Gaussian free-energy dependence of electron-transfer rates in iridium complexes

The kinetics of photoinduced electron-transfer (ET) reactions have been measured in a series of synthetic donor-acceptor complexes. The electron donors are singlet or triplet excited iridium(I) dimers (Ir(2)), and the acceptors are N-alkylpyridinium groups covalently bound to phosphinite ligands on the Ir(2) core. Rate constants for excited-state ET range from 3.5 x 10(6) to 1.1 x 10(11) per second, and thermal back ET (pyridinium radical to Ir(2)(+)) rates vary from 2.0 x 10(10) to 6.7 x 10(7) per second. The variation of these rates with driving force is in remarkably good agreement with the Marcus theory prediction of a Gaussian free-energy dependence.     

Thermodynamic efficiency of brittle frictional mountain building

An active fold-and-thrust belt in unchanging tectonic and climatic conditions attains a dynamic steady-state in which the influx of accreted material at the toe is balanced by the erosive efflux off the top. The overall balance of energy in such a steady-state fold-and-thrust belt is described by the equation E = W(G) + Q, where E is the rate at which both mechanical and heat energy are added from external sources, W(G) is the rate of work performed against gravitational body forces, and Q is the rate at which waste heat flows out of the upper and lower boundaries. The total amount of power being supplied to the active Taiwan fold-and-thrust belt by the subducting Eurasian plate and in situ radioactivity is 4.2 gigawatts. Because only 0.5 gigawatts are expended in doing useful work against gravity and the remaining 3.7 gigawatts are ejected as heat, the efficiency of brittle frictional mountain building in Taiwan is 11 percent.     

紫蛇尾胶原蛋白提取工艺的研究

以紫蛇尾Ophiopholis mirabilis为原料检测其基本成分,并用盐酸对紫蛇尾进行脱钙处理,通过L9(34)正交试验对其胶原蛋白的提取工艺进行了优化。结果表明:紫蛇尾含水分51.80%,灰分42.91%,蛋白质1.68%,脂肪0.29%,总糖0.03%;酶促溶性胶原蛋白(PSC)提取工艺的优化条件为脱钙后的紫蛇尾干粉(g)与提取液(mL)的固液比为1∶15,胃蛋白酶加酶量3%,17℃下提取4 d,PSC得率为52.65%。对纯化后的酸促溶性胶原蛋白(ASC)和PSC进行紫外扫描分析,结果显示,ASC、PSC的最大吸收波长均在235 nm左右。对PSC的氨基酸组成分析表明,脯氨酸和羟脯氨酸的含量分别为10.1%和2.13%,是较典型的Ⅰ型胶原蛋白。     

紫蛇尾胶原蛋白提取工艺的研究

以紫蛇尾Ophiopholis mirabilis为原料检测其基本成分,并用盐酸对紫蛇尾进行脱钙处理,通过L9(34)正交试验对其胶原蛋白的提取工艺进行了优化。结果表明:紫蛇尾含水分51.80%,灰分42.91%,蛋白质1.68%,脂肪0.29%,总糖0.03%;酶促溶性胶原蛋白(PSC)提取工艺的优化条件为脱钙后的紫蛇尾干粉(g)与提取液(mL)的固液比为1∶15,胃蛋白酶加酶量3%,17℃下提取4 d,PSC得率为52.65%。对纯化后的酸促溶性胶原蛋白(ASC)和PSC进行紫外扫描分析,结果显示,ASC、PSC的最大吸收波长均在235 nm左右。对PSC的氨基酸组成分析表明,脯氨酸和羟脯氨酸的含量分别为10.1%和2.13%,是较典型的Ⅰ型胶原蛋白。     

紫蛇尾皂苷的初步纯化和生物学活性研究

对紫蛇尾Ophiopholis mirabilis皂苷粗提物进行初步纯化,并对所得产物的抑菌活性、抑制α-葡萄糖苷酶活性和细胞毒活性进行了研究。采用AB-8大孔吸附树脂初步纯化紫蛇尾皂苷粗提物,采用香草醛—高氯酸法测定总皂苷含量,采用滤纸片法测定抑菌活性,采用比色法和MTT法分别测定α-葡萄糖苷酶和MCF-7人乳腺癌细胞的抑制率。结果表明:纯化后的紫蛇尾皂苷纯度增加至48.57%;皂苷粗提物及纯化物的抑菌活性表现一致,均对枯草芽孢杆菌Bacillus subtilis具有明显的抑制作用,且纯化物的抑菌效果略强;皂苷粗提物对α-葡萄糖苷酶的抑制效果明显,大孔树脂95%乙醇洗脱所得纯化物的抑制率达到94.62%;皂苷粗提物及纯化物对MCF-7人乳腺癌细胞均表现出了很强的细胞毒活性,其中大孔树脂60%、75%、95%乙醇洗脱所得纯化物的浓度为300μg/m L时,细胞抑制率均高达97%以上。研究表明,紫蛇尾皂苷粗提物及纯化物均表现出了很强的选择性抑菌活性、α-葡萄糖苷酶抑制活性和对MCF-7人乳腺癌细胞的细胞毒活性,且纯化物的活性增强。     

