Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylthio]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenylthio]propanamides Y-PhSCH(Me)C(O)N(OMe)Me (Y=OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by B3LYP/cc-pVDZ calculations of 3, indicated the existence of two gauche conformers (g(1) and g(2)), the g(1) conformer being the more stable and the less polar one (in gas phase and in solution). Both conformers are present in solution of the polar solvents (CH(2)Cl(2) and CH(3)CN) for 1-5 and in solution of the less polar solvent (CHCl(3)) for 1-4, while only the g(1) conformer is present in solution of non polar solvents (n-C(6)H(14) and CCl(4)) and in solution of CHCl(3) for 5. NBO analysis shows that both the sigma(C-S) -> pi*(C=O) (hyperconjugative) and the pi(C=O) -> sigma*(C-S) orbital interactions contribute almost to the same extent for the stabilization of g(1) and g(2) conformers. The pi*(C=O) -> sigma*(C-S), n(S) -> pi*(C=O) and the n(S) -> pi*(C=O) orbital interactions stabilize more the g(1) conformer than the g(2) one. Moreover, the suitable geometry of the g(1) conformer leads to its stabilization through the LP(O2) -> sigma*(C8-H11) orbital interaction (hydrogen bond) along with the strong O([CO])(delta-) center dot center dot center dot H([O-Ph])(delta+) electrostatic interaction. On the other hand, the appropriate geometry of the g(2) conformer leads to its stabilization by the LP(O22) -> sigma*(C9-H13) orbital interaction (hydrogen bond) along with the weak O([OMe])(delta-) center dot center dot center dot H([o`-Ph])(delta+) electrostatic static interaction. As for the 4`-nitro derivative 5 the ortho-phenyl hydrogen atom becomes more acidic, leading to a stronger O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) interaction and, thus, into a larger stabilization of the g(1) conformer in the whole series. This trend is responsible for the unique IR carbonyl band in CHCl(3) solution of 5. The larger occupancy of the pi*(C=O) orbital of the g(1) conformer relative to that of the g(2) conformer, along with the O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) electrostatic interaction (hydrogen bond) justifies the lower carbonyl frequency of the g(1) conformer with respect to the g(2) one, in gas phase and in solution. (C) 2008 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Sensing of 2,4-dichlorophenoxyacetic acid by surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) spectra of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was obtained by employing a bi-layer gold substrate, assembled by the reduction of Au(III) over gold-seeded nanoparticles immobilized on functionalized glass substrates. The SERS signal was linear with the logarithm of the solution concentrations between 1.0 x 10(-7) mol L(-1) and 1.0 x 10(-3) mol L(-1), indicating that the bi-layer gold substrate affords a significant dynamic range for SERS, providing an excellent analytical response within this concentration range, and revealing the high sensitivity of the gold surface towards such analyte. In addition, using the same gold substrate, a similar calibration curve was obtained for crystal-violet (CV), and it was possible to identify the concentration limit corresponding to the transition from the average SERS to the nonlinear SERS response. (C) 2010 Elsevier B.V. All rights reserved.

Stereochemical and electronic interaction studies of some N-methoxy-N-methyl-2-[(4 `-substituted)phenylsulfinyl]propanamides

The (1)H NMR spectra of N-methoxy-N-methyl-2-[(4`-substituted)phenylsulfinyl]-propanamides [Y-Ph-S(O)CH(Me)C(O)N(OMe)Me; Y = OMe 1, Me 2, H 3. Cl 4, NO(2) 5] along with the X-ray diffraction analysis of the nitro-derivative (5). have shown the existence of two pairs of diastereomers (racemic mixture) [C(R)S(S)/C(S)S(R) (diast(1)) and C(R)S(R)/C(S)S(S) (diast(2))] in the ratio of ca. 7:3. respectively. The v(CO) IR analysis of the title compounds supported by HF and B3LYP/6-31G** calculations of 3 and of the parent N-methoxy-N-methyl-propanamide (6) by HF, have shown that diast(1) exists in an equilibrium between the two more polar and more stable quasi-cis (q-c(1) and q-c(2)) conformers and the gauche(g) conformer. The population of the g conformer in the equilibrium increases with the increase in the solvent polarity, which is attributed to a larger solvation effect on the carbonyl and sulfinyl groups. Diast(2) of compound 3 occurs in the gas phase as an equilibrium between the most stable quasi-gauche (q-g) conformer and the quasi-cis (q-c) conformer, both presenting very similar dipole moments. The former is stabilized by electrostatic and charge transfer interactions, which results in a less solvated spatial arrangement. Moreover, all conformers of both diastereomers are stabilized by several intramolecular hydrogen bonds. X-ray single crystal analysis performed for diast(1) and for diast(2) of 5 indicates that both stereoisomers assume, in the solid state, the anti-clinal (gauche) conformation. For the crystal packing, diast(1) of 5 is made up of three molecules joined through two centro-symmetric H center dot center dot center dot O hydrogen bonds. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis, spectral studies and X-ray crystal structure of N,N `-(+/-)-trans-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) H-2(t-3-EtOsalchxn)

The synthesis, spectra and X-ray crystal structure of N,N`-(+/-)-trans-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) H-2(t-3-EtOsalchxn), a salen-type ligand, are reported. The Schiff base was characterized by elemental analysis, m.p., IR, electronic spectra, H-1 and C-13 NMR spectra. The spectra are discussed and compared with those of N,N`-(+/-)-trans-1,2-cyclohexylenebis(salicylideneamine), H-2(t-salchxn). The electronic and IR spectra were also resolved by deconvolution. The influence of the ethoxy group on the IR, electronic spectrum, H-1 and C-13 NMR spectra is discussed. Strong intramolecular forces are present as supported by the IR and H-1 NMR spectra and the X-ray crystal structure. An intermolecular hydrogen bond is observed and appears twice in a pair of molecules in the unit cell. (c) 2007 Elsevier B.V. All rights reserved.

