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164.
We have carried out very accurate density measurements (with a precision of ±5 × 10-5g cm-3) near the smectic A-nematic transition in binary mixtures of 4-n-nonyl-4'-cyanobiphenyl (9CB) and 4-n-decyl-4'-cyanobiphenyl (10CB). The transition crosses over from second to first order as the temperature range of the nematic phase decreases. For mixtures with the shortest nematic range the data deviate noticeably from a single power law behaviour. Such a deviation is an indication of the first order nature of the transition. Very good fits to a single power law have been obtained for pure 9CB and the x = 0·04 mixture where x is the mole fraction of 10CB in 9CB. The critical exponent obtained from the power law fitting has enabled us to locate the tricritical point to be very close to x=0·04, which is in agreement with the results obtained previously by high resolution calorimetric [1] and X-ray scattering studies [2]. 相似文献
165.
B. Raju V. Ramesh A. Sudhakar M. Ramesh V. U. M. Sarma S. Chandrasekhar R. Srinivas 《Rapid communications in mass spectrometry : RCM》2009,23(18):2965-2974
A new class of diastereomeric pairs of non‐natural amino acid peptides derived from butyloxycarbonyl (Boc‐)protected cis‐(2S,3R)‐ and trans‐(2S,3S)‐β‐norbornene amino acids including a monomeric pair have been investigated by electrospray ionization (ESI) tandem mass spectrometry using quadrupole time‐of‐flight (Q‐TOF) and ion‐trap mass spectrometers. The protonated cis‐BocN‐β‐nbaa (2S,3R) (1) (βnbaa = β‐norbornene amino acid) eliminates the Boc group to form [M+H–Boc+H]+, whereas an additional ion [M+H–C4H8]+ is formed from trans‐BocN‐β‐nbaa (2S,3S) (2). Similarly, it is observed that the peptide diastereomers (di‐, tri‐ and tetra‐), with cis‐BocN‐β‐nbaa (2S,3R)‐ at the N‐terminus, initially eliminate the Boc group to form [M+H–Boc+H]+ which undergo further fragmentation to give a set of product ions that are different for the peptides with trans‐BocN‐β‐nbaa (2S,3S)‐ at the N‐terminus. Thus the Boc group fragments differently depending on the configuration of the amino acid present at the N‐terminus. It is also observed that the peptide bond cleavage in these peptides is less favoured and most of the product ions are formed due to retro‐Diels‐Alder fragmentation. Interestingly, sodium‐cationized peptide diastereomers mainly yield a series of retro‐Diels‐Alder fragment ions which are different for each diastereomer as they are formed starting from [M+Na–Boc+H]+ in peptides with cis‐BocN‐β‐nbaa (2S,3R)‐ at the N‐terminus, and [M+Na–C4H8]+ in peptides with trans‐BocN‐β‐nbaa (2S,3S)‐ at the N‐terminus. All these results clearly indicate that these diastereomeric pairs of peptides yield characteristic product ions which help distinguish the isomers. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
166.
A modular ligand design allowed the assembly of four phosphorus-supported pyrene-containing ligands. The number of pyrene arms could be varied from 1 to 6 depending on the phosphorus support. While ligands containing one and three pyrene arms are excellent fluorescence-based sensors of Cu2+, the ligand containing two pyrene arms shows a high specificity for Mg2+. 相似文献
167.
Kinetic isotope effects suggest that the thermal C2-C6 cyclization of enyne-allenes proceeds through a stepwise diradical mechanism. This is even true if steric bulk at the alkyne terminus is large, contrary to theoretical predictions by Engels. 相似文献
168.
For studies of RNA structure, folding, and catalysis, site-specific modifications are typically introduced by solid-phase synthesis of RNA oligonucleotides using nucleoside phosphoramidites. Here, we report the preparation of two complete series of RNA nucleoside phosphoramidites; each has an appropriately protected amine or thiol functional group. The first series includes each of the four common RNA nucleotides, U, C, A, and G, with a 2'-(2-aminoethoxy)-2'-deoxy substitution (i.e., a primary amino group tethered to the 2'-oxygen by a two-carbon linker). The second series encompasses the four common RNA nucleotides, each with the analogous 2'-(2-mercaptoethoxy)-2'-deoxy substitution (i.e., a tethered 2'-thiol). The amines are useful for acylation and reductive amination reactions, and the thiols participate in displacement and oxidative cross-linking reactions, among other likely applications. The new phosphoramidites will be particularly valuable for enabling site-specific introduction of biophysical probes and constraints into RNA. 相似文献
169.
Chandrasekhar V Nagendran S Azhakar R Kumar MR Srinivasan A Ray K Chandrashekar TK Madhavaiah C Verma S Priyakumar UD Sastry GN 《Journal of the American Chemical Society》2005,127(8):2410-2411
Lipophilic hexaporphyrin free-base and copper-metalated assemblies supported on a Sn6O6 core have been synthesized and characterized. The nuclease activity of the copper derivative has been studied. 相似文献
170.
We have identified a possible electronic origin of metal filaments, invoked to explain the switching behavior of organic devices. Interfaces of two representative organics polyparaphenylene (PPP) and poly(2-methoxy-5-2-ethyl-hexyloxy-1,4-phenylenevinylene) with Ag are investigated using ballistic emission microscopy. Nanometer scale spatial nonuniformity of carrier injection is observed in ballistic electron emission microscopy images of both interfaces. The measured Schottky barrier (SB) appears to be consistent with metal states tailing into the gap of the PPP. We find that the SB values exhibit a distribution, even for the diodes with low ideality factors. The implications of this distribution on the measured physical properties of the diode are discussed, in light of work on devices of similar geometry, published in the literature. We also demonstrate that patches of low SB are likely to nucleate current filaments which can cause local ionization and are reported to be responsible for the switching behavior observed in metal-organic, metal-CuS and Ag-AgSe structures. 相似文献