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Trans Form (trans + form)
Selected AbstractsPhotoregulation of DNA transcription by using photoresponsive T7 promoters and clarification of its mechanismFEBS JOURNAL, Issue 6 2010Xingguo Liang With the use of photoresponsive T7 promoters tethering two 2,-methylazobenzenes or 2,,6,-dimethylazobenzenes, highly efficient photoregulation of DNA transcription was obtained. After UV-A light irradiation (320,400 nm), the rate of transcription with T7 RNA polymerase and a photoresponsive promoter involving two 2,,6,-dimethylazobenzenes was 10-fold faster than that after visible light irradiation (400,600 nm). By attaching a nonmodified azobenzene and 2,,6,-dimethylazobenzene at the two positions, respectively, and by utilizing the different cis,trans thermal stability between cis -nonmodified azobenzene and cis- 2,,6,-dimethylazobenzene, four species of T7 promoter (cis,cis, trans,cis, cis,trans, and trans,trans) were obtained. The four species showed transcriptional activity in the order of cis,cis > cis,trans > trans,cis > trans,trans. Kinetic analysis revealed that the Km for the cis,cis promoter (both of the introduced azobenzene derivatives were in the cis form) and T7 RNA polymerase was 68 times lower than that for the trans,trans form, indicating that high photoregulatory efficiency was mainly due to a remarkable difference in affinity for RNA polymerase. The present approach is promising for the creation of biological tools for artificially controlling gene expression, and as a photocontrolled system for supplying RNA fuel for RNA-powered molecular nanomachines. [source] Preparation of HPLC chiral packing materials using cellulose tris(4-methylbenzoate) for the separation of chrysanthemate isomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2006Chiyo Yamamoto Abstract We investigated the separation of chrysanthemate isomers (1), particularly the (1R)-trans form, by high-performance liquid chromatography (HPLC) using polysaccharide derivatives, such as the phenylcarbamates and benzoates of cellulose and amylose, as the chiral stationary phases (CSPs). The chiral packing materials (CPMs) having a high chiral recognition for the chrysanthemic acid ethyl ester (1a) were prepared by coating cellulose tris(4-methylbenzoate) (2a) dissolved in solvents containing methyl benzoate or acetophenone as an additive on silica gel. The separation factor for 1a significantly depended on the preparation conditions of CPM 2a, such as the coating amount of 2a and the type and amount of additives. The chiral recognition ability created by imprinting the additives was lost when the CPM was heated at a high temperature, and was recovered by contacting it with the additive in a packed column. The structural change in 2a during these treatments was not clearly detected by spectroscopic methods. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5087,5097, 2006 [source] Density functional and vibrational spectroscopic analysis of ,-caroteneJOURNAL OF RAMAN SPECTROSCOPY, Issue 6 2003S. Schlücker Abstract We report a computational study on the structural, energetic and vibrational spectroscopic characteristics of ,-carotene employing density functional theory (DFT). The optimized geometry and the complete vibrational spectrum calculated at the BPW91/6,31G* level, including infrared (IR) intensities and Raman activities, are presented. The centrosymmetric structure of ,-carotene is verified both theoretically and experimentally, by identifying a stable calculated structure with Ci symmetry and the mutually exclusive occurrence of bands in the experimental Fourier transform IR and Raman spectrum, respectively. The calculated vibrational spectra reflect the major characteristic features observed experimentally. Differences in the calculated IR intensities and Raman activities for a few dominant modes of two ,-carotene configuration isomers, the all- trans and the natural abundant (C6,C7) s- cis form, are explained qualitatively by the corresponding eigenvectors. At the level of theory employed, s- cis -,-carotene was found to be 8.8 kJ mol,1 more stable than the all- trans form. Calculations on ,-carotene model systems were performed to separate electronic from steric contributions. The higher stability of s- cis -,-carotene is explained by an energetically favored ,-ionone ring conformation, compensating for its shorter conjugation length in comparison with the all- trans form. Copyright © 2003 John Wiley & Sons, Ltd. [source] Extraction of pure lycopene from industrial tomato by-products in water using a new high-pressure processJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 14 2008Daniele