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Circular Dichroism (circular + dichroism)
Kinds of Circular Dichroism Terms modified by Circular Dichroism Selected AbstractsMagnetic Materials: X-Ray Magnetic Circular Dichroism Picks out Single-Molecule Magnets Suitable for Nanodevices (Adv. Mater.ADVANCED MATERIALS, Issue 2 20092/2009) The surface sensitivity of X-ray magnetic circular dichroism in extreme conditions has been exploited to investigate the first layers of bulk single-molecule magnets (SMMs), as reported by Roberta Sessoli and co-workers on p. 167. Striking differences have emerged between two classes of SMM having different structural constraints, thus highlighting the importance of molecular design in the realization of molecular spintronic devices. [source] X-Ray Magnetic Circular Dichroism Picks out Single-Molecule Magnets Suitable for NanodevicesADVANCED MATERIALS, Issue 2 2009Matteo Mannini The surface sensitivity of X-ray Magnetic Circular Dichroism in extreme conditions is exploited to investigate the first layers of bulk single-molecule magnets (SMM). Striking differences emerge between two classes of SMM with different structural constraints, thus highlighting the importance of molecular design in the realization of molecular spintronic devices [source] Circular Dichroism of the Photoreceptor Pigment OxyblepharisminPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 6 2005Osvaldo Pieroni ABSTRACT Circular dichroism (CD) was used to study the structure of oxyblepharismin (OxyBP), the photoreceptor chromophore for the photophobic response of the blue form of Blepharisma japonicum. Both the chromophore associated to its native protein and the free chromophore in ethanol solution were investigated. CD spectra in the far-UV range indicate that OxyBP induces a slight increase in the ,-helix content of the protein matrix. CD spectra in the near-UV and visible region of the spectrum show that OxyBP adopts a chiral conformation with a preferential geometry not only when associated to its protein matrix, but also when isolated and dissolved in ethanol. This experimental result is related to the existence of a high-energy interconversion barrier between two enantiomeric structures of the molecule and discussed on the basis of an asymmetric biosynthesis of its precursor, blepharismin. [source] Circular Dichroism of Designed Peptide Helices and ,-Hairpins: Analysis of Trp- and Tyr-Rich PeptidesCHEMBIOCHEM, Issue 12 2005Radhakrishnan Mahalakshmi VCD versus ECD spectroscopy. Peptides rich in aromatic residues yield anomalous far-UV electronic circular dichroism (ECD) spectra that preclude secondary structure assignment. The utility of vibrational circular dichroism (VCD) in conformation analysis is demonstrated by using a set of well-defined peptide helices and hairpins containing proximal aromatic residues. [source] Determination of the Absolute Configurations of Natural Products via Density Functional Theory Calculations of Vibrational Circular Dichroism, Electronic Circular Dichroism, and Optical Rotation: The Iridoids Plumericin and Isoplumericin.CHEMINFORM, Issue 37 2007P. J. Stephens Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Magnetic Circular Dichroism and Absorption Spectra of Phosphinidene in Noble-Gas MatricesCHEMINFORM, Issue 17 2005Jeremy J. Harrison Abstract For Abstract see ChemInform Abstract in Full Text. [source] One-Pot Synthesis of Helical Aromatics: Stereoselectivity, Stability Against Racemization, and Assignment of Absolute Configuration Assisted by Experimental and Theoretical Circular Dichroism.CHEMINFORM, Issue 12 2005Masashi Watanabe Abstract For Abstract see ChemInform Abstract in Full Text. [source] Electronic Structure, Spectra, and Magnetic Circular Dichroism of Cyclohexa-, Cyclohepta-, and CyclooctapyrroleCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2005Alexander Gorski Abstract Three recently obtained expanded porphyrins represent nice examples of compounds for which the electronic and spectral properties can be predicted from symmetry considerations alone. Perimeter-model-based theoretical analysis of the electronic structure of doubly protonated cyclo[6], cyclo[7], and cyclo[8]pyrrole leads to the anticipation of qualitatively the same electronic absorption and magnetic circular dichroism patterns for all three compounds. These predictions are fully confirmed by experiments, as well as DFT and INDO/S calculations. Due to a characteristic pattern of frontier molecular orbitals, a degenerate HOMO and a strongly split LUMO pair, the three cyclopyrroles show comparable absorption intensity in the Q and Soret regions. Magnetic circular dichroism spectra reveal both A and B Faraday terms, of