VOLT-AMPERE CHARACTERISTICS OF CIS-POLY(PHENYL ACETYLENE)

The volt-ampere (Ⅰ-Ⅴ) characteristics of the c/s-poly (phenyl acetylene) (PPA) of cis-transoidal structure has been studied in the temperature range of 253-288K. An ITO/ PPA/ Au sandwich configuration was used for the measurements. Under an applied field of less than 10~5V/ cm it showed ohmic behavior, while the space charge limited current (SCLC) was observed at applied fields above 5×10~5V/ cm. In the ohmic region a conductivity of 1.37×10~(-16)S/ cm was obtained at room temperature with an activation energy of 0.5eV. These data indicate that the conduction is not intrinsic one but is the result of thermal release of trapped carriers. In fact the data in the SCLC region treated according to the theory for a single Gaussian distribution of traps gave a mean trap energy of 0.48 eV with a half-width of 0.4 eV and a total density of trapping states of 5×10~(16)/cm~3.     

On the Reaction of Some Saccharin Derivatives with Hydrazine and Other Nucleophils

Summary.  The reaction of methyl saccharin-2-acetate with hydrazine gave no 3-hydrazino derivative of saccharin as reported in literature, but yielded with ring opening the benzohydrazide derivative. The analogue reaction was observed when saccharin-2-(2-propionate) was reacted with hydrazine. Furthermore, using an excess of hydrazine, the ester group was transformed into the carbohydrazide too. All hydrazides were fully characterized as hydrazones by reactions with different ketones. The 3-thioxo compounds were prepared by reactions with P₂s₅, but the yield was improved by using Lawesson’s reagent. No attack at the ester group was observed. Finally, reactions of the saccharin-2-carboxylate with some amino acids gave substituted benzamides by attack at position 3 and ring opening. In none of the reactions of the saccharin derivatives with nitrogen nucleophiles a formal substitution of the 3-oxo group was observed. Corresponding author. E-mail: ottohh@pharmazie.uni-greifswald.de Received July 4, 2002; accepted August 1, 2002 Published online February 20, 2003     

Facile synthesis of (±)-, (+)-, and (-)-galanthamine

The Amarylidacea alkaloid galanthamine ( 1a ) is an acetylcholinesterase inhibitor that has been evaluated as a potential agent for the treatment of Alzheimer's disease. We report a very efficent synthesis of (±)-galanthamine [(±)- 1a ] from readily available isovanillin and tyramine. We have separated racemic galanthamine into its diastereoisomeric (1S)-camphanate esters and obtained both natural (-)- and unnatural (+)-galanthamine by lithium aluminum hydride removal of the acyl group.     

Use of [hydroxy(tosyloxy)iodo]benzene in a novel and facile synthesis of 1,4-diaryl-2-(arylamino)but-2-ene-1,4-diones

The reaction of acetophenones 1 with [hydroxy(tosyloxy)iodo]benzene followed by treatment of the resulting α-tosyloxyacetophenones 2 thus formed with anilines 3 in the presence of sodium carbonate in ethanol provides a novel one-pot synthesis of 1,4-diaryl-2-(arylamino)but-2-ene-1,4-diones 4.     

Bicyclo[3.2.1]amide-DNA: a chiral,nonchiroselective base-pairing system

The design, synthesis, and base-pairing properties of bicyclo[3.2.1]amide-DNA (bca-DNA), a novel phosphodiester-based DNA analogue, are reported. This analogue consists of a conformationally constrained backbone entity, which emulates a B-DNA geometry, to which the nucleo-bases were attached through an extended, acyclic amide linker. Homobasic adenine-containing bca decamers form duplexes with complementary oligonucleotides containing bca, DNA, RNA, and, surprisingly, also L-RNA backbones. UV and CD spectroscopic investigations revealed the duplexes with D- or L-complements to be of similar stability and enantiomorphic in structure. Bca oligonucleotides that contain all four bases form strictly antiparallel, left-handed complementary duplexes with themselves and with complementary DNA, but not with RNA. Base-mismatch discrimination is comparable to that of DNA, while the overall thermal stabilities of bca-oligonucleotide duplexes are inferior to those of DNA or RNA. A detailed molecular modeling study of left- and right-handed bca-DNA-containing duplexes showed only minor changes in the backbone structure and revealed a structural switch around the base-linker unit to be responsible for the generation of enantiomorphic duplex structures. The obtained data are discussed with respect to the structural and energetic role of the ribofuranose entities in DNA and RNA association.     

High-throughput analysis of telomerase by capillary electrophoresis

The enzyme telomerase is expressed in (85-90)% of all human cancers, but not in normal, non-stem cell somatic tissues. Clinical assays for telomerase in easily obtained body fluids would have great utility as noninvasive, cost-effective methods for the early detection of cancer. The most commonly used method for the detection and quantification of telomerase enzyme activity is the polymerase chain reaction (PCR)-based assay known as the telomerase repeat amplification protocol or TRAP assay. Most of the TRAP assay systems use a slab-gel based electrophoresis system to size and quantify the PCR-amplified extension products. We are developing high-throughput capillary electrophoresis (CE) methods for the analysis of TRAP/PCR products. The TRAP assay was conducted on lysates of the human lung cancer cell line A-549 in reactions containing 5-100 cells. TRAP/PCR products were generated using a fluorescent 4,7,2'4'5'7',-hexachloro-6-carboxyfluorescein(HEX)-labeled TS primer and analyzed on the Applied Biosystems Model 310 CE system using POP4 polymer. After analysis with GeneScan and Genotyper software, the total peak areas of the TRAP ladder extension products were computed using Microsoft Excel. Results were compared with unlabeled TRAP/PCR products analyzed on the Bio-Rad BioFocus 3000 CE system using 6% high molecular weight polyvinylpyrrolidone (HMW PVP) polymer and SYBR Green I dye. Both CE systems were able to resolve the TRAP ladder products with high reproducibility and sensitivity (5-15 cells). With the appropriate robotic sample handling system, these CE methods would enable performing the telomerase TRAP assay with increased sensitivity, reproducibility and automation over slab-gel methods.     

