Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative disallowed conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)-helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib*-Oxa) of 2, in a conformation (phi, =180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)-helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (c) 2014 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 104: 21-36, 2015.

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative ``disallowed'' conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)- helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib(star)-Oxa) of 2, in a conformation (phi, psi = 180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)- helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (C) 2014 Wiley Periodicals, Inc. Biopolymers

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative ``disallowed'' conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)- helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib(star)-Oxa) of 2, in a conformation (phi, psi = 180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)- helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (C) 2014 Wiley Periodicals, Inc. Biopolymers

Evolutionary and structural analyses of heterodimeric proteins composed of subunits with same fold

Heterodimeric proteins with homologous subunits of same fold are involved in various biological processes. The objective of this study is to understand the evolution of structural and functional features of such heterodimers. Using a non-redundant dataset of 70 such heterodimers of known 3D structure and an independent dataset of 173 heterodimers from yeast, we note that the mean sequence identity between interacting homologous subunits is only 23-24% suggesting that, generally, highly diverged paralogues assemble to form such a heterodimer. We also note that the functional roles of interacting subunits/domains are generally quite different. This suggests that, though the interacting subunits/domains are homologous, the high evolutionary divergence characterize their high functional divergence which contributes to a gross function for the heterodimer considered as a whole. The inverse relationship between sequence identity and RMSD of interacting homologues in heterodimers is not followed. We also addressed the question of formation of homodimers of the subunits of heterodimers by generating models of fictitious homodimers on the basis of the 3D structures of the heterodimers. Interaction energies associated with these homodimers suggests that, in overwhelming majority of the cases, such homodimers are unlikely to be stable. Majority of the homologues of heterodimers of known structures form heterodimers (51.8%) and a small proportion (14.6%) form homodimers. Comparison of 3D structures of heterodimers with homologous homodimers suggests that interfacial nature of residues is not well conserved. In over 90% of the cases we note that the interacting subunits of heterodimers are co-localized in the cell. Proteins 2015; 83:1766-1786. (c) 2015 Wiley Periodicals, Inc.

Physiological role of FolD (methylenetetrahydrofolate dehydrogenase), FchA (methenyltetrahydrofolate cyclohydrolase) and Fhs (formyltetrahydrofolate synthetase) from Clostridium perfringens in a heterologous model of Escherichia coli

Most organisms possess bifunctional FolD 5,10-methylenetetrahydrofolate (5,10-CH2-THF) dehydrogenase-cyclohydrolase] to generate NADPH and 10-formyltetrandrofolate (10-CHO-THF) required in various metabolic steps. In addition, some organisms including Clostridium perfringens possess another protein, Fhs (formyltetrahydrofolate synthetase), to synthesize 10-CHO-THF. Here, we show that unlike the bifunctional FolD of Escherichia coli (Eco FolD), and contrary to its annotated bifunctional nature, C. perfringens FolD (Cpe FoID) is a monofunctional 5,10-CH2-THF dehydrogenase. The dehydrogenase activity of Cpe FoID is about five times more efficient than that of Eco FolD. The 5,10-methenyltetrahydrofolate (5,10-CH+-THF) cyclohydrolase activity in C. perfringens is provided by another protein, FchA (5,10-CH+-THF cyclohydrolase), whose cyclohydrolase activity is similar to 10 times more efficient than that of Eco FolD. Kinetic parameters for Cpe Fhs were also determined for utilization of all of its substrates. Both Cpe FoID and Cpe FchA are required to substitute for the single bifunctional FolD in E. coli. The simultaneous presence of Cpe FoID and Cpe FchA is also necessary to rescue an E coli folD deletion strain (harbouring Cpe Fhs support) for its formate and glycine auxotrophies, and to alleviate its susceptibility to trimethoprim (an antifolate drug) or UV light. The presence of the three clostridial proteins (FolD, FchA and Fhs) is required to maintain folate homeostasis in the cell.

A criação dos novos Estados do Araguaia e Mato Grosso do Norte : PDC nº 850, de 2001

Estuda as características populacionais, territoriais e socioeconômicas dos futuros Estados de Mato Grosso do Norte e do Araguaia, em conformidade com o proposto pelo Projeto de Decreto Legislativo nº 850, de 2001, de autoria do Senador Mozarildo Cavalcanti, que convoca plebiscito sobre a criação do Estado do Araguaia.

Controllable group velocity of the probe light in a Lambda-type system with two fold levels

The group velocities of the probe laser field are studied in a A-type system where one lower state has two fold levels coupled by a control field. It is found that the interaction of double dark states leads to controllable group velocity of the probe field in this system. It can be easily realized, due to the interacting double dark resonances, that one of the group velocities at transparency positions is much slower than the other by tuning the control field to be off resonance. In particular, when the control field is on resonance. we can obtain two equal slow group velocities with a broader EIT width, which provides potential applications in quantum storage and retrieval of light. (c) 2005 Elsevier B.V. All rights reserved.