which the signs and magnitudes are in remarkably good agreement with theoretical expectations. The values of the magnetic moments of the two lowest degenerate excited states have also been obtained. [source] Conformational Effects on Circular Dichroism in the Photoelectron Angular DistributionCHEMPHYSCHEM, Issue 4 2006Devis Di Tommaso Dr. Abstract The B-spline density-functional method has been applied to the conformers of the (1R,,2R)-1,2-dibromo-1,2-dichloro-1,2-difluoroethane molecule. The cross section, asymmetry, and dichroic parameters relative to core and valence orbitals, which do not change their nature along the conformational curve, have been systematically studied. While the cross section and the asymmetry parameter are weakly affected, the dichroic parameter appears to be rather sensitive to the particular conformer of the molecule, suggesting that this dynamical property could be a useful tool for conformational analysis. The computational method has also been applied to methyl rotation in methyloxirane. Unexpected and dramatic sensitivity of the dichroic-parameter profile to the methyl rotation, both in the core and valence states, has been found. Boltzmann averaging over the conformers reproduces quite closely the profiles previously obtained for the minimum-energy conformation, which is in good agreement with the experimental results. [source] 11th International Conference on Circular DichroismCHIRALITY, Issue 9 2008Professor Ben L. Feringa Guest Editor No abstract is available for this article. [source] Molecular Interaction between a Gadolinium,Polyoxometalate and Human Serum AlbuminEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 34 2009Li Zheng Abstract Polyoxometalates (POMs) show promising antibacterial, antiviral (particularly anti-HIV), antitumor, and anticancer activities, but the mechanism of these potential therapeutic effects remains to be elucidated at the molecular level. The interaction between the Gd-containing tungstosilicate [Gd(,2 -SiW11O39)2]13, and human serum albumin (HSA) was studied by several techniques. Fluorescence spectroscopy showed an energy transfer between the single tryptophan residue of HSA and the POM. Circular dichroism led to the conclusion that the POM significantly altered the secondary structure of HSA. Isothermal titration calorimetry revealed an enthalpy-driven binding reaction between HSA and the POM, resulting in the formation of a 1:1 complex.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Structure,activity relationship of the p55 TNF receptor death domain and its lymphoproliferation mutantsFEBS JOURNAL, Issue 5 2001Gert De Wilde Upon stimulation with tumor necrosis factor (TNF), the TNF receptor (TNFR55) mediates a multitude of effects both in normal and in tumor cells. Clustering of the intracellular domain of the receptor, the so-called death domain (DD), is responsible for both the initiation of cell killing and the activation of gene expression. To characterize this domain further, TNFR55 DD was expressed and purified as a thioredoxin fusion protein in Escherichia coli. Circular dichroism, steady-state and time-resolved fluorescence spectroscopy were used to compare TNFR55 DD with DDs of the Fas antigen (Fas), the Fas-associating protein with DD (FADD) and p75 nerve growth factor receptor, for which the 3-dimensional structure are already known. The structural information derived from the measurements strongly suggests that TNFR55 DD adopts a similar fold in solution. This prompted a homology modeling of the TNFR DD 3-D structure using FADD as a template. In vivo studies revealed a difference between the two lymphoproliferation (lpr) mutations. Biophysical techniques were used to analyze the effect of changing Leu351 to Ala and Leu351 to Asn on the global structure and its impact on the overall stability of TNFR55 DD. The results obtained from these experiments in combination with the modeled structure offer an explanation for the in vivo observed difference. [source] A Tripodal Peptidic Titanium Phosphonate as a Homochiral Porous Solid Medium for the Heterogeneous Enantioselective Hydration of EpoxidesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Anat Milo Abstract A porous, homochiral titanium-phosphonate material based on a tripodal peptide scaffold was used as a heterogeneous reaction medium for the enantioselective hydration (>99%) of styrene oxide. This titanium-phosphonate material, which was shown to contain confined chiral spaces, was prepared by polymerization of L -leucine onto a tris(2-aminoethyl)amine initiator, followed by capping with phosphonate groups and completed by non-aqueous condensation with titanium isopropoxide. Circular dichroism confirmed that the