Naviglio Abstract BACKGROUND: Lycopene, a precursor of ,-carotene with a well-known antioxidant activity, contained in many natural products such as tomato (Lycopersicon esculentum Mill.), watermelon, red pepper and papaya, is usually recovered from natural vegetal sources using organic solvents and a purification step. In this paper an innovative process for the extraction of pure lycopene from tomato waste in water that uses the Naviglio® extractor and water as extracting phase is presented. RESULTS: Lycopene was obtained in the all- trans form at a very high grade of purity, not less than 98% (w/w), with an average recovery of 14% (w/w). The availability of high-purity trans -lycopene allowed measurement of the molar absorption coefficient. An alternative procedure for high-performance liquid chromatographic analysis using a phenyl-hexyl silicone phase as inverse phase and a linear gradient in water and acetonitrile is also described. CONCLUSIONS: The use of water as extracting phase considerably reduces the cost of the entire process when compared with the commonly used solvent-based procedure or with the newer supercritical extraction process of lycopene from tomato waste. Lycopene, not soluble in water, was recovered in a quasi-crystalline solid form and purified by solid-phase extraction using a small amount of organic solvent. Copyright © 2008 Society of Chemical Industry This article was published online on September 15, 2008. Errors in Figures 2 - 4 were subsequently identified. The publishers wish to apologise for these errors. This notice is included in the online and print versions to indicate that both have been corrected [September 19, 2008] [source] Trans Fatty Acids, Insulin Resistance, and Type 2 DiabetesNUTRITION REVIEWS, Issue 8 2006Andrew O. Odegaard BA Type 2 diabetes, a growing global health problem, has a complex etiology involving many interactions between genetic and environmental factors. Essential to the development of the disease is insulin resistance of the peripheral tissues. Insulin resistance may be partly modified by the specific types of dietary fatty acids. Trans fatty acids (TFAs), created through the transformation of polyunsaturated fatty acids from their natural cis form to the trans form, are abundant in the Western diet. TFAs take on similar properties as saturated fats, and appear to be more atherogenic. High intakes of saturated fats may promote insulin resistance. It is therefore reasonable to hypothesize that high intakes of TFAs would have similar, or stronger, effects. In this review, all current evidence on the topic of TFAs, insulin resistance, and type 2 diabetes is summarized and interpreted. Although there is some support from observational and experimental studies for the hypothesis that high intakes of TFAs may increase the risk for type 2 diabetes, inconsistencies across studies and methodological problems make it premature to draw definitive conclusions at this time. More experimental research in humans is needed to further address this question. [source] Structure and Photoreaction of Photoactive Yellow Protein, a Structural Prototype of the PAS Domain Superfamily,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2007Yasushi Imamoto Photoactive yellow protein (PYP) is a water-soluble photosensor protein found in purple photosynthetic bacteria. Unlike bacterial rhodopsins, photosensor proteins composed of seven transmembrane helices and a retinal chromophore in halophilic archaebacteria, PYP is a highly soluble globular protein. The ,/, fold structure of PYP is a structural prototype of the PAS domain superfamily, many members of which function as sensors for various kinds of stimuli. To absorb a photon in the visible region, PYP has a p -coumaric acid chromophore binding to the cysteine residue via a thioester bond. It exists in a deprotonated trans form in the dark. The primary photochemical event is photo-isomerization of the chromophore from trans to cis form. The twisted cis chromophore in early intermediates is relaxed and finally protonated. Consequently, the chromophore becomes electrostatically neutral and rearrangement of the hydrogen-bonding network triggers overall structural change of the protein moiety, in which local conformational change around the chromophore is propagated to the N-terminal region. Thus, it is an ideal model for protein conformational changes that result in functional change, responding to stimuli and expressing physiological activity. In this paper, recent progress in investigation of the photoresponse of PYP is reviewed. [source] Stereoselective modulatory actions of oleamide on GABAA receptors and voltage-gated Na+ channels in