Addition-Rearrangement of Aryl- and Alkoxysulfonyl Isocyanates with 5-Methyl-Substituted 3,4-Dihydro-2-methoxy-2H-pyrans. Selective Synthesis of Functionalized 2-Piperidones(1)

3,4-Dihydro-2-methoxy-5-methyl-2H-pyran and 3,4-dihydro-2-methoxy-5,6-dimethyl-2H-pyran undergo addition-rearrangement reactions with arylsulfonyl isocyanates to generate the corresponding 3-formyl- and 3-acetyl-6-methoxy-3-methyl-1-(arylsulfonyl)-2-piperidones. For example, 3,4-dihydro-2-methoxy-5-methyl-2H-pyran and phenylsulfonyl isocyanate afforded 3-formyl-6-methoxy-3-methyl-1-(phenylsulfonyl)-2-piperidone as a separable trans/cis mixture in high yield. The more reactive phenoxysulfonyl and alkoxysulfonyl isocyanates provided analogous results.     

Hydrocarbon dispersions of acrylic microspheres with polar surface functionality

Submicron and micron sized particles containing a crosslinked core and a polar shell were prepared by 3-stage nonaqueous dispersion [NAD] polymerization in an aliphatic hydrocarbon medium. When a poly (12-hydroxystearic acid) [PHS] comb stabilizer was used in all three stages, the particles produced were spherical, submicron in size, and had a relatively broad size distribution. If the monomer mixture in the third stage contained relatively large amounts of butyl acrylate, stable dispersions of sponge-like aggregates, 3–5 μm in size, were obtained. When butyl rubber was employed as a stabilizer precursor in the seed formation step, the shape of the final particles depended upon whether a crosslinker was employed in the second stage polymerization. When a crosslinker was present, the second-stage particles and the subsequent third-stage particles had a shrunken, raisin-like appearance. When no crosslinker was present, spherical particles were obtained. In both cases, the resulting third-stage particles were easily dispersed in water containing a small amount of amine base, indicating that ? COOH and ? OH groups are located at the surface (or in a shell at the surface) in these NAD particles. © 1994 John Wiley & Sons, Inc.     

The many-body problem within the Lee model

The structure of a field theoretical many-body problem is studied within the (non-static) Lee model. The explicit solvability of the renormalization problem allows the investigation of renormalization corrections in many-particle systems. Herefore, the renormalized equations are worked out for the N-V scattering and for the binding-energy problem of “N-V matter” — these cases taken in analogy to nucleon-nucleon scattering and nuclear matter. The N-V matter equations are obtained from a cluster expansion suitably defined for the field theoretical case. The ansatz for the correlated wave functions is chosen in such a way as to generate a two-hole-line expansion of the binding energy. The renormalized form of this field theoretical extension of Brueckner theory is discussed in detail revealing the medium effects on renormalization.     

阵列探测器对斜入射激光的功率测量不确定度

为了对斜入射情况下的激光功率进行准确测量,采用了对阵列探测器的功率响应度依角度进行修正的方法。推导了依赖于光源位置、阵列探测器位置和阵列探测器姿态角的激光光线方向余弦和入射角的数学表达式,推导了光线方向余弦和入射角的测量不确定度表达式以及阵列探测器功率修正因子的不确定度表达式,并根据功率表达式进一步推导了功率测量不确定度表达式。由此建立了斜入射情况下激光功率阵列探测器测量方法及功率测量不确定度评定的一套较完整的方法。以典型参数为例,计算了斜入射下阵列探测器测量激光功率的不确定度,结果表明采用修正方法可显著减小激光功率测量不确定度。     

Genetically encoded fluorescent reporters of histone methylation in living cells

We report the design and characterization of two genetically encoded fluorescent reporters of histone protein methylation. The reporters are four-part chimeric proteins consisting of a substrate peptide from the N-terminus of histone H3 fused to a chromodomain (a natural methyllysine-specific recognition domain), sandwiched between a fluorescence resonance energy transfer (FRET)-capable pair of fluorophores, cyan fluorescent protein (CFP) and yellow fluorescent protein (YFP). Enzymatic methylation by a methyltransferase induces complexation of the methylated substrate peptide to the chromodomain, changing the FRET level between the flanking CFP and YFP domains. Reporters developed using the chromodomains from HP1 and Polycomb respond to enzymatic methylation at the lysine 9 and lysine 27 positions of histone H3, respectively, giving 60% and 28% YFP/CFP emission ratio increases in vitro or in single living cells. These reporters should be useful for studying gene silencing and X-chromosome inactivation with high spatial and temporal resolution in intact cells and may also aid in the search for conjectured histone demethylase activity.     