peptide tethers yielded a secondary structure. X-ray powder diffraction and transmission electron microscopy supported by a semi-empirical model showed the likely formation of a porous, lamellar material that was quantified by nitrogen adsorption. [source] Folding in solution of the C-catalytic protein fragment of angiotensin-converting enzymeJOURNAL OF PEPTIDE SCIENCE, Issue 8 2009Sotirios-Spyridon M. Vamvakas Abstract Angiotensin-converting enzyme (ACE) is a key molecule of the renin,angiotensin,aldosterone system which is responsible for the control of blood pressure. For over 30 years it has become the target for fighting off hypertension. Many inhibitors of the enzyme have been synthesized and used widely in medicine despite the lack of ACE structure. The last 5 years the crystal structure of ACE separate domains has been revealed, but in order to understand how the enzyme works it is necessary to study its structure in solution. We present here the cloning, overexpression in Escherichia coli, purification and structural study of the Ala959 to Ser1066 region (ACE_C) that corresponds to the C-catalytic domain of human somatic angiotensin-I-converting enzyme. ACE_C was purified under denatured conditions and the yield was 6 mg/l of culture. Circular dichroism (CD) spectroscopy indicated that 1,1,1-trifluoroethanol (TFE) is necessary for the correct folding of the protein fragment. The described procedure can be used for the production of an isotopically labelled ACE959,1066 protein fragment in order to study its structure in solution by NMR spectroscopy. Copyright © 2009 European Peptide Society and John Wiley & Sons, Ltd. [source] Mass spectrometric identification of the trypsin cleavage pathway in lysyl-proline containing oligotuftsin peptidesJOURNAL OF PEPTIDE SCIENCE, Issue 4 2007Marilena Manea Abstract Trypsin cleaves specifically peptide bonds at the C -terminal side of lysine and arginine residues, except for -Arg-Pro- and -Lys-Pro- bonds which are normally resistant to proteolysis. Here we report evidence for a -Lys-Pro- tryptic cleavage in modified oligotuftsin derivatives, Ac-[TKPKG]4 -NH2) (1), using high-resolution mass spectrometry and HPLC as primary methods for analysis of proteolytic reactions. The proteolytic susceptibility of -Lys-Pro- bonds was strongly dependent on flanking residues, and the flexibility of the peptide backbone might be a prerequisite for this unusual cleavage. While -Lys-Gly- bonds in 1 were rapidly cleaved, the modification of these Lys residues by the attachment of a ß-amyloid(4,10) epitope to yield -Lys(X)-Gly derivatives prevented cleavage of this bond, and provided trypsin cleavage of -Lys-Pro- bonds, the pathway of this degradation being independent on the type of Lys- N, -side chains (acetyl group, amino acid, peptide). Substitution of the Lys residues by Ala at the P,2 positions decreased the tryptic cleavage, while replacement of the bulky side chain of Thr at the P2 positions strongly increased the cleavage of -Lys-Pro- bonds. Circular dichroism (CD) data of the modified oligotuftsin derivatives are in accord with enhanced flexibility of the peptide backbone, as a prerequisite for increased susceptibility to cleavage of -Lys-Pro- bonds. These results obtained of oligotuftsin derivatives might have implications for the proteolytic degradation of target peptides that require specific conformational preconditions. Copyright © 2007 European Peptide Society and John Wiley & Sons, Ltd. [source] A genome-inspired DNA ligand for the affinity capture of insulin and insulin-like growth factor-2JOURNAL OF SEPARATION SCIENCE, JSS, Issue 10 2009Junfeng Xiao Abstract The insulin-linked polymorphic region (ILPR) of the human insulin gene contains tandem repeats of similar G-rich sequences, some of which form intramolecular G-quadruplex structures in vitro. Previous work showed affinity binding of insulin to an intramolecular G-quadruplex formed by ILPR variant a. Here, we report on interactions of insulin and the highly homologous insulin-like growth factor-2 (IGF-2) with ILPR variants a, h, and i. Circular dichroism indicated intramolecular G-quadruplex formation for variants a and h. Affinity MALDI MS and surface plasmon resonance were used to compare protein capture and binding strengths. Insulin and IGF-2 exhibited high binding affinity for variants a and h but not i, indicating the involvement of intramolecular G-quadruplexes. Interaction between insulin and variant a was unique in the appearance of two binding interactions with KD , 10,13 M and KD , 10,7 M, which was not observed for insulin with variant h (KD , 10,8 M) or IGF-2 with either variant (KDs , 10,9 M). The results provide a basis for the design of DNA