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1.
21,31-O-(Propane-1,2-diyl)cyclomaltoheptaose has been prepared from 2-O-allylcyclomaltoheptaose by mercuration in trifluoroacetic acid, followed by reduction with sodium borohydride. 2-O-(2,3-Epoxypropyl)cyclomaltoheptaose, prepared from 2-O-allylcyclomaltoheptaose by oxidation with dimethyldioxirane, was converted into 21,31-O-(3-hydroxypropane-1,2-diyl)cyclomaltoheptaose by treatment with trifluoroacetic acid. Both derivatives containing fused 1,4-dioxane rings are mixtures of stereoisomers, in which the methyl and hydroxymethyl group, respectively, that is linked to this ring, occupies an axial or an equatorial position.  相似文献   

2.
The reaction of perrhenate with 2-hydrazinopyrimidine in MeOH–HCl yields [ReCl31-NNC4H3N2H)(η2-HNNC4H3N2)] (1). The analogous reaction with Na2MoO4 yields [MoCl31-NNC4H3N2H)(η2-HNNHC4H3N2)] (1a). The reaction of 1 with pyrimidine-2-thiol and triethylamine produces [Re(η1-C4H3N2S)(η2-C4H3N2S)(η1-NNC4H3N2)(η2-HNNC4H3N2)] (2), while reaction of 1 with the Schiff base HSC6H4N=C(H)C6H4OH provides [Re(η3-SC6H4N=C(H)C6H4O)(η1-NNC4H3N2)(η2-HNNC4H3N2)]·0.6CH2Cl2 (3·0.6CH2Cl2). The analogous hydrazinopyridine complex of the Schiff base, [Re(η3-SC6H4N=C(H)C6H4O)(η1-NNC5H4N)(η2-HNNC5H4N)] (4), was also synthesized by reacting [ReCl31-NNC5H4NH)(η2-HNNC5H4N)] with HSC6H4N=C(H)C6H4OH. The crystal structures of 1–4 have been determined.  相似文献   

3.
Transverse triple-quantum filtered NMR spectroscopy (TTQF) of 17O-water was used to study the properties of water in insulin solutions at different Zn2+ concentrations and pH values. It was established that strongly bound water molecules are already present in Zn-free insulin. On the assumption that the effective correlation time of a strongly bound water molecule, τsb, is 10 ns, the apparent number of strongly bound water molecules was 3 to 4 per insulin monomer. Addition of Zn2+ equivalent to 2 g-atoms per hexamer did not produce substantial increases in the overall 17O-water TTQF signal intensity and apparent fraction of bound water. The dramatic enhancement of the TTQF signals observed for samples with a Zn2+/hexamer ratio greater than 2:1 could be attributed to the increase in correlation time of the strongly bound water, due to the formation of higher-order oligomers of the protein.  相似文献   

4.
以东北森林两种典型的阔叶树种风力传播种子——花曲柳和色木槭种子为研究对象,通过室内15N尿素浸泡试验和温室盆栽试验,设置4个浓度(0、0.05、0.1和0.2 g·L-1)、3个浸泡时间(4、8和12 d)与4个叶期(2、4、6和8叶)处理,研究种子浸泡浓度、浸泡时间和幼苗叶期对种子和幼苗15N富集的影响.结果表明: 浸泡浓度和浸泡时间对两树种种子δ15N值均有显著的正反馈作用,高浓度和长时间(0.2 g·L-1+12 d)更有利于种子15N总量的富集,花曲柳和色木槭种子15N同位素最大富集倍数的浸泡浓度和浸泡时间组合分别为0.1 g·L-1+(4、8 d)和0.05 g·L-1+(4、8 d);δ15N值稀释率随幼苗株高的增加先急剧减少(2~6叶)后趋于稳定,幼苗从8叶开始叶片15N总量降低,表明6叶幼苗更适合追踪幼苗的来源;幼苗叶片δ15N值与种子浸泡浓度、浸泡时间和种子的δ15N值呈显著正相关.花曲柳和色木槭种子及幼苗均能成功富集到15N信号,采用0.1 g·L-1+8 d+6叶组合最适合追踪花曲柳和色木槭种子和幼苗.  相似文献   