Effect of a coadsorbent on the performance of dye-sensitized TiO2 solar cells: shielding versus band-edge movement

The mechanism by which the adsorbent chenodeoxycholate, cografted with a sensitizer onto TiO2 nanocrystals, alters the open-circuit photovoltage and short-circuit current of dye-sensitized solar cells was investigated. The influence of tetrabutylammonium chenodeoxycholate on dye loading was studied under a variety of conditions in which the TiO2 films were exposed to the sensitizing dye and coadsorbent. Photocurrent--voltage measurements combined with desorption studies revealed that adding chenodeoxycholate reduces the dye loading by as much as 60% while having a relatively small effect on the short-circuit photocurrent. Calculations along with measurements showed that even at low loading, enough dye is present to absorb a significant fraction of the incident light in the visible spectrum. In concurrence with the observations of others, we find evidence for weakly and strongly adsorbed forms of the dye resulting from either different binding conformations or aggregates. The most strongly adsorbed dyes are less susceptible to displacement by chenodeoxycholate than those that are weakly adsorbed. While having no observable effect on dye coverage, multiple exposures of a TiO2 film to a dye solution substantially increased the fraction of strongly adsorbed dye as judged by the resistance of the adsorbed dye to displacement by chenodeoxycholate. Measurements of the open-circuit voltage as a function of the photocharge density, determined by infrared transmittance, showed that chenodeoxycholate not only shifts the conduction band edge to negative potentials, but also significantly increases the rate of recombination. The net effect of adding chenodeoxycholate is, however, to improve the photovoltage.     

Study on chemical separation of67Ga VIAnatZn(p,xn) reaction

A potential⁶⁸Ge/⁶⁸Ga generator system has orginally been established by using adsorption chromatography on inorganic adsorbent SiO₂. This type of generator delivers 90% of⁶⁸Ga with the breakthrough levels of⁶⁸Ge lower than 10^–3% per 10 ml of collection volume and readily provides tracer for this experimental study. Three routes for the separation of⁶⁷Ga from Zn target, including solvent extraction with allylether and cation exchange with Dowex 50W-×8 as well as anion exchange with AG1-×8, have been investigated and compared. The simulated experiments were performed with synthetic solutions containing appropriate amounts of Zn, the possible impurities, Fe, Cu and their radioactive tracers. The results show that a single stage allylether solvent extraction permits an extremely high recovery yield of 99% of⁶⁷Ga with a desired radionuclidic purity and almost complete removal of the chemical impurities. By a combination of cation-exchange separation followed with allylether extraction, a slightly lower yield (89%) but highest purity of the product can be obtained. The anion exchange process is of less interest due to its low recovery of⁶⁷Ga and poor decontamination of the impurities.     

Molecular polarizability estimates for vibrational spectral interpretation

A scheme is outlined for obtaining estimates of molecular polarizabilities, quadrupole moments, and their derivatives from restricted Hartree-Fock calculations. Results are presented for the test cases H₂, F₂ and Cl₂, and the compared with experiment. This results are found to be lower limits to these quantities, and they are expected to be of use in the interpretation of Raman and of collision-induced infrared absorption spectra.     

Optical characterization of pristine poly(3‐hexyl thiophene) films

We describe a comprehensive model for the optical properties of pristine films of poly‐(3‐hexylthiophene) (P3HT). The presented model is anisotropic with the optical axis normal to the substrate plane, which is consistent with previous x‐ray diffraction studies that show preferential edge‐on packing of the polymer chains on the substrate. Peak locations and spacings are defined using a Huang‐Rhys vibronic progression consistent with known phonon energies. We demonstrate that the model fits variable‐angle spectroscopic ellipsometry and normal‐incidence transmission data well, and accurately predicts angle‐ and polarization‐dependent transmission and reflection data. The spectral features of the optical constants used in the model are in excellent agreement with published spectroscopic data on P3HT. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010