binding ligands for insulin and IGF-2 and support a new approach to discovery of DNA affinity binding ligands based on genome-inspired sequences rather than the traditional combinatorial selection route to aptamer discovery. [source] Circular Dichroism of the Photoreceptor Pigment OxyblepharisminPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 6 2005Osvaldo Pieroni ABSTRACT Circular dichroism (CD) was used to study the structure of oxyblepharismin (OxyBP), the photoreceptor chromophore for the photophobic response of the blue form of Blepharisma japonicum. Both the chromophore associated to its native protein and the free chromophore in ethanol solution were investigated. CD spectra in the far-UV range indicate that OxyBP induces a slight increase in the ,-helix content of the protein matrix. CD spectra in the near-UV and visible region of the spectrum show that OxyBP adopts a chiral conformation with a preferential geometry not only when associated to its protein matrix, but also when isolated and dissolved in ethanol. This experimental result is related to the existence of a high-energy interconversion barrier between two enantiomeric structures of the molecule and discussed on the basis of an asymmetric biosynthesis of its precursor, blepharismin. [source] Measurement of critical concentration for mesophase formation of chitosan derivatives in both aqueous and organic solutionsPOLYMER INTERNATIONAL, Issue 12 2006Yan-ming Dong Abstract A novel chitosan derivative, acryloyl chitosan (AcCs), and two N -maleoyl chitosans, MaCs-1 and MaCs-2, with different degrees of substitution were synthesized using completely deacetylated chitosan as raw material under different reaction conditions. AcCs is an amphiphilic chitosan derivative, but MaCs-1 and MaCs-2 are soluble in water and organic solvents respectively. The concentrated solutions of AcCs, MaCs-1 and MaCs-2 all demonstrated mesophases and were investigated using polarizing optical microscopy (POM). Circular dichroism (CD) was also employed for determining the critical concentration for mesophase formation. A broad peak in the visible light region of CD spectra had its origin in the appearance of the mesophase, and arose from the selective reflection of cholesteric helix pitches. The results of CD measurements agreed with those of POM. The critical concentration values for aqueous solutions were much lower than those for organic solutions, which was explained by the strong interactions between the chitosan derivatives and water. Copyright © 2006 Society of Chemical Industry [source] Polymerization of the SAM domain of MAPKKK Ste11 from the budding yeast: Implications for efficient signaling through the MAPK cascadesPROTEIN SCIENCE, Issue 3 2005Surajit Bhattacharjya Abstract The sterile ,-motif (SAM) is a protein module ,70 residues long and mainly involved in the protein,protein interactions of cell signaling and transcriptional repression. The SAM domain of the yeast MAPKKK Ste11 has a well-folded dimeric structure in solution. Interestingly, the well-folded dimer of the Ste11 SAM undergoes a time-dependent self-assembly upon lowering of the pH, leading to the formation of high molecular weight oligomers. The oligomeric structures rapidly disassemble to the well-folded dimer upon reversal of the pH to close to neutral conditions. Circular dichroism (CD) and atomic force microscopy (AFM) experiments demonstrate that the oligomeric structure formed at pH 5.0 appears to be highly helical and has architecture akin to proto-fibrils. Residue-specific kinetics of pH-triggered oligomerization obtained from real-time 15N- 1H HSQC experiments indicate that the dimer-oligomer transition appears to involve all residues of the well-folded dimeric structure of the Ste11 SAM. Very interestingly, the interactions of the Ste11 and Ste50 SAM domains also lead to the formation of non-homogeneous hetero-complexes with significant populations of high molecular weight aggregates. AFM imaging shows that the Ste11-Ste50 hetero-polymeric aggregates assume the shapes of circular nano-particles with dimensions of 50,60 nano-meters (nm), in contrast to the proto-fibrils formed by the Ste11 SAM domain alone. Such intrinsic propensity for dimer to oligomer transition of the Ste50-binding SAM domain of Ste11 may endow the MAPKKK Ste11 with unique functional properties required for efficient and high fidelity signal transduction in the budding yeast. [source] Conformations of Betanova in aqueous trifluoroethanol,BIOPOLYMERS, Issue 10 2010Danny P. Chagolla Abstract Conformations of the designed peptide Betanova in 42% trifluoroethanol/water (v/v) were explored. Circular dichroism (CD) observations provided no evidence for the presence