β-Glucosidase production by Trichoderma reesei

The hydrolysis of cellulose to the water-soluble products cellobiose and glucose is achieved via synergistic action of cellulolytic proteins. The three types of enzymes involved in this process are endoglucanases, cellobiohydrolases, and β-glucosidases. One of the best fungal cellulase producers is Trichoderma reesei RUT C30. However, the amount of β-glucosidases secreted by this fungus is insufficient for effective cellulose conversion. We investigated the production of cellulases and β-glucosidases in shake-flask cultures by applying three pH-controlling strategies: (1) the pH of the production medium was adjusted to 5.8 after the addition of seed culture with no additional pH adjustment performed, (2) the pH was adjusted to 6.0 daily, and (3) the pH was maintained at 6.0 by the addition of Tris-maleate buffer to the growth medium. Different carbon sources—Solka Floc 200, glucose, lactose, and sorbitol—were added to standard Mandels nutrients. The lowest β-glucosidase activities were obtained when no pH adjustment was done regardless of the carbon source employed. Somewhat higher levels of β-glucosidase were measured in the culture filtrates when daily pH adjustment was carried out. The effect of buffering the culture medium on β-glucosidase liberation was most prominent when a carbon source inducing the production of other cellulases was applied.     

Implied Open-circuit Voltage Imaging via a Single Bandpass Filter Method—Its First Application in Perovskite Solar Cells

A novel, camera-based method for direct implied open-circuit voltage (iV_OC) imaging via the use of a single bandpass filter (s-BPF) is developed for large-area photovoltaic solar cells and precursors. The photoluminescence (PL) emission is imaged using a narrow BPF with centre energy inside the high-energy tail of the PL emission, utilising the close-to-unity and nearly constant absorptivity of typical photovoltaic devices in this energy range. As a result, the exact value of the sample's absorptivity within the BPF transmission band is not required. The use of an s-BPF enables a fully contactless approach to calibrate the absolute PL photon flux for spectrally integrated detectors, including cameras. The method eliminates the need for knowledge of the imaging system spectral response. Through an appropriate choice of the BPF centre energy, a range of absorber compositions or a single absorber with different surface morphologies, such as planar and textured, can be imaged, all without the need for additional detection optics. The feasibility of this s-BPF method is first validated. The relative error in iV_OC is determined to be ≤1.5%. The method is then demonstrated on device stacks with two different perovskite compositions commonly used in single-junction and monolithic tandem solar cells.     

AlR2Cl/MgR2 combinations as universal cocatalysts for Ziegler–Natta,metallocene, and post‐metallocene catalysts

Combinations of dialkylaluminum chlorides and dialkylmagnesium compounds, when used at molar [AlR₂Cl]:[MgR₂] ratios ≥ 2, act as universal cocatalysts for all three presently known types of alkene polymerization catalysts—Ziegler–Natta, metallocene, and post‐metallocene. When these cocatalysts are used with supported Ti‐based Ziegler–Natta catalysts, they produce catalyst systems which are 1.5–2 times more active than the systems utilizing AlR₃ compounds as cocatalysts. Combinations of AlR₂Cl/MgR₂ cocatalysts and various metallocene complexes produce single‐center catalyst systems similar to those formed in the presence of MAO. The same cocatalysts activate numerous post‐metallocene Ti complexes containing bidentate ligands of a different nature and produce multicenter systems of very high activity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3271–3285, 2009     

Surface analysis of particulates from laboratory hood exhaust manifold

Particulate samples collected from a laboratory ventilation manifold during routine maintenance were analyzed to determine if particulate composition had changed as a result of changes in the laboratory's atmosphere. This ventilation manifold exhausts more than 100 fume hoods. The particulate samples were analyzed using static secondary ion mass spectrometry (SIMS). The negative SIMS spectra showed abundant Cl^?, NO₃^?, and HSO₄^?, consistent with the use of mineral acids in the laboratory. Cluster anions containing primarily Zn (but also other transition metals) were detected, which signaled corrosion of the manifold's galvanized steel by the volatilized acids. The most abundant ions in the cation SIMS spectra were derived from cyclohexylamine (CHA), which had been used as an antiscaling agent in the facility's boiler. Steam from the boiler, which contained CHA, was used to humidify the building air; this practice stopped in 1997. The abundances of the CHA‐derived ions were significantly lower in the samples collected in 2004 and 2006 than in the 1992 samples, indicating that the CHA is being slowly depleted. Changes in the relative abundances suggest exponential depletion from the manifold with rate constants that are on the order of 0.01 to 0.04 month^?1. Published in 2007 John Wiley & Sons, Ltd.