5.
以东北森林两种典型的阔叶树种风力传播种子——花曲柳和色木槭种子为研究对象,通过室内15N尿素浸泡试验和温室盆栽试验,设置4个浓度(0、0.05、0.1和0.2 g·L-1)、3个浸泡时间(4、8和12 d)与4个叶期(2、4、6和8叶)处理,研究种子浸泡浓度、浸泡时间和幼苗叶期对种子和幼苗15N富集的影响.结果表明: 浸泡浓度和浸泡时间对两树种种子δ15N值均有显著的正反馈作用,高浓度和长时间(0.2 g·L-1+12 d)更有利于种子15N总量的富集,花曲柳和色木槭种子15N同位素最大富集倍数的浸泡浓度和浸泡时间组合分别为0.1 g·L-1+(4、8 d)和0.05 g·L-1+(4、8 d);δ15N值稀释率随幼苗株高的增加先急剧减少(2~6叶)后趋于稳定,幼苗从8叶开始叶片15N总量降低,表明6叶幼苗更适合追踪幼苗的来源;幼苗叶片δ15N值与种子浸泡浓度、浸泡时间和种子的δ15N值呈显著正相关.花曲柳和色木槭种子及幼苗均能成功富集到15N信号,采用0.1 g·L-1+8 d+6叶组合最适合追踪花曲柳和色木槭种子和幼苗.  相似文献   

6.
Pure sucrose is inexpensive and readily available, making this disaccharide a highly desirable starting material for new polymers. In order to achieve a clean polymerization, the disaccharide must be regioselectively monofunctionalized in good yield. This paper describes the practical, enzyme-mediated synthesis of sucrose-1 '-methacrylate 2 from sucrose and vinyl methacrylate using subtilisin Carlsberg (Sigma, Protease VIII), a readily available bacterial serine protease. A key aspect of this process, ascertaining the positional selectivity of acylation, was unambiguously accomplished using 1H-detected (1H, 13C) one-bond shift correlation (HMQC) spectroscopy and1H-detected (1H, 13C) multiple bond correlation (HMBC) spectroscopy.  相似文献   

7.
The seasonal effects on the chemical structure and rheological properties of Gracilaria pseudoverrucosa agar have been investigated using a sequential solvent extraction, 13C NMR and infrared spectroscopy, and gel strength measurements. The results showed that agar enriched in precursor to the agarobiose repeat unit were obtained from algae collected in summer. In contrast, algae collected in winter contained agar molecules richer in alkali-stable sulfate groups attributed in part to -galactose-4-sulfate. A similar total concentration of 6-O-methylated agarobiose repeat units was present in the agar from both algal samples but the distribution of the methylated disaccharide varied in the fractions. Agar fractions from the summer-collected sample had higher gel strength than those of the winter ones. Alkali treatment markedly improved the gel strength of the agar from the summer harvested seaweed. Different gel strengths were observed for the native and alkali-treated agar fractions extracted from the same algal sample and a gel strength comparable to that obtained for a commercial bacteriological grade agar was obtained from the alkali-treated 40% ethanol extract agar from the summer collected alga. The chemical and rheological variations due to seasonal changes are interpreted as reflecting the ratio of actively-growing (young) to resting (old) tissue in the alga and are proposed to represent a type of ‘secondarization’ of the algal cell-wall.  相似文献   

8.
The lithiation of indole, using a slight excess of n-butyl lithium in THF, followed by methylation and reaction with [Cr(CO)6] in refluxing dibutyl ether, resulted in the formation of [Cr(η6-N-methylindole)(CO)3] (1a) and [Cr(η6-N-methyl-2-methylindole)(CO)3] (1b). In contrast, lithiation of quinoline in THF, silylation and the subsequent reaction with [Cr(CO)6] under similar reaction conditions, afforded [Cr(η6-N-trimethylsilyl-2-butyl-1,2-dihydroquinoline)(CO)3] (2) and [Cr(η6-{2-butyl-1,2,3,4-tetrahydroquinoline})(CO)3] (3). The formation of [Cr(η6-2,2′-bis{N-methylindolyl})(CO)3] (4) implied lithiation at the 2-position of 1a. However, metallation at the 7-position was also indicated during the same reaction. In the presence of [Mn(CO)5Br], product 4 and the transmetallation product [Cr(η6-{7-(N-methylindolyl)Mn(CO)5})(CO)3] (5) were isolated. Reaction with titanocene dichloride gave [Cr(η6-{2-(N-methylindolyl)TiCp2Cl})(CO)3] (6), which slowly converted into [TiCp2{Cr(η6-2-(N-methylindolyl)(CO)3}2] (7).  相似文献   

