镧离子及其配合物对植物花粉细胞质膜透性及花粉萌发的影响

以植物花粉细胞为试验体系 ,研究La3 及其配合物对花粉质膜透性及花粉萌发的影响。La3 浓度为 1× 10 - 7～ 1× 10 - 4 mol·L- 1 ,可显著减小细胞的质膜透性 ;稀土稳定配合物La3 EDTA对细胞质膜透性基本无影响 ,而La3 柠檬酸、La3 酒石酸的配合物对质膜透性的影响与其配比有关 ,当配比不大于 1∶3时 ,明显降低质膜透性 ,达到 1∶10时 ,无任何作用。La3 浓度在合适的范围内 ( 2 5～ 2 0 μmol·L- 1 )对花粉萌发有明显的促进作用。因此 ,La3 及其某些配合物浓度在 1× 10 - 6 ～ 1× 10 - 5 mol·L- 1 范围内不仅可以减小花粉细胞的质膜透性 ,而且还能促进花粉萌发。     

LaCl3对轮藻光合色素含量及抗氧化酶活性的影响

研究了LaCl3对轮藻光合色素含量及抗氧化酶活性的影响,La3+浓度分别为0,0.2,1.0和5.0 μmol·L-1.结果表明0.2和5.0 μmol·L-1La3+处理降低了轮藻叶绿素b的含量,5.0 μmol·L-1 La3+处理降低了叶绿素a+b的含量;类胡萝卜素含量在1.0 μmol·L-1 La3+处理组显著高于对照.随着La处理浓度的提高超氧化物歧化酶的活性逐渐升高,处理组谷胱苷肽过氧化物酶活性均显著高于对照,且在1.0 μmol·L-1La处理组达到最大值,0.2和5.0 μmol·L-1 La3+处理将抑制过氧化氢酶活性,其变化规律与叶绿素b相似.实验浓度的La3+处理可能引起了轮藻植株的氧化损伤,作为应激反应,GSH-Px酶活性及类胡萝卜素含量的升高在一定程度上缓解了氧化损伤.     

镧、铕对白沙枇杷试管苗生根效应的研究

将不同浓度的La(NO3 ) 3 ,Eu(NO3 ) 3 加入白沙枇杷组培苗生根培养基中 ,2 0d后分别调查各处理的生根率、生根数 ,并记录根系生长动态 ;44d后切下各处理的根称重并测定其过氧化物酶及硝酸还原酶的活性。结果表明 ,白沙枇杷生根培养基 1/2MS +IBA 0 5 μmol·L- 1 中加入 1 0～ 3 0 μmol·L- 1 La (NO3 ) 3 ,2 0～ 3 0 μmol·L- 1 Eu(NO3 ) 3 均可显著提高其生根率、促进根的伸长生长和根重量的增加 ,增强根系过氧化物酶及硝酸还原酶的活性。但La(NO3 ) 3 和Eu(NO3 ) 3 对白沙枇杷组培苗生根效应有些差异 ,La(NO3 ) 3 对生根数、根长的增加作用及对过氧化物酶的激活作用比Eu(NO3 ) 3 显著 ,而Eu(NO3 ) 3 对根鲜重的增加、硝酸还原酶的激活作用比La(NO3 ) 3 明显得多     

在二甲亚砜中La—Fe合金膜电化学制备的研究

研究了二甲亚砜 (DMSO)中La3 和Fe2 在Pt ,Cu和Ni电极上的电化学行为。Fe2 在Pt电极上一步不可逆还原为Fe ,La3 在Pt电极上表现为准可逆电极过程。在 2 98K时 ,利用循环伏安法测定了 0 0 1mol·L- 1 FeCl2 0 1mol·L- 1 LiCl DMSO溶液中Fe2 的扩散系数、传递系数分别为 2 5 4× 10 - 6 cm2 ·s- 1 和 0 2 4;利用计时电流法测定了 0 0 1mol·L- 1 LaCl3 0 1mol·L- 1 LiCl DMSO溶液中La3 的扩散系数为 3 10×10 - 6 cm2 ·s- 1 。在铜电极上于 -1 75 0～ -2 45 0V (vs .SCE)下恒电位电解 ,可获得La含量达 2 2 7%～ 3 7 1%的La Fe合金膜 ;应用脉冲电解技术于 2～ 6mA·cm- 2 也可获得La Fe合金膜。这些合金膜是均匀的 ,粘附性好并有金属光泽     

镧、铈对酸雨胁迫下龙眼(Dimocarpus longana Lour.)花粉萌发和坐果的影响

研究了La3+和Ce3+对酸雨胁迫下龙眼花粉萌发和坐果的影响.结果表明,酸雨胁迫下,低浓度(0.1～1 μmol·L-1)的La(NO3)3或Ce(NO3)3可以减轻酸雨对花粉的伤害,提高花粉萌发率,高浓度(10 μmol·L-1)则加重了酸雨的伤害作用;0.1～10 mmol·L-1的La(NO3)3和Ce(NO3)3均可以提高龙眼的坐果率,减轻酸雨对龙眼果实的伤害.     