vitro: a putative endogenous ligand for depressant drug sites in CNSBRITISH JOURNAL OF PHARMACOLOGY, Issue 2 2000Bernard Verdon cis -9,10-octadecenoamide (,oleamide') accumulates in CSF on sleep deprivation. It induces sleep in animals (the trans form is inactive) but its cellular actions are poorly characterized. We have used electrophysiology in cultures from embryonic rat cortex and biochemical studies in mouse nerve preparations to address these issues. Twenty ,Mcis -oleamide (but not trans) reversibly enhanced GABAA currents and depressed the frequency of spontaneous excitatory and inhibitory synaptic activity in cultured networks. cis -oleamide stereoselectively blocked veratridine-induced (but not K+ -induced) depolarisation of mouse synaptoneurosomes (IC50, 13.9 ,M). The cis isomer stereoselectively blocked veratridine-induced (but not K+ -induced) [3H]-GABA release from mouse synaptosomes (IC50, 4.6 ,M). At 20 ,Mcis -oleamide, but not trans, produced a marked inhibition of Na+ channel-dependent rises in intrasynaptosomal Ca2+. The physiological significance of these observations was examined by isolating Na+ spikes in cultured pyramidal neurones. Sixty-four ,Mcis -oleamide did not significantly alter the amplitude, rate of rise or duration of unitary action potentials (1 Hz). cis -Oleamide stereoselectively suppressed sustained repetitive firing (SRF) in these cells with an EC50 of 4.1 ,M suggesting a frequency- or state-dependent block of voltage-gated Na+ channels. Oleamide is a stereoselective modulator of both postsynaptic GABAA receptors and presynaptic or somatic voltage-gated Na+ channels which are crucial for synaptic inhibition and conduction. The modulatory actions are strikingly similar to those displayed by sedative or anticonvulsant barbiturates and a variety of general anaesthetics. Oleamide may represent an endogenous modulator for drug receptors and an important regulator of arousal. British Journal of Pharmacology (2000) 129, 283,290; doi:10.1038/sj.bjp.0703051 [source] Pentiptycene-Derived Light-Driven Molecular Brakes: Substituent Effects of the Brake ComponentCHEMISTRY - A EUROPEAN JOURNAL, Issue 38 2010Wei-Ting Sun Abstract Five pentiptycene-derived stilbene systems (1,R; R=H, OM, NO, Pr, and Bu) have been prepared and investigated as light-driven molecular brakes that have different-sized brake components (1,H<1,OM<1,NO<1,Pr<1,Bu). At room temperature (298,K), rotation of the pentiptycene rotor is fast (krot=108,109,s,1) with little interaction with the brake component in the trans form ((E)- 1,R), which corresponds to the brake-off state. When the brake is turned on by photoisomerization to the cis form ((Z)- 1,R), the pentiptycene rotation can be arrested on the NMR spectroscopic timescale at temperatures that depend on the brake component. In the cases of (Z)- 1,NO, (Z)- 1,Pr, and (Z)- 1,Bu, the rotation is nearly blocked (krot=2,6,s,1) at 298,K. It is also demonstrated that the rotation is slower in [D6]DMSO than in CD2Cl2. A linear relationship between the free energies of the rotational barrier and the steric parameter A values is present only for (Z)- 1,H, (Z)- 1,OM, and (Z)- 1,NO, and it levels off on going from (Z)- 1,NO to (Z)- 1,Pr and (Z)- 1,Bu. DFT calculations provide insights into the substituent effects in the rotational ground and transition states. The molar reversibility of the E,Z photoswitching is up to 46,%, and both the E and Z isomers are stable under the irradiation conditions. [source] Structural characterization of isomeric 2,3,5-substituted tetrahydropyrrolo[3,4- d]isoxazole-4,6-diones prepared by cycloaddition of N -methyl- C -arylnitrones to N -phenyl- or N -methylmaleimideJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 5 2004Kalevi Pihlaja 1,3-Dipolar cycloaddition reactions of N -methyl- C -arylnitrones with N -phenyl- or N -methylmaleimide were studied. The reaction of p -dimethylamino-, 4-benzyloxy-3-methoxy-, p -nitro- and p -chloro-substituted phenylnitrones with N -phenylmaleimide gave cis and trans cycloadducts but that of the corresponding phenylnitrones with N -methylmaleimides only the cis adducts in the case of p -dimethylamino and 4-benzyloxy-3-methoxy substitution. All cis adducts attain a biased conformation whereas the trans forms are shown (by 1H NMR at 233 K and 13C NMR at 208 K) to be mixtures of two invertomers, namely o -(N-lone pair antiperiplanar to 3H; minor) and i -conformations (3H-C-C-3aH dihedral angle close to 90°; major). PM3 and DFT calculations at the B3LYP/6,31G(d) level of theory prove qualitatively that these two conformers of the trans adduct are of comparable stability and represent energy minima. [source] | |||||||||||||