9.
The ability of 2-n-propyl-4-pentenoic acid (Δ4-VPA) and 2-n-propyl-2(E)-pentenoic acid ([E]-Δ2-VPA), two unsaturated metabolites of valproic acid (VPA), to form reactive intermediates, deplete hepatic glutathione (GSH) and cause accumulation of liver triglycerides was investigated in the rat. With the aid of ionspray liquid chromatography-tandem mass spectrometry (LC-MS/MS), three GSH adducts were detected in the bile of Δ4-VPA-treated animals and were identified as 4-hydroxy-5-glutathion-S-yl-VPA-γ-lactone, 5-glutathion-S-yl-(E)-Δ3-VPA and 3-oxo-5-glutathion-S-yl-VPA. A fourth conjugate was identified tentatively as 4-glutathion-S-yl-5-hydroxy-VPA. Quantitative analysis of the corresponding N-acetylcysteine (NAC) conjugates in urine indicated that metabolism of Δ4-VPA via the GSH-dependent pathways accounted for approximately 20% of an acute dose (100 mg kg−1 i.p.). In contrast, when rats were given an equivalent dose of (E)-Δ2-VPA, only one GSH adduct (5-glutathion-S-yl-(E)-Δ3-VPA) was detected at low concentrations in bile. In vitro experiments with rat liver mitochondria demonstrated that Δ4-VPA undergoes coenzyme A- and ATP-dependent metabolic activation in this organelle via the β-oxidation pathway to intermediates which bind covalently to proteins. When liver homogenates and hepatic mitochondria from rats injected with Δ4-VPA, (E)-Δ2-VPA or VPA were analyzed for GSH content, it was found that only Δ4-VPA depleted GSH pools significantly. Treatment of rats with Δ4-VPA and (to a lesser extent) VPA led to an accumulation of liver triglycerides, whereas (E)-Δ2-VPA had no measurable effect. It is concluded that Δ4-VPA undergoes metabolic activation by both microsomal cytochrome P-450-dependent and mitochondrial coenzyme A-dependent processes, and that the resulting electrophilic intermediates, which are trapped in part by GSH, may mediate the hepatotoxic effects of this compound. In contrast, (E)-Δ2-VPA is not transformed to any appreciable extent to reactive metabolites, which thus accounts for the apparent lack of hepatotoxicity of this positional isomer in the rat.  相似文献   

10.
分别以1年生苹果砧木M9T337幼苗和5年生烟富3/SH6/平邑甜茶为试材,开展盆栽和田间试验,并结合15N、13C同位素示踪技术,研究不同浓度(0、0.5、1、1.5 mmol·L-1,分别用CK、T1、T2和T3表示)硝酸还原酶(NR)抑制剂钨酸钠对苹果幼苗15N吸收利用、13C积累和成熟期果实品质的影响。结果表明: 盆栽试验中,喷施0.5~1.0 mmol·L-1钨酸钠可显著抑制幼苗地上部生长,但对根系生长影响不显著;当钨酸钠浓度达到1.5 mmol·L-1时可显著抑制根系生长。同一时期各处理叶片NR活性与钨酸钠浓度呈负相关,均表现为CK>T1>T2>T3。随处理时间的延长,叶片硝态氮含量总体表现为先升高后降低的趋势,同一时期各处理硝态氮含量与钨酸钠浓度呈正相关,均表现为T3>T2>T1>CK。喷施钨酸钠可不同程度地降低幼苗各器官15N吸收量和15N利用率,且钨酸钠浓度越高,抑制幼苗氮素吸收和利用的效果越显著。随钨酸钠浓度的提高,地上部13C积累量呈先升高后降低的趋势,在T2处理时达到最高;幼苗整株13C积累量呈相似的规律。田间试验结果表明,喷施钨酸钠可降低成熟期叶片和果实的氮含量,果皮花青苷含量、果实可溶性固形物、可溶性糖含量和糖酸比均不同程度提高,其中T2处理的效果最好。综上,T2处理(1.0 mmol·L-1钨酸钠)可有效抑制幼苗地上部生长,降低15N吸收利用,提高13C积累,有利于果实品质的提高。  相似文献   

