Photocurrent generation in multilayer organic-inorganic thin films with cascade energy architectures

Zirconium organobisphosphonate multilayer thin films of viologen derivatives were grown on copper dithiolate multilayers of 5,15-di(p-thiolphenyl)-10,20-di(p-tolyl)porphyrin (POR) and 5,15-di(p-thiolphenyl)-10,20-di(p-tolyl)porphyrinzinc (ZOR) on a variety of substrates (e.g. Au, SiO(2)), using solution depositions methods. The multilayer structures were studied by atomic force microscopy, UV-vis spectroscopy, and ellipsometry. In the case of copper dithiolate thin films, layer-by-layer lamellar growth with low surface roughness resulted, while higher surface roughness was observed in the growth of Zr viologen bisphosphonate films. Gold electrodes modified with zirconium bisphosphonate multilayers of viologen on top of copper dithiolate multilayers of porphyrin derivatives (ZOR or POR) were photoelectroactive and produced efficient and stable photocurrents using visible light. By arranging the zinc-porphyrin (ZOR) and the free base porphyrin (POR) donors in an energetically favorable fashion, according to their redox potentials and optical energy gaps, the photoinduced charge separation was improved, and higher photocurrent quantum yields ( approximately 4%) and fill factor ( approximately 50%) of the photoelectrode were achieved.     

Asymmetric inter- and intramolecular cyclopropanation of alkenes catalyzed by chiral ruthenium porphyrins. Synthesis and crystal structure of a chiral metalloporphyrin carbene complex.

Extensive investigations of asymmetric intermolecular cyclopropanation of terminal alkenes with diazoacetates catalyzed by ruthenium porphyrin [Ru(P*)(CO)(EtOH)] (1, H2P = 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracene-9-yl]porphyrin) and the application of catalyst 1 to asymmetric intramolecular cyclopropanation of allylic or homoallylic diazoacetates are described. The intermolecular cyclopropanation of styrene and its derivatives with ethyl diazoacetate afforded the corresponding cyclopropyl esters in up to 98% ee with high trans/cis ratios of up to 36 and extremely high catalyst turnovers of up to 1.1 x 10(4). Examination of the effects of temperature, diazoacetate, solvent, and substituent in the intermolecular cyclopropanation reveals that (i) both enantioselectivity and trans selectivity increase with decreasing temperature, (ii) sterically encumbered diazoacetates N2CHCO2R, such as R = Bu(t), and donor solvents, such as diethyl ether and tetrahydrofuran, are beneficial to the trans selectivity, and (iii) electron-donating para substituents on styrene accelerate the cyclopropanations, with the log(k(X)/k(H)) vs sigma(+) plot for para-substituted styrenes p-X-C6H4CH=CH2 (X = MeO, Me, Cl, CF3) exhibiting good linearity with a small negative rho(+) value of -0.44 +/- 0.09. In the case of intramolecular cyclopropanation, complex 1 promoted the decomposition of a series of allylic diazoacetates to form the cyclopropyl lactones in up to 85% ee, contributing the first efficient metalloporphyrin catalyst for an asymmetric intramolecular cyclopropanation. Both the inter- and intramolecular cyclopropanations were proposed to proceed via a reactive chiral ruthenium carbene intermediate. The enantioselectivities in these processes were rationalized on the basis of the X-ray crystal structures of closely related stable chiral carbene complexes [Ru(P*)(CPh2)] (2) and [Ru(P*)(C(Ph)CO2CH2CH=CH2)] (3) obtained from reactions of complex 1 with N2CPh2 and N2C(Ph)CO2CH2CH=CH2, respectively.     

