N3-((R)-1-phenylethyl)isophthalamide; Ki=1.6 nm , selectivity over BACE1: >500-fold] displayed outstanding potency and selectivity. Inhibitor 3 l is nonpeptide in nature and may pave the way to the development of a new class of potent and selective BACE2 inhibitors with clinical potential. 相似文献
16.
Kazuyuki Takahashi Hidekazu Kozuki Akira Onoda Taka-aki Okamura Hitoshi Yamamoto Norikazu Ueyama 《Journal of Inorganic and Organometallic Polymers》2002,12(3-4):99-108
A novel poly(carboxylate) ligand was synthesized as a ligand for a crystalline CaCO3-organic composite. Poly[1-carboxylate-2-(N-t-butylcarbamoyl)ethylene-alt-ethylene] has a 7-membered ring with an intramolecular NH·O hydrogen bond between the carboxylate group and the neighboring amide NH proton in the anionic carboxylate form. The configuration of the polymer ligand was estimated with polymer repeat-unit models, (S,S)- or (R,R)-2-(N-t-butylcarbamoyl)-cyclohexanecarboxylic acid ((S,S)- or (R,R)-TBCA) and (S,R)- 2-(N-t-butylcarbamoyl)-cyclohexanecarboxylic acid ((S,R)-TBCA). The proton NMR spectum of the carboxylate anion of (S,S)- or (R,R)-TBCA exhibits a non-hydrogen bonded NH signal at 7.31 ppm in Me2SO-d
6. (S,R)-TBCA shows a strongly NH·O hydrogen-bonded NH signal at 8.50 ppm. The observation of one strongly NH·O hydrogen bonded NH signal at 11.3 ppm indicates that the polymer anion has a threo-form in the zigzag polymer main chain. Moreover, a polymer ligand-CaCO3 composite was synthesized. The composite was characterized by 13C cross polarization/magic angle spinning (CP/MAS) and scanning electron microscopy (SEM). The polymer ligand stabilizes the Ca–O (carboxylate) bond in the CaCO3 composite. This prevents dissociation due to pKa shifts of the NH·O hydrogen bond and controls the crystal growth toward metastable vaterite. 相似文献
17.
M. S. Morad 《Journal of Applied Electrochemistry》2007,37(6):661-668
The corrosion resistance of mild steel in 1 M H2SO4 solution was evaluated after addition of Sn2+ and Zn2+, N-acetylcystein (ACC) and S-benzylcystein (BzC) as a function of concentration (5–1000 μM) and solution temperature (35–50°C). Eight blends were also
investigated. Both polarization resistance (R
p) and electrochemical impedance spectroscopy (EIS) were employed. For single additives, Zn2+ ions acted as accelerator for mild steel corrosion while the other additives showed good performance. The most effective
additive was Sn2+. Adsorption of Sn2+, ACC and BzC obeyed the Temkin adsorption isotherm and had a very high negative value of free energy of adsorption (−ΔG°ads). All blends provided good inhibition which increased with rise in temperature. Corrosion kinetic parameters such as activation
energy (E
a) and the pre-exponential factor (λ) were calculated and discussed. EIS revealed that the interface of the uninhibited and
inhibited systems can be represented by the simple equivalent circuit R
e(R
ct
Q
dl). 相似文献
18.
Polymerization of isoprene (IP) with alkyllithium (RLi) catalysts in the presence of amines such as triethylamine (TEA), 1,2-dipiperidinoethane (DPPE) and N,N,N′,N′-tetramethyldiaminoalkanes [(CH3)2N(CH2)nN(CH3)2 where n=1, 2, 3, 4 and 6 (TMDAA)] has been studied. By adding the amines, the polymerization rate of IP was accelerated, and the contents of 3,4- and 1,2-units in the resulting polymers increased. The effects of methylene chain length of the TMDAA on the polymerization were examined. It was found that both the polymerization rates and the microstructure of the polymers depend on the methylene length of the TMDAA. The amines having 2 and 3 methylenes in (CH3)2N(CH2)nN(CH3)2 favoured production of the polymer consisting of predominantly 1,2- and 3,4-units. It was proposed that two types of active sites for the polymerization of IP were produced depending on the number n of the TMDAA. Two types of active species were confirmed to be produced with sec-BuLi in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) depending on the TMEDA/sec-BuLi mole ratios. © 1998 SCI. 相似文献
19.
Botao Zheng Xinjun Wu Xuebing Ma Lingshan Xiao Yeling Ji Xiangkai Fu 《Catalysis communications》2007,8(12):1923-1928
The chiral (1R,2S)-(−)-2-amino-1,2-diphenylethanol and (1S,2R)-(+)-2-amino-1,2-diphenylethanol had been immobilized on the layered frame of zirconium phosphate to obtain zirconium phosphonates (1R,2S)-(−)-4a and (1S,2R)-(+)-4b. The enantioselective addition of Et2Zn to benzaldehyde using zirconium phosphonates (1R,2S)-(−)-4a and (1S,2R)-(+)-4b as heterogeneous catalysts yielded secondary alcohol in 80.1% yield and e.e. values of up to 54.3%, which was only 7.6% e.e. lower than that using the corresponding ligands (1R,2S)-(−)-2a and (1S,2R)-(+)-2b as homogeneous catalysts. The zirconium phosphonates (1R,2S)-(−)-4a and (1S,2R)-(+)-4b were characterized by IR, SEM, XRD and TG analysis. SEM and XRD data showed that the catalysts (1S,2R)-(+)-4b and (1R,2S)-(−)-4a were in aggregate and mesopore structure with the same interlayer spacing 2.48 nm and pore diameter 5.6 nm. 相似文献
20.
Saliha Alehyen Fatima Bensajjay Mohammed El Achouri Lourdes Pérez Aurora Pinazo María Rosa Infante 《Journal of surfactants and detergents》2010,13(3):339-348
A new oligomeric surfactant: N,N,N′,N″,N″- pentamethyl diethyleneamine—N,N″-di-[tetradecylammonium bromide] referred to as 14-2-N(CH3)-2-14 was synthesized, purified and characterized by Elemental Analysis, 1H and 13C NMR and Electrospray. The micellar properties of this compound were determined by electrical conductivity and surface tension
methods. Optical microscopy was also employed to study the behavior of anhydrous surfactant and the binary water/surfactant
system as a function of temperature. The critical micellar concentration (cmc), degree of counterion binding and thermodynamic
parameters of micellization (standard molar Gibbs energy, enthalpy and entropy of micellization) were determined by electrical
conductivity measurements in the temperature range [24–54 °C]. Surface tension measurements also provide information about
the dependence of the surface tension at the cmc (γcmc), pC20 (negative logarithm of the surfactant’s molar concentration C20, required to reduce the surface tension by 20 mN/m, the surface excess (Γmax) at air/solution interface, the minimum area per surfactant molecule at the air/solution interface (Amin), surface pressure
at the cmc (Пcmc), critical packing parameter(CPP) and the standard free energies of micellization (
\Updelta Gm0\Updelta G_{m}^{0}) and of adsorption (
\Updelta G\textads0 \Updelta G_{\text{ads}}^{0} ). 相似文献