11.
Two novel cellulose esters were prepared with fluorine (F)-containing substituents using homogeneous phase reaction chemistry in DMAc/LiCl. The partially substituted derivatives and their corresponding perpropionates proved to be thermoplastic polymers. The 2,2-difluoroethoxy and 2,2,3,3,4,4,5,5-octafluoropentoxy substituents were easily identified by 1H- and 19F-NMR spectroscopy without disclosing their precise location on the anhydroglucose unit. Thermal analysis revealed modest or no crystallinity; glass transition temperatures between 53 and 113°C; and improved thermal stability as compared to their F-free counterparts.  相似文献   

12.
以霍格兰营养液为培养基质,采用15N同位素示踪技术,研究不同浓度15NO3--N (0、2.5、5、10和20 mmol·L-1,分别以N0、N1、N2、N3和N4表示)对平邑甜茶幼苗生长、光合作用、15N吸收、利用及分配的影响.结果表明:与其他处理相比,N2处理幼苗叶绿素含量、叶面积及各器官干质量最大.叶片净光合速率(Pn)随15NO3--N浓度的增加显著增大,但15NO3--N浓度超过N2处理后Pn略有下降.处理20 d时,N2处理幼苗根系活力最大,根系长度、根系总表面积和根尖数也显著高于其他处理.各处理间15N分配率差异显著,N2处理幼苗各器官间15N分配率最均衡,15N利用率也较高;随15NO3--N浓度增加,各处理幼苗全氮量和15N吸收量呈先升高后降低的趋势,且在N2处理时最大,分别为103.77和21.57 mg.处理12 d后,叶片硝酸还原酶(NR)活性以N2处理最高,N4处理最低,至第16天时,N4处理较N2处理降低了84.9%.因此,15NO3--N供应过低抑制幼苗光合作用及氮素吸收,15NO3--N供应过高则抑制幼苗体内硝态氮同化及根系生长,均不利于苹果幼苗生长及氮素营养吸收利用,适量供氮有利于苹果幼苗的生长、光合作用的提高,以及氮素的吸收、利用和分配.  相似文献   

13.
The reaction between [(η6-p-cymene)Ru(H2O)3]X2 and 4,7-phenanthroline (phen) leads to the formation of the rectangular tetranuclear complexes [(η6-p-cymene)4Ru4(μ-4,7-phen-N4,N7)2(μ-OH)4]X4 (X = NO3, 1a; SO3CF3, 1b) which have been structurally characterised by X-ray crystallography. 1H NMR spectroscopic studies suggest the presence of a partially dissociated dinuclear species of type [(η6-p-cymene)2Ru2(μ-4,7-phen-N4,N7)(solv)4]4+ in equilibrium with the tetranuclear cyclic species found in the solid state. The temperature effect for this equilibrium was studied by variable temperature 1H NMR experiments in D2O and MeOD. The results reveal that the proportion of the tetranuclear species increases with the polarity of the solvent which favour stacking interactions between the phenanthroline moieties. In addition, the reactivity of the tetranuclear species towards the nucleosides guanosine (Guo), cytidine (Cyt), 2′-deoxythymidine (Thy) and 2′-deoxyadenosine (dAdo) has been monitored by 1H NMR as a potential model for the interaction of the 1 species with the probable DNA target. The results reveal that the 1 systems are able to bind the nucleobases endocyclic nitrogen atoms of Guo Cyt, and dAdo.  相似文献   

