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971.
Reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] (Ln=Y, Yb, and Lu) with one equivalent of Me(2)Si(C(5)Me(4)H)NHR' (R'=Ph, 2,4,6-Me(3)C(6)H(2), tBu) affords straightforwardly the corresponding half-sandwich rare-earth metal alkyl complexes [{Me(2)Si(C(5)Me(4))(NR')}Ln(CH(2)SiMe(3))(thf)(n)] (1: Ln = Y, R' = Ph, n=2; 2: Ln = Y, R' = C(6)H(2)Me(3)-2,4,6, n=1; 3: Ln = Y, R' = tBu, n=1; 4: Ln = Yb, R' = Ph, n=2; 5: Ln = Lu, R' = Ph, n=2) in high yields. These complexes, especially the yttrium complexes 1-3, serve as excellent catalyst precursors for the catalytic addition of various primary and secondary amines to carbodiimides, efficiently yielding a series of guanidine derivatives with a wide range of substituents on the nitrogen atoms. Functional groups such as C[triple chemical bond]N, C[triple chemical bond]CH, and aromatic C--X (X: F, Cl, Br, I) bonds can survive the catalytic reaction conditions. A primary amino group can be distinguished from a secondary one by the catalyst system, and therefore, the reaction of 1,2,3,4-tetrahydro-5-aminoisoquinoline with iPrN==C==NiPr can be achieved stepwise first at the primary amino group to selectively give the monoguanidine 38, and then at the cyclic secondary amino unit to give the biguanidine 39. Some key reaction intermediates or true catalyst species, such as the amido complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y(NEt(2))(thf)(2)] (40) and [{Me(2)Si(C(5)Me(4))(NPh)}Y(NHC(6)H(4)Br-4)(thf)(2)] (42), and the guanidinate complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrNC(NEt(2))(NiPr)}(thf)] (41) and [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrN}C(NC(6)H(4)Br-4)(NHiPr)}(thf)] (44) have been isolated and structurally characterized. Reactivity studies on these complexes suggest that the present catalytic formation of a guanidine compound proceeds mechanistically through nucleophilic addition of an amido species, formed by acid-base reaction between a rare-earth metal alkyl bond and an amine N--H bond, to a carbodiimide, followed by amine protonolysis of the resultant guanidinate species. 相似文献
972.
973.
免疫亲和柱净化-柱后光化学衍生-高效液相色谱法同时检测粮谷中的黄曲霉毒素、玉米赤霉烯酮和赭曲霉毒素A 总被引:14,自引:0,他引:14
建立了同时检测粮谷中黄曲霉毒素(B1、B2、G1和G2)、玉米赤霉烯酮和赭曲霉毒素A的免疫亲和柱净化-柱后光化学衍生-高效液相色谱方法。样品经过甲醇-水(体积比为80∶20)提取,通过免疫亲和柱富集和净化,采用Waters Nova-Pak色谱柱(3.9 mm i.d.×150 mm,4 μm),以甲醇、乙腈和1%的磷酸溶液为流动相,梯度洗脱,柱后光化学衍生、改变波长荧光检测。黄曲霉毒素(B1、B2、G1和G2)、玉米赤霉烯酮和赭曲霉毒素A检出限分别为0.24,4.0和0.5 μg/kg,标准曲线的线性范围分别为0.24~6.0,4.0~100.0和0.5~40.0 μg/L;在小麦、玉米、黑麦样品中,平均加标回收率为70.8% ~94.0%,相对标准偏差为2.79% ~9.38%。 相似文献
974.
Huilin Hou Xiangkang Zeng Xiwang Zhang 《Angewandte Chemie (International ed. in English)》2020,59(40):17356-17376
Hydrogen peroxide (H2O2) has received increasing attention because it is not only a mild and environmentally friendly oxidant for organic synthesis and environmental remediation but also a promising new liquid fuel. The production of H2O2 by photocatalysis is a sustainable process, since it uses water and oxygen as the source materials and solar light as the energy. Encouraging processes have been developed in the last decade for the photocatalytic production of H2O2. In this Review we summarize research progress in the development of processes for the photocatalytic production of H2O2. After a brief introduction emphasizing the superiorities of the photocatalytic generation of H2O2, the basic principles of establishing an efficient photocatalytic system for generating H2O2 are discussed, highlighting the advanced photocatalysts used. This Review is concluded by a brief summary and outlook for future advances in this emerging research field. 相似文献
975.
两级载荷下复合材料层板疲劳与寿命预测 总被引:4,自引:0,他引:4
研究了复合材料层板疲劳过程中的累积应变演化规律,建立了以累积应变为基础的非线性积累损伤法则,实验结果表明:文中提出的累积应变方法能够较好地反映加载次序效应,准确地预测了复合材料层板在两级载荷下的疲劳寿命。 相似文献
976.