of significant amounts of ,-structures in water, in TFE/water, or in ethanol/water. Nuclear magnetic resonance (NMR) diffusion experiments showed no significant difference in the hydrodynamic radius of the peptide in water and in 42% TFE/water. However, calculations indicated that the hydrodynamic radii of the triple-stranded ,-sheet, originally proposed for Betanova by Kortemme et al. (Science 1998, 281, 253-256), and a variety of partially folded forms of Betanova would be similar and likely could not be convincingly distinguished by diffusion experiments. Temperature coefficients (,,/,T) of the peptide NH chemical shifts are similar in water and 42% TFE/water, implying that most of these protons are highly solvent exposed in both solvents and likely do not participate in intramolecular hydrogen bonding interactions. Possible exceptions to this conclusion are the Lys9 and Lys15 residues, where a more positive coefficient may indicate that these residues are involved to some extent in local turn structures. Peptide proton,solvent fluorine intermolecular nuclear Overhauser effect (NOE)s at 25°C were consistent with the presence of a mixture of conformations, which could include the triple-stranded ,-sheet structure as a minor component. At 0°C, peptide-TFE NOEs indicated that TFE interacts strongly enough with many protons of Betanova that alcohol-peptide interactions persist for times of the order of nanoseconds, appreciably longer than the encounter time characteristic of mutual diffusion of TFE and the solute. © 2010 Wiley Periodicals, Inc. Biopolymers 93: 893,903, 2010. [source] Evaluation of binding selectivities and affinities of platinum-based quadruplex interactive complexes by electrospray ionization mass spectrometryBIOPOLYMERS, Issue 4 2009Sarah E. Pierce Abstract The quadruplex binding affinities and selectivities of two large ,-surface PtII phenanthroimidazole complexes, as well as a smaller ,-surface platinum bipyridine complex and a larger RuII complex, were evaluated by electrospray ionization mass spectrometry. Circular dichroism (CD) spectroscopy was used to determine the structures of various quadruplexes and to study the thermal denaturation of the quadruplexes in the absence and presence of the metal complexes. In addition, chemical probe reactions with glyoxal were used to monitor the changes in the quadruplex conformation because of association with the complexes. The platinum phenanthroimidazole complexes show increased affinity for several of the quadruplexes with elongated loops between guanine repeats. Quadruplexes with shorter loops exhibited insubstantial binding to the transition metal complexes. Similarly binding to duplex and single strand oligonucleotides was low overall. Although the ruthenium-based metal complex showed somewhat enhanced quadruplex binding, the PtII complexes had higher quadruplex affinities and selectivities that are attributed to their square planar geometries. The chemical probe reactions using glyoxal indicated increased reactivity when the platinum phenanthroimidazole complexes were bound to the quadruplexes, thus suggesting a conformational change that alters guanine accessibility. © 2008 Wiley Periodicals, Inc. Biopolymers 91: 233,243, 2009. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Protein instability during HIC: Hydrogen exchange labeling analysis and a framework for describing mobile and stationary phase effectsBIOTECHNOLOGY & BIOENGINEERING, Issue 1 2007Yunzhi Xiao Abstract Unfolding of marginally stable proteins is a significant factor in commercial application of hydrophobic interaction chromatography (HIC). In this work, hydrogen-deuterium isotope exchange labeling has been used to monitor protein unfolding on HIC media for different stationary phase hydrophobicities and as a function of ammonium sulfate concentration. Circular dichroism and Raman spectroscopy were also used to characterize the structural perturbations experienced by solution phase protein that had been exposed to media and by protein adsorbed on media. As expected, greater instability is seen on chromatographic media with greater apparent hydrophobicity. However, increased salt concentrations also led to more unfolding, despite the well-known stabilizing effect of ammonium sulfate in solution. A thermodynamic framework is proposed to account for the effects of salt on both adsorption and stability during hydrophobic chromatography. Using appropriate estimates of input quantities, analysis with the framework can explain how salt effects on stability in chromatographic systems may contrast with solution stability. Biotechnol. Bioeng. 