14.
以霍格兰营养液为培养基质,采用15N同位素示踪技术,研究不同浓度15NO3--N (0、2.5、5、10和20 mmol·L-1,分别以N0、N1、N2、N3和N4表示)对平邑甜茶幼苗生长、光合作用、15N吸收、利用及分配的影响.结果表明:与其他处理相比,N2处理幼苗叶绿素含量、叶面积及各器官干质量最大.叶片净光合速率(Pn)随15NO3--N浓度的增加显著增大,但15NO3--N浓度超过N2处理后Pn略有下降.处理20 d时,N2处理幼苗根系活力最大,根系长度、根系总表面积和根尖数也显著高于其他处理.各处理间15N分配率差异显著,N2处理幼苗各器官间15N分配率最均衡,15N利用率也较高;随15NO3--N浓度增加,各处理幼苗全氮量和15N吸收量呈先升高后降低的趋势,且在N2处理时最大,分别为103.77和21.57 mg.处理12 d后,叶片硝酸还原酶(NR)活性以N2处理最高,N4处理最低,至第16天时,N4处理较N2处理降低了84.9%.因此,15NO3--N供应过低抑制幼苗光合作用及氮素吸收,15NO3--N供应过高则抑制幼苗体内硝态氮同化及根系生长,均不利于苹果幼苗生长及氮素营养吸收利用,适量供氮有利于苹果幼苗的生长、光合作用的提高,以及氮素的吸收、利用和分配.  相似文献   

15.
Addition of (Cp*2YH)2 (4) to 2-methyl-1,4-pentadiene produced the yttrium-alkyl-alkene chelate complex Cp*2YCH2CH2CH2C(CH3)=CH2 (2) in which a disubstituted alkene is complexed to the metal center. Evidence for coordination of the alkene unit of 2 comes from the 1H and 13C NMR chemical shifts of the vinyl units and from observation of nOe effects between Cp* protons and vinyl hydrogens. The disubstituted alkene ligand of 2 is weakly bound, and evidence for an equilibrium with substantial amounts of complex 3 with a free alkene was obtained from variable temperature 1H NMR spectroscopy.  相似文献   

16.
17.
Several novel dimers of the composition [M2Cl4(trans-dppen)2] (M=Ni (1), Pd (2), Pt (3)) containing trans-1,2-bis(diphenylphosphino)ethene (trans-dppen) have been prepared and characterized by X-ray diffraction methods, NMR spectroscopy (195Pt{1H}, 31P{1H}), elemental analyses, and melting points. The intramolecular [2+2] photocycloaddition of the two diphosphine-bridges in 3 produces [Pt2Cl4(dppcb)] (4), where dppcb is the new tetradentate phosphine cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane. Neither 1 nor the free diphosphine trans-dppen shows this reaction. In the case of 2 the photocycloaddition is slower than in 3. This difference can be explained by the shorter distance between the two aliphatic double bonds in 3 than in 2, but also different transition probabilities within ground and excited states of the used metals could be involved. Furthermore, variable-temperature 31P{1H} NMR spectroscopy of 2 or 3 reveals a negative activation entropy of 2 for the [2+2] photocycloaddition, but a positive of 3. The removal of chloride from 4 by precipitating AgCl with AgBF4, and subsequent treatment with 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) leads to [Pt2(dppcb)(bipy)2](BF4)4 (5) and [Pt2(dppcb)(phen)2](BF4)4 (6), respectively. In an analogous reaction of 4 with PMe2Ph or PMePh2, [Pt2(dppcb)(PMe2Ph)4](BF4)4 (7) and [Pt2(dppcb)(PMePh2)4](BF4)4 (8) are formed. Complexes 1–8 show square–planar coordinations, where the compounds 4–8 have also been characterized by the above mentioned methods together with fast atom bombardment mass spectrometry (7, 8). The crystal structure of 4 reveals two conformations, which arise from an energetic competition between the sterical demands of dppcb and an ideal square–planar environment of Pt(II). The free tetraphosphine dppcb can be obtained easily from 4 by treatment with NaCN. It has been characterized fully by the above methods including 13C{1H} and 1H NMR spectroscopy. The X-ray structure analysis shows the pure MMMP-enantiomer in the solid crystal, which is therefore optically active. This chirality is induced by a conformation of dppcb, where all four PPh2 groups are non-equivalent. Variable-temperature 31P{1H} NMR spectroscopy of dppcb confirms this explanation, since the single signal at room temperature is split into two doublets at 183 K. The goal of this article is to demonstrate the facile production of a new tetradentate phosphine from a diphosphine precursor via Pt(II) used as a template.  相似文献   