Dr. Xiao‐Jiao Kang Dr. Yun‐Lu Dai Dr. Ping‐An Ma Dr. Dong‐Mei Yang Dr. Chun‐Xia Li Dr. Zhi‐Yao Hou Dr. Zi‐Yong Cheng Prof. Jun Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(49):15676-15682
Monodisperse poly(acrylic acid)‐modified Fe3O4 (PAA@Fe3O4) hybrid microspheres with dual responses (magnetic field and pH) were successfully fabricated. The PAA polymer was encapsulated into the inner cavity of Fe3O4 hollow spheres by a vacuum‐casting route and photo‐initiated polymerization. TEM images show that the samples consist of monodisperse porous spheres with a diameter around 200 nm. The Fe3O4 spheres, after modification with the PAA polymer, still possess enough space to hold guest molecules. We selected doxorubicin (DOX) as a model drug to investigate the drug loading and release behavior of as‐prepared composites. The release of DOX molecules was strongly dependent on the pH value due to the unique property of PAA. The HeLa cell‐uptake process of DOX‐loaded PAA@Fe3O4 was observed by confocal laser scanning microscopy (CLSM). After being incubated with HeLa cells under magnet magnetically guided conditions, the cytotoxtic effects of DOX‐loaded PAA@Fe3O4 increased. These results indicate that pH‐responsive magnetic PAA@Fe3O4 spheres have the potential to be used as anticancer drug carriers. 相似文献
977.
Partitionally assembled organosulfur monolayers were prepared by using an electrochemically assisted assembly method on gold films that were preseparated into two regions insulated from each other. Cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the n-dodecanethiol (DDT) and the 11-mercaptoundecanoic acid (MUA) monolayers, which were separately assembled on different substrate regions. CV results indicated that both the DDT- and MUA-coated gold electrodes showed a blocking property toward the negatively charged redox probe Fe(CN)6(3-). However, when positively charged Ru(NH3)6(3+) was used as the redox probe, the MUA- and DDT-modified electrodes showed quasireversible and blocking CV features, respectively. These phenomena were attributed to different interactions between the negatively charged MUA surface and the negatively or positively charged redox probes. XPS spectra obtained on the MUA modified region exhibited an O(1s) peak and a small discrete C(1s) peak, which arose from the oxygen and the carbon atoms in the carboxylic acid groups, respectively. For the DDT-modified region, these two peaks were absent. CV and XPS experimental results provided strong evidence that different SAMs were selectively deposited onto different regions of the preexisting patterns of the substrate by electrochemically partitioned assembly. The partitionally assembled sulfur-based monolayers with different terminal groups were used to form location-selective nanoparticle assemblies. This electrochemically partitioned assembly technique has great potential in controllable constructions of molecular layers and nanostructures on different surface microarchitectures that are closely integrated on one substrate but insulated from each other. 相似文献
978.
Shihui Jiao Guangsheng Pang Hongwei Liang Yan Chen Shouhua Feng 《Journal of nanoparticle research》2007,9(4):605-610
Nanoparticles and nanorods of CuSb2O6 are prepared by hydrothermal method and its high temperature α-phase is stabilized at room temperature. The average size
of the nanoparticles is ca. 13.7 nm. The nanorods, with a width of ca. 20 nm and an aspect ratio of ca. 5, are the agglomerates
composing of smaller nanoparticles with an average size of ca. 8.3 nm. Compared with the high temperature α-phase of bulk
sample at 400 K, the lattice of nanophases elongated in ab plane and compressed along c direction. The CuSb2O6 nanoparticles exhibit predominant paramagnetic phenomenon. The difference in magnetic properties of the nanoparticles and
nanorods indicates the interfacial interaction of agglomerated nanoparticles. 相似文献
979.
A theoretical analysis of the pump-induced temperature change and associated thermal phase shift occurring in a fiber laser is presented. The temperature rise and thermal phase shift from the moment when pump is turned on to steady-state in fiber lasers, such as Yb-doped fiber laser, are numerical calculated.With the same parameters, the numerical solution is in good agreement with the finite-element (ANSYS software) simulation. 相似文献
980.
Go A Bay A Abe K Aihara H Anipko D Aulchenko V Aushev T Bakich AM Barberio E Belous K Bitenc U Bizjak I Blyth S Bozek A Bracko M Browder TE Chang P Chao Y Chen A Chen KF Chen WT Cheon BG Chistov R Choi Y Choi YK Cole S Dalseno J Danilov M Dash M Drutskoy A Eidelman S Epifanov D Fratina S Gabyshev N Gershon T Gokhroo G Golob B Gorisek A Ha H Hastings NC Hayasaka K Hayashii H Hazumi M Heffernan D Hokuue T Hoshi Y Hou S Hou WS Iijima T Ikado K Imoto A Inami K Ishikawa A Ishino H Itoh R Iwasaki M 《Physical review letters》2007,99(13):131802
The neutral B meson pair produced at the Upsilon(4S) should exhibit a nonlocal correlation of the type discussed by Einstein, Podolsky, and Rosen. We measure this correlation using the time-dependent flavor asymmetry of semileptonic B(0) decays, which we compare with predictions from quantum mechanics and two local realistic models. The data are consistent with quantum mechanics, and inconsistent with the other models. Assuming that some B pairs disentangle to produce B(0) and B(0) with definite flavor, we find a decoherent fraction of 0.029 +/ -0.057, consistent with no decoherence. 相似文献