Att arbeta med begreppsförståelse i naturvetenskapsundervisning : En studie om hur lärare i årskurs 2-4 arbetar med naturvetenskapliga begrepp

Syftet med undersökningen är att undersöka hur lärare anger att de arbetar med att skapa begreppsbildning inom NO-ämnena för elever i årskurs 2-4, hur man arbetar för att eleverna ska anamma och förstå begrepp som bearbetas i undervisningen. Studien har genomförts med 8 pedagoger, varav 2 arbetar i årskurs 2, 2 som arbetar i årskurs 3, 3 lärare som arbetar i årskurs 4 och en lärare som arbetar i årskurs 1-3. Tanken med studien var att som blivande lärare i NO-ämnena få ta del av lärares goda exempel på hur begreppsförståelse skapas. Resultatet visar att samtliga lärare har många goda exempel på metoder för att arbeta med begreppsbildning men att alla metoder inte används av alla lärare. Samtliga lärare belyser vikten av kommunikation i begreppsbildningen och att det är något som måste ske kontinuerligt i undervisningen.

Níveis de julgamento de alunos de 1., 2. e 3. graus de ensino

Os níveis de julgamen to dos alunos de 1 2 , 22 e ,:3 2 graus de ensino da Rede de E'sco las Particulares e da ~~ndação Universitária da cidade de Lages - Santa Catari ~a -, é um estudo teórico e de investigação prática, que -pretende verificar e discutir as relações entre a quali~ . dade ou maturidade de julgamento .. ' . e as var~ave~s idade grau de escolaridade, capacidade intelectual e nível só- --ci.o-econômico dos alunos ,sujeitos da pesquisa. A amostra foi sorteada aleatoriamente entre to- dos os alunos da 8! série do 12 grau, 2~' série do 29 grau e 3! série do 3 2 grau, num percentual aproximado de 20% da população total visada. Constituiu-se, assim, uma amos tra de 152 sujeitos, extTa{da de uma população de 898 a~ . . lunos. Os objetivos específicos que orientaram o estu- , ." ... . .' ,.., . do resumem-se na anal~se e discussao das relaçoes entreo nível de julgamento e as demais variáveis, isto é, ida~ de, grau de escolaridade, capacidade intelectual e nível sócio-econômico dos ,alunos pesquisados. Os resultados indicam que: 1) a maioria absolu- , ta dos sujeitos tanto de 12 e 22 graus qcinnto os de .j2 grau não alcançou'os níveis de julgamento mais maduros - ou seja - julgamento imaginativo-explicativo e imaginati vo-explicati vo-compreensi vo.· .2) Os sujei tos revelam -a- centuada dificuldade de raciocínio e julgamento' em ,rela ção ao texto-teste de estrutura lógica. 3) As variáveis' ~dade, grau de escolaridade, nível 56cio~ecortômico rela- ',c~onam-se,. em geral, positivamente com o nível de julga- ~mento, embora, no caso desta pesquisa, essa relação seja :fraca, possivelmente em função da pou.ca dispersão ougra!! de homog'eneic.ade' dos escores obtidos pelos sujeitos. Es- -sa homogeneidade de resultados levanta problemas que me- receriam novos estudos para maiores esclarecimentos sobre as condiç;es de desenvolvimento do processo de julga- mento, sejam internas ou externas à escola. são levantadas questões relativas, principalmen- te, à ação da escola, aos livros textos nela utilizados às condições precárias dos professores, à concepção tradi ciônal de educação e sobre o sistema ou contexto social a tual dentro do qual a escola é um sub-sistema. são sugeridas, no final do trabalho, pesquisas e estudos que visem amplioar o c onhecimento a raspei to do d~ senvolvimento do processo de julgar, bem como, pesquisas que procurem relacionar o nível sócio-econômico do profes sor e a quantidade e qualidade de leituras feitas por ele com o desempenho dos alunos.

New Ventures Brasil (Forum 2008) - Abertura (Partes 1,2 e 3)

Abertura: Raymundo Magliano Filho - Instituto BM&FBOVESPA, Andrew Aulisi - World Resources Institute - WRI, Marcelo Torres - Banco Real, Anthony Ingham - Citi Foundation

New Ventures Brasil (Forum 2008) - Sustentabilidade empresarial (Parte 1, 2, 3)

Sustentabilidade empresarial: do capital somente à Bolsa de Valores - Luiz Maia - Instituto BM&FBOVESPA - Mario Monzoni - GVces / FGV-EAESP

New Ventures Brasil (Forum 2008) - Mesa redonda (Parte 1, 2, 3)

Mesa redonda - Cenário de investimento em negócios verdes - André Vitti - Axial Gestão