18.
During the last decade, lipase has gained interest as a biocatalyst for synthesis in organic solvent systems. The paper describes the lipase catalyzed oligocondensation of bis(2-chloroethyl) succinate and 1,4-butanediol to obtain poly (1,4-butanediol succinate). The reaction was carried out at 37°C in organic solvents without any addition of water. Various lipases and solvents were screened to obtain a maximum degree of polymerization. Based on gel permeation chromatography, the highest average molecular weight of the oligomer obtained was 1570 g/mol with a polydispersity of 1.2 when a mixture of 70% diisopropyl ether and 30% chloroform was used as a solvent. The degree of polymerization was 8 in this case. According to thin-layer chromatography, a trimer (HO(CH2)4OCO(CH2)2COO(CH2)4OH) was formed at an early stage, with a subsequent condensation with bis(2-chloroethyl) succinate to give higher oligomers. The structure of the oligomers was confirmed by 13C NMR and IR spectra.  相似文献   

19.
河水氢氧稳定同位素特征是研究水体转化和示踪水循环过程的重要内容.为研究河水氢氧稳定同位素特征,揭示河水补给来源,于2017年4—8月对亚热带农业小流域脱甲河4级河段(S_1、S_2、S_3和S_4)水体氢(D)、氧(18O)稳定同位素进行了监测,分析其时空动态特征和过量氘(d-excess)的变化规律,并探讨了它们与降水、高程和水质等影响因子的相关关系.结果表明:δD、δ18O和d-excess的变化范围分别在-43.17‰^-26.43‰(-35.50‰±5.44‰)、-7.94‰^-5.70‰(-6.86‰±0.74‰)和16.77‰~23.49‰(19.39‰±1.95‰).受季风环流的影响,δD和δ18O具有明显的季节变化特征,即春季(δD和δ18O为-29.88‰±3.31‰和-6.18‰±0.57‰)>夏季(δD和δ18O为-39.25‰±2.65‰和-7.32‰±0.42‰);空间上,δD和δ18O表现出明显的沿程变化,随着采样点的位置到河流源头的距离波动增加,δD为S_118O为S_118O与水温呈显著负相关(δD:r=-0.92;δ18O:r=-0.88);δ18O与海拔呈显著负相关(r=-0.96);在空间上,δ18O与水温呈显著正相关(r=0.98);δD和δ18O与降水量呈不显著负相关.  相似文献   

20.
为明确协同提高冬小麦产量和水分利用效率的适宜灌水量和种植密度,选用大穗型品种‘泰农18’(T18)和中穗型品种‘山农22’(S22)为试验材料,设置4个灌溉水平(不灌水、每次灌水45、60、75 mm)和4个种植密度,其中泰农18选用135×104、270×104、405×104、540×104 株·hm-2,山农22选用90×104、180×104、270×104、360×104株·hm-2,研究了籽粒产量、麦田耗水特性和水分利用效率对灌水量和密度互作效应的响应。结果表明: 籽粒产量、总耗水量、土壤贮水消耗量和水分利用效率均受到灌溉水平、种植密度及两者互作效应的显著影响。每次灌水量为45 mm,泰农18种植密度为405×104株·hm-2、山农22种植密度为270×104株·hm-2时,两品种籽粒产量均达到最高,拔节后棵间蒸发量占阶段农田总耗水量的比例最小,1 m以下土壤水消耗比例、水分利用效率高。种植密度与灌溉量合理组合,有利于降低水分无效损耗,提高水分利用效率。  相似文献   

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