紫蛇尾皂苷的初步纯化和生物学活性研究

对紫蛇尾Ophiopholis mirabilis皂苷粗提物进行初步纯化,并对所得产物的抑菌活性、抑制α-葡萄糖苷酶活性和细胞毒活性进行了研究。采用AB-8大孔吸附树脂初步纯化紫蛇尾皂苷粗提物,采用香草醛—高氯酸法测定总皂苷含量,采用滤纸片法测定抑菌活性,采用比色法和MTT法分别测定α-葡萄糖苷酶和MCF-7人乳腺癌细胞的抑制率。结果表明:纯化后的紫蛇尾皂苷纯度增加至48.57%;皂苷粗提物及纯化物的抑菌活性表现一致,均对枯草芽孢杆菌Bacillus subtilis具有明显的抑制作用,且纯化物的抑菌效果略强;皂苷粗提物对α-葡萄糖苷酶的抑制效果明显,大孔树脂95%乙醇洗脱所得纯化物的抑制率达到94.62%;皂苷粗提物及纯化物对MCF-7人乳腺癌细胞均表现出了很强的细胞毒活性,其中大孔树脂60%、75%、95%乙醇洗脱所得纯化物的浓度为300μg/m L时,细胞抑制率均高达97%以上。研究表明,紫蛇尾皂苷粗提物及纯化物均表现出了很强的选择性抑菌活性、α-葡萄糖苷酶抑制活性和对MCF-7人乳腺癌细胞的细胞毒活性,且纯化物的活性增强。     

Selective cleavage of human DNA: RecA-assisted restriction endonuclease (RARE) cleavage

Current methods for sequence-specific cleavage of large segments of DNA are severely limited because of the paucity of possible cleavage sites. A method is described whereby any Eco RI site can be targeted for specific cleavage. The technique is based on the ability of RecA protein from Escherichia coli to pair an oligonucleotide to its homologous sequence in duplex DNA and to form a three-stranded complex. This complex is protected from Eco RI methylase; after methylation and RecA protein removal, Eco RI restriction enzyme cleavage was limited to the site previously protected from methylation. When pairs of oligonucleotides are used, a specific fragment can be cleaved out of genomes. The method was tested on lambda phage, Escherichia coli, and human DNA. Fragments exceeding 500 kilobases in length and yields exceeding 80 percent could be obtained.     

Gallium, germanium, indium, and iridium in lunar samples

Neutron activation analyses of gallium, germanium, indium, and iridium in eight lunar samples and in meteorites and rocks (including four calciulnrich achondrites and five terrestrial basalts) with similar bulk compositions are reported. Lunar gallium concentrations are remarkably constant at about 5 parts per million, three times higher and four times lower than those in eucritic (calcium-rich) achondrites and terrestrial basalts, respectively. Lunar germanium concentrations range from 相似文献   

Synthesis and characterization of the nitrides of platinum and iridium

Transition metal nitrides are of great technological and fundamental importance because of their strength and durability and because of their useful optical, electronic, and magnetic properties. We have evaluated a recently synthesized platinum nitride (PtN) that was shown to have a large bulk modulus, and we propose a structure that is isostructural with pyrite and has the stoichiometry PtN2. We have also synthesized a recoverable nitride of iridium under nearly the same conditions of pressure and temperature as PtN2. Although it has the same stoichiometry, it exhibits much lower structural symmetry. Preliminary results suggest that the bulk modulus of this material is also very large.     

Photolytic cleavage of sulfonamide bonds

It has been found that the sulfonamide bond is relatively susceptible to photolytic cleavage. The breakdown was effected either by irradiation with a source having a continuous emission above the wavelengths of 1800 angstroms or by another source emitting principally at 2537 angstroms. Less destruction of the amino acids was seen with the latter relative to the sulfonamide bond cleavage. The cleavage was not effected by irradiation at wavelengths greater than about 3000 angstroms. Side reactions were noted involving decarboxylation, demination, and destruction of certain susceptible amino acids such as tryptophan. In only one case was a product found that arose from cleavage of a carboxamide bond; glycyltyrosine gave glycine and tyrosine upon irradiation. A yield of 75 percent of the corresponding amino acid has been obtained by irradiation of tosylhistidine; yields of 75 to 100 percent have been obtained from sulfamic acid (NH(2)SO(3)H). A qualitative method for identifying sulfonylated amino acids is described.     

Origin of Tektites

A comet of the size recently postulated by H. C. Urey would leave a large crater. It is shown, from aerodynamic theory, from observations of distribution around terrestrial impact craters, and from experimental nuclear explosions, that the observed distribution of tektites cannot be the result of impact on the earth, whether cometary or meteoritic. It is further shown, from aerodynamic theory, from observation of a meteor shower, and from study of the breakup of artificial satellites, that the distribution of tektites can be accounted for as a result of fusion stripping of a satellite, as originally suggested by Suess.