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M.C. Ubaldi V. Stasi U. Colombo D. Piccinin M. Martinelli 《Photonics and Nanostructures》2007,5(2-3):145-148
Roughness reduction of a submicron waveguide profile in chemically amplified negative resist is here performed by proper selection of an alkali-based developer, taking into account that its smaller molecules lead to smoother resist surface by altering the developing mechanism of aggregate extraction performed with standard quaternary ammonium hydroxide. Roughness is then analyzed by means of classical Atomic Force Microscope inspection; furthermore, a non-invasive line edge roughness analysis approach based on top-down scanning electron microscope acquisition gives comparable results, in terms of standard deviation and molecular aggregate periodicity. 相似文献
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Stefano Vecchio Alessia Catalani Vanessa Rossi Mauro Tomassetti 《Thermochimica Acta》2004,420(1-2):99-104
The thermal behaviour of acetanilide (Ac) and two of its analogues, namely the para-ethoxyacetanilide (p-Eto Ac) and the para-bromoacetanilide (p-Br Ac), which are used as analgesics in the pharmaceutical industry was studied with a simultaneous TG/DSC unit. The examined analgesics showed two endothermic DSC peaks due to melting and vaporization. By combining the experimental TG data with the corresponding reference vapour pressure data obtained with the Antoine equation the plot of P versus v was derived. From the slope of this equation the constant k-value was determined for Ac. Then, using the same k-value the vapour pressures of p-Eto Ac and p-Br Ac were determined in the same temperature range. The vaporization enthalpies for all the studied compounds were obtained from different methods and a very good agreement was found. Vaporization follows a zero-order kinetics. The activation energy of vaporization (Evap) was calculated from the dynamic TG experiments, using the Arrhenius equation. 相似文献
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P. Colombo L. E. Kukacka J. Fontana R. N. Chapman M. Steinberg 《Journal of polymer science. Part A, Polymer chemistry》1966,4(1):29-57
The γ-radiation-induced free-radical copolymerization of ethylene and CO has been investigated over a wide range of pressure, initial gas composition, radiation intensity, and temperature. At 20°C., concentrations of CO up to 1% retard the polymerization of ethylene. Above this concentration the rate reaches a maximum between 27.5 and 39.2% CO and then decreases. The copolymer composition increases only from 40 to 50% CO when the gas mixture is varied from 5 to 90% CO. A relatively constant reactivity ratio is obtained at 20°C., indicating that CO adds 23.6 times as fast as an ethylene monomer to an ethylene free-radical chain end. For a 50% CO gas mixture, the above value of 23.6 and the copolymerization rate decrease with increasing temperature to 200°C. The kinetic data indicate a temperature-dependent depropagation reaction. Infrared examination of copolymers indicates a polyketone structure containing ? CH2? CH2? and ? CO? units. The crystalline melting point increases rapidly from 111 to 242°C., as the CO concentration in the copolymer increases from 27 to 50%. Molecular weight of copolymer formed at 20°C. increased with increasing CO, indicating M?n values >20,000. Increasing reaction temperature results in decreasing molecular weight. Onset of decomposition for a 50% CO copolymer was measured at ≈250°C. 相似文献
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Specific programming of automated HPLC systems allows total on-line qualification, validation and stability monitoring using the concept of deferred standards. Setting up such a process for routine analyses in an automated HPLC system requires specific autosampler programming as well as specific monitoring software. With an autosampler, a double injection procedure is programmed, the first introducing the sample, and the second, a few minutes deferred, the deferred control standard. Two additional compounds are therefore added to the sample before and during the chromatographic process: the intemal standard for sample quantification and the deferred standard for system control. Specific methodologies are described of how to obtain classical quantitative analysis information as well as system qualification validation stability information. Experiments were performed to develop specified methodologies to monitor the quality of quantitative analysis during the life of the column by using the deferred standard concept to probe the effects of column ageing on separation characteristics. 相似文献
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Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
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Zanoni G Porta A Meriggi A Franzini M Vidari G 《The Journal of organic chemistry》2002,67(17):6064-6069
Regioconvergent synthesis of the key lactone 1 from an equimolar mixture of the two olefins 4 and 5 was achieved by unique Pd(II) chemistry. The synthetic versatility of lactone 1 has been demonstrated in the synthesis of iridoids and of the endo-Corey lactone 2, which is a key intermediate for the F(2)-isoprostane synthesis. Upon exposure of the sodium salts of 4 and 5 to a catalytic amount of Pd(OAc)(2) under oxygen, in the presence of AcOH, an isomeric lactone 12 was obtained in addition to the title compound 1. The Pd(II) lactonization was optimized by fine-tuning all the factors participating in the catalytic cycle: solvent, oxidant, co-oxidant, and Pd(II) source. The Hosokawa's heterobimetallic couple emerged as the catalyst of choice. With a Cu(II)-Pd(II) couple, the redox process was transferred to copper, and the formal oxidation state of palladium remained constant during the reaction. By virtue of this new methodology, lactone 1 was obtained in a rewarding 60% yield, along with isomeric lactone 12 in 30% yield. A detailed mechanistic study was carried out in order to elucidate the formation of lactones 1 and 12. Lactone 1 was formed from either olefin 8 or olefin 10; on the other hand, lactone 12 was formed exclusively from olefin 10. An intramolecular 1,2-acyloxypalladiation was invoked for the transformation of 8 into 1, whereas the pi-allyl complexes 13 and 11 were involved in the transformation of olefin 10 into 12 and 1, respectively. 相似文献
9.
The synthesis of two S-proline derivatives is described together with their use as chiral ligands for lithium in reactions of n-butyllithium with benzaldehyde to give 1-phenyl-1-pentanol with moderate optical purity. The presence of lithium salts in the reaction mixture causes a decrease in asymmetric induction. 相似文献
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