Evolução geológica do Complexo Quirino, Terreno Paraíba do Sul, Setor Central da Faixa Ribeira, com base em dados isotópicos de Sm-Nd e Sr

A área estudada está inserida na Faixa Ribeira, Segmento Central da Província Mantiqueira (Almeida et al., 1973, 1977, 1981), que representa um cinturão de dobramentos e empurrões gerado no Neo-proterozóico/Cambriano, durante a Orogênese Brasiliana, na borda sul/sudeste do Cráton do São Francisco (Almeida, 1971, 1977; Cordani et al., 1967, 1973; Cordani & Brito Neves, 1982; Teixeira & Figueiredo, 1991). Neste contexto, o Complexo Quirino é o embasamento retrabalhado do Terreno Paraíba do Sul (Heilbron et al., 2004). O Complexo Quirino é formado por extensos corpos de ortognaisses foliados a homogêneos, leuco a mesocráticos, de granulometria média à grossa, composicionalmente variando entre granitóides tonalíticos/granodioríticos a graníticos, e apresentando enclaves de rochas ultramáficas, máficas e cálcio-silicáticas (ricas em tremolita). Os ortognaisses tonalíticos/granodioríticos apresentam porfiroblastos de plagioclásio e a hornblenda como máfico principal, contrastando com os de composição granítica que apresentam porfiroblastos de K-feldspato e biotita predominante. Como acessórios aparecem zircão, titanita, apatita e epidoto. Também estão associados a estes ortognaisses, granitóides neoproterozóicos que formam corpos individualizados ou lentes anatéticas no conjunto paleoproterozóico. Estes são compostos predominantemente por biotita gnaisse e hornblenda-biotita gnaisse. A análise litogeoquímicas dos ortognaisses do Complexo Quirino demonstrou a existência de duas séries magmáticas distintas. A primeira pertencente à série cálcio-alcalina de alto-K apresenta uma composição mais expandida granítica-adamelítica/granodioritica/tonalítica e é correlacionável aos bt-ortognaisses e alguns hb-bt-ortognaisses. Os ortognaisses da série médio-K apresentam composição predominantemente tonalítica, sendo correlacionáveis à maioria dos hornblenda-biotita gnaisses. Enclaves lenticulares de metapiroxeníticos e anfibolíticos ocorrem em muitos afloramentos. Também ocorrem granitóides neoproterozóicos de composição graníticas a quartzo-monzoníticas O estudo isotópico de Sm-Nd e Sr demonstrou que os ortognaisses da série cálcio-alcalina de alto-K e aqueles da série cálcio-alcalina de médio-K possuem idades modelo TDM variando entre paleoproterozóicas a arqueanas, consistentes com dados U-Pb em zircão publicados na literatura. A série cálcio-alcalina de alto-K é mais antiga (2308 9,2 Ma a 2185 8 Ma) do que a série calcio-alcalina de médio-K (2169 3 a 2136 14 Ma) e a existência de zircões herdados com idades mínimas de 2846 Ma e 2981 Ma para série de médio-K e 3388 16 para série de alto-K. Os granitóides brasilianos possuem idades de cristalização neoproterozóica correlacionada a Orogênese Brasiliana (602 a 627 Ma) (Viana, 2008; Valladares et al., 2002)./Com base nos dados de Sr e Sm-Nd foi possível caracterizar 4 grupos distintos. Os grupos 1 e 2 são formados por rochas de idade paleoproterozóica (2,1 a 2,3 Ga) com idades modelo TDM variando de 2,9 e 3,4 Ga, εNd entre -8,1 e -5,8 e 87Sr/86Sr(t) = 0,694707 (Grupo 1) e TDM variando de 2,5 a 2,7 Ga, εNd entre -5,8 e -3,1 e 87Sr/86Sr(t) = 0,680824 (Grupo 2), formados no paleoproterozóico com contribuição de uma crosta arqueana. O grupo 3 é formado por rochas juvenis de idade paleoproterozóica, com idades de cristalização variando entre 2,0 e 2,2 Ga e com idades modelo TDM variando de 2,1 a 2,2 Ga e εNd entre + 1,5 e + 1,2. O grupo 4 é formado durante o neoproterozóico (645 Ma) por rochas possivelmente de idade paleoproterozóico com idades modelo TDM igual a 1,7 Ga e εNd igual a -8,3.

Nd-glass belt lasers with improved beam quality

Nd-doped phosphate glass belt lasers pumped by laser diodes are demonstrated. The Nd-glass belt with a large cross-section and a small Fresnel number is air-cooled to provide around 18-W continuous wave (CW) output power with a beam quality factor of My2

Geomicrobiology of meromictic, metal-mine pit lakes in the Iberian Pyrite Belt and biotechnological applications

220 p.