2007;96: 80,93. © 2006 Wiley Periodicals, Inc. [source] Chemical Synthesis of Triple-Labelled Three-Helix Bundle Binding Proteins for Specific Fluorescent Detection of Unlabelled ProteinCHEMBIOCHEM, Issue 6 2005Torun Engfeldt Abstract Site-specifically triple-labelled three-helix bundle affinity proteins (affibody molecules) have been produced by total chemical synthesis. The 58 aa affinity proteins were assembled on an automated peptide synthesizer, followed by manual on-resin incorporation of three different reporter groups. An orthogonal protection strategy was developed for the site-specific introduction of 5-(2-aminethylamino)-1-naphthalenesulfonic acid (EDANS) and 6-(7-nitrobenzofurazan-4-ylamino)-hexanoic acid (NBDX), constituting a donor/acceptor pair for fluorescence resonance energy transfer (FRET), and a biotin moiety, used for surface immobilization. Circular dichroism and biosensor studies of the synthetic proteins and their recombinant counterparts revealed that the synthetic proteins were folded and retained their binding specificities. The biotin-conjugated protein could be immobilized onto a streptavidin surface without loss of activity. The synthetic, doubly fluorescent-labelled affinity proteins were shown to function as fluorescent biosensors in an assay for the specific detection of unlabelled human IgG and IgA. [source] High Stability of the Polyproline,II Helix in Polypeptide BottlebrushesCHEMISTRY - A EUROPEAN JOURNAL, Issue 29 2008Afang Zhang Prof. Abstract Polymer bottlebrushes with monodisperse oligoproline side chains were efficiently synthesized, and the conformation of the peptide side chains in different solvents was investigated. Polymers with number-average degrees of polymerization (DPn) of 89 and 366 were obtained by polymerization of the macromonomer in iPrOH/MeCN (1:1) and hexafluoroisopropanol, respectively. Circular dichroism (CD) spectra of the bottlebrush polymers in the neutral and charged states reveal that the oligoproline side chains attain stable polyproline,II (PPII) helical conformations not only in aqueous solution, but also in aliphatic alcohol solutions. Dense attachment of oligopeptides onto a linear polymer chain did not lead to an increase in helix content. The possible effects of the main-chain length on the conformational stability were examined. The switching between the polyproline,I (PPI) and PPII helical conformations for the oligoproline side chains in aliphatic alcohol solutions is believed to be inhibited by the overcrowded structure in the polymer bottlebrushes. [source] Cyclen-Based Side-Chain Homopolymer Self-Assembly with Plasmid DNA: Protection of DNA from Enzymatic DegradationCHEMISTRY & BIODIVERSITY, Issue 5 2009Kun Li Abstract In this study, a 1,4,7,10-tetraazacyclododecane (cyclen)-based side-chain homopolymer was developed for the first time; this polymer can self-assembly with plasmid DNA to form polyelectrolyte complexes (polyplex), which can protect DNA from enzymatic degradation. Moreover, the polyplex can disassembly and release free DNA when NaCl solution is added to this system. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) are used for imaging of the surface structure of the polyplex, and results indicated that the polyplex structures respond to the polymer concentration. Circular dichroism (CD) spectrum suggested that the DNA configuration in the polyplex was retained. [source] Circular dichroism of diglycosyl dichalcogenides in solution and solid state,CHIRALITY, Issue 3-4 2008Tibor Kurtán Abstract Solution and solid-state CD spectra of nine peracetylated and deacetalyted diglycosyl disulfides were measured to study the relationship between the low-energy CD transitions (n1,,*SS and n2,,*SS) and helicity of the inherently chiral disulfide chromophore as perturbed by chiral carbohydrate moieties. The solid-state CD spectra were directly correlated with the reported X-ray structures of Ac4GlcSSGlcAc4 and Ac4GlcSSGalAc4, and the CD data revealed that all the disulfides have M helicity with C1SSC1, dihedral angles ,90° < , < 0° both in solution and in the solid state. A TDDFT CD study was carried out on dimethyl diselenide which confirmed that the same quadrant rule is relevant between the signs of the low-energy CD transitions and the diselenide torsional angle as formulated previously for the disulfide chromophore. The CD spectra of Ac4GlcSeSeGlcAc4 measured in solution and in the solid state were correlated with its X-ray structure and reproduced well by TDDFT CD calculations performed on its tetra- O -acetyl derivative. Chirality, 2008. © 2007 Wiley-Liss, Inc. [source] Measured and calculated CD spectra of G-quartets stacked with the same or opposite polarities,,CHIRALITY, Issue 3-4 2008Donald M. Gray Abstract Circular dichroism (CD) spectroscopy