LaCl3对大豆Cu, Zn-SOD活性影响研究

研究证明0～100μmol·L-1的LaCl3对于大豆Cu,Zn SOD的NBT光还原活性抑制作用具有明显影响,即受La3+作用,大豆Cu,Zn SOD活性动力学曲线为S形,同时受La3+作用Cu,Zn SOD的热稳定性明显提高。大豆Cu,Zn SOD受La3+作用的阈值浓度和饱和浓度分别为cLa3+=18μmol·L-1,cLa3+=65μmol·L-1。根据Hill系数3.9和荧光光谱分析,大豆Cu,Zn SOD分子中存在4个La3+的强结合位点。证明了La3+对Cu,Zn SOD具有明显的正协同效应。     

钆对Tb3+-2,3-吡啶二羧酸体系荧光的增敏及其分析应用

研究了Tb3 + Gd3 + 2 ,3 吡啶二羧酸体系的荧光特性。结果表明 ,钆对该体系中Tb3 +的特征荧光有显著增敏作用 ,当钆浓度为 4 .0× 10 - 4mol·L- 1,pH为 8.0 ,2 ,3 吡啶二羧酸浓度为3.5× 10 - 4mol·L- 1时 ,体系荧光强度最大。该体系用于稀土样品中痕量Tb3 + 的测定 ,铽浓度在 1× 10 - 9～ 2× 10 - 7mol·L- 1范围内与荧光强度呈线性关系 ,检出限为 5× 10 - 10 mol·L- 1。     

镧对水稻磷吸收及其形态的影响

用分根营养液培养法研究了镧对水稻生长, 根、茎、籽粒磷含量, 磷吸收及体内磷形态的影响. 结果表明低浓度镧(0.05～1.5 mg·L-1)提高水稻产量;高浓度镧 (9 mg·L-1～30 mg·L-1) 降低水稻产量. 当镧浓度为0.05～0.75 mg·L-1时, La对水稻茎杆和根干重没有显著促进作用. 在La浓度为6～30 mg·L-1时, 水稻根重显著降低. 镧显著增加根中磷的含量, 降低茎和籽粒中磷的含量, 显著增加根对磷的吸收. 低浓度镧 (0.05～3 mg·L-1) 促进籽粒磷吸收, 而高浓度镧 (6～30 mg·L-1) 减少籽粒磷吸收. 镧显著增加茎和根中络合态磷(EDTA-P)和无机态磷(inorganic-P)含量, 且根中络合态磷和无机态磷的增加占根中总磷增加的80%以上. 当镧浓度为0.05～0.75 mg·L-1, La增加根中核磷(nucleic-P)含量, 而当镧浓度为30 mg·L-1, La降低根中核磷和酯磷(ester-P)含量; La增加根和茎中残渣态磷(residue-P)含量. 文中还讨论了磷的形态与作物磷吸收的关系.     

偶氮氯膦-DBF吸光光度法测定药物中铋

在 0 .36mol·L- 1H2 SO4 0 .6 0mol·L- 1H3PO4 混合酸介质中 ,DBF 偶氮氯膦与铋形成蓝色配合物 ,最大吸收波长位于 6 38nm ,表观摩尔吸光系数为 9.4× 10 4 L·mol- 1·cm- 1,铋浓度在 0 30 μg/2 5ml范围内符合比耳定律。用直接光度法测定了果胶铋胶囊、陈香路白路片、枸橼酸铋钾颗粒等药物中铋 ,结果满意。     

抗坏血酸为阻断剂肾上腺素法测定微量元素对SOD活性的影响

Vitamin阻断法测定了不同浓度Se、Mn、F- 对SOD活性的影响。结果显示 :①Se浓度由0 0 0 μg·L- 1增加到 40 0 μg·L- 1时 ,SOD活性由 5 1 0 0u·mg- 1上升到 5 40 0u·mg- 1;Se浓度继续增加到 60 0 μg·L- 1,SOD活性下降至 5 1 40u·mg- 1;②Mn浓度由 0 0 0 μg·L- 1增加到 40 0 μg·L- 1,SOD活性由 5 1 0 0u·mg- 1上升到 5 90 0u·mg- 1;Mn浓度继续增加到 5 0 0 μg·L- 1,SOD活性下降到 5 2 0 0u·mg- 1;③F- 浓度由 0 0 0 μg·L- 1增加到 1 0 0 μg·L- 1,SOD活性由 5 1 0 0u·mg- 1上升至 5 2 80u·mg- 1,继续增加F- 浓度到 2 0 0 μg·L- 1,SOD活性下降为 5 1 70u·mg- 1,再增加F- 浓度到 40 0 μg·L- 1,60 0μg·L- 1,80 0 μg·L- 1,SOD活性基本维持在 5 2 0 0～ 5 1 80u·mg- 1之间     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.