Time series modelling of the Singapore population data

Trends in population have important implications for a government in formulating its manpower-related policies. A business may also need to adjust its long-term market strategies according to these trends. This paper analyses the Singapore population data using time series regression model with autoregressive error term. In addition to a linear trend, other regressors included in the model are (i) a seasonal component of period 12 to account for the effect of the auspicious “dragon” years in the Chinese calendar; (ii) level-shift interventions to account for the effect of the government campaigns on family planning. Two methods of estimating the autoregressive parameter are considered: maximum likelihood (ML) and restricted maximum likelihood (REML). For a time series of short or moderate sample length, it is shown in Cheang and Reinsel (2000) that the REML estimator is generally much less biased than the ML estimator. Consequently, the REML approach leads to more accurate inferences for the regression parameters. This paper compares the ML and REML estimation results, and examines the implications for the nature of nonstationarity (deterministic or stochastic trend component) exhibited by the Singapore population data series. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Brown–York Mass of Revolution Surfaces in Asymptotically Schwarzschild Manifolds

In this paper, we will show that the limit of the Brown–York mass of a family of convex revolution surfaces in an asymptotically Schwarzschild manifold is the ADM mass.     

Identities for Bernoulli polynomials and Bernoulli numbers

We prove that if m and \({\nu}\) are integers with \({0 \leq \nu \leq m}\) and x is a real number, then

1. $$\sum_{k=0 \atop k+m \, \, odd}^{m-1} {m \choose k}{k+m \choose \nu} B_{k+m-\nu}(x) = \frac{1}{2} \sum_{j=0}^m (-1)^{j+m} {m \choose j}{j+m-1 \choose \nu} (j+m) x^{j+m-\nu-1},$$ where B _n (x) denotes the Bernoulli polynomial of degree n. An application of (1) leads to new identities for Bernoulli numbers B _n . Among others, we obtain
2. $$\sum_{k=0 \atop k+m \, \, odd}^{m -1} {m \choose k}{k+m \choose \nu} {k+m-\nu \choose j}B_{k+m-\nu-j} =0 \quad{(0 \leq j \leq m-2-\nu)}. $$ This formula extends two results obtained by Kaneko and Chen-Sun, who proved (2) for the special cases j = 1, \({\nu=0}\) and j = 3, \({\nu=0}\) , respectively.

     

Ultracompact and fabrication-tolerant integrated polarization splitter

Design and fabrication of a 2×2 two-mode interference (TMI) coupler based on-chip polarization splitter is presented. By changing the angle between the access waveguides, one can tune the effective TMI length for the mode with less optical confinement (transverse magnetic, TM) to coincide with the target TMI length for a desired transmission of the mode with higher optical confinement (transverse electric, TE). The fabricated 0.94?μm long 2×2 TMI splits the input power into TM (bar) and TE (cross) outputs with splitting ratio over 15?dB over 50?nm bandwidth. Fabrication tolerance analysis shows that the device is tolerant to fabrication errors as large as 60?nm.     

Iterative in situ click chemistry assembles a branched capture agent and allosteric inhibitor for Akt1

We describe the use of iterative in situ click chemistry to design an Akt-specific branched peptide triligand that is a drop-in replacement for monoclonal antibodies in multiple biochemical assays. Each peptide module in the branched structure makes unique contributions to affinity and/or specificity resulting in a 200 nM affinity ligand that efficiently immunoprecipitates Akt from cancer cell lysates and labels Akt in fixed cells. Our use of a small molecule to preinhibit Akt prior to screening resulted in low micromolar inhibitory potency and an allosteric mode of inhibition, which is evidenced through a series of competitive enzyme kinetic assays. To demonstrate the efficiency and selectivity of the protein-templated in situ click reaction, we developed a novel QPCR-based methodology that enabled a quantitative assessment of its yield. These results point to the potential for iterative in situ click chemistry to generate potent, synthetically accessible antibody replacements with novel inhibitory properties.     

薄层色谱法鉴定APC药片组分的实验条件优化

对薄层色谱法鉴定复方乙酰水杨酸(APC)药片组分的展开剂进行了探索实验,用石油醚和乙酸乙酯替换了乙醚和二氯甲烷。新的展开剂对药片组分的分离更容易观察,并且比原展开剂挥发性低、毒性小,既提高了教学效果又减少了实验室污染。