is widely used to characterize the structures of DNA G-quadruplexes. CD bands at 200,300 nm have been empirically related to G-quadruplexes having parallel or antiparallel sugar-phosphate backbones. We propose that a more fundamental interpretation of the origin of the CD bands is in the stacking interactions of neighboring G-quartets, which can have the same or opposing polarities of hydrogen bond acceptors and donors. From an empirical summation of CD spectra of the d(G)5 G-quadruplex and of the thrombin binding aptamer that have neighboring G-quartets with the same and opposite polarities, respectively, the spectra of aptamers selected by the Ff gene 5 protein (g5p) appear to arise from a combination of the two types of polarities of neighboring G-quartets. The aptamer CD spectra resemble the spectrum of d(G3T4G3), in which two adjacent quartets have the same and two have opposite polarities. Quantum-chemical spectral calculations were performed using a matrix method, based on guanine chromophores oriented as in d(G3T4G3). The calculations show that the two types of G-quartet stacks have CD spectra with features resembling experimental spectra of the corresponding types of G-quadruplexes. Chirality, 2008. © 2007 Wiley-Liss, Inc. [source] Circular dichroism as a reliable tool for anomeric assignment of glycosyl-2-phenyl-2H- 1,2,3-triazole C -nucleoside analogs.CHIRALITY, Issue 10 2006A rule for prediction of their anomeric configuration Abstract The circular dichroism (CD) of a series of acyclic C -nucleoside analogs; 4-(pentahydroxypentyl-1-yl)-2-phenyl-2H -1,2,3-triazoles [1,5] and 4-(D - glycero - D - gulo)-2-phenyl-2H -1,2,3-triazole 6, are reported. A correlation between the sign of the Cotton effect at the maximal UV absorption and the absolute configuration of the carbon atom ,- to the triazole base moiety is reported. The CD of anomeric 4-(,,,- D -arabinofuranosyl)- and 4-(,,,- D -arabinopyranosyl)-2-phenyl-2H -1,2,3-triazole C -nucleosides are reported. The assignment of the anomeric configuration of C -glycosyl-2-phenyl-2H -1,2,3-triazoles from their CD spectra was found to be a simple method that relies on comparison of the sign of the Cotton effect at the maximal UV absorption and the absolute configuration of the anomeric carbon atom. A correlation between the anomeric configuration and the sign of the Cotton effect at the maximal UV absorption is deduced and generalized as a rule for prediction of the anomeric configuration of C -glycosyl-2-phenyl-2H -1,2,3-triazoles. Nuclear Overhauser effect and 13C NMR spectra supported the CD assignment rule. Chirality, 2006. © 2006 Wiley-Liss, Inc [source] Circular dichroism of heterochromophoric and partially regenerated purple membrane: Search for exciton couplingCHIRALITY, Issue 2 2006Elena Karnaukhova Abstract In order to determine the origin of the bisignate CD spectra of native purple membrane, heterochromophoric analogues containing bacteriorhodopsin regenerated with native all-trans -retinal and retinal analogues were investigated. The data collected for the purple membrane samples containing two different chromophores suggest the additive character of the CD spectra. This conclusion was supported by a series of spectra using 5,6-dihydroretinal and 3-dehydroretinal and by using 33% regenerated PM in buffer and in presence of osmolytes. Our results support the idea of conformational heterogeneity of the chromophores in the bR in the trimer, suggesting that the three bR subunits in the trimer are not conformationally equal, and therefore, the bisignate CD spectrum of bR in the purple membrane occurs rather due to a superposition of the CD spectra from variously distorted bR subunits in the trimer than interchromophoric exciton-coupling interactions. © 2005 Wiley-Liss, Inc. Chirality 18:72,83, 2006. [source] Circular dichroism and the interactions of water soluble porphyrins with DNA,A minireviewCHIRALITY, Issue 4 2003Robert F. Pasternack Abstract The size, sign, and profile of induced circular dichroism (CD) features in the Soret region are reliable indicators of the binding modes of porphyrins and metalloporphyrins to DNA. Porphyrins shown (using such CD criteria) to be intercalators in monodispersed DNA duplexes prove extremely useful for the detection and characterization of organized, condensed forms of nucleic acids (,-condensates). In addition, certain select porphyrin derivatives can form extended assemblies on nonaggregated DNA templates. A combination of CD and resonance light scattering (RLS) measurements allows for sensitive detection and characterization of these porphyrin arrays. Chirality 15:329,332, 2003. © 2003 Wiley-Liss, Inc. [source] | ||||||||||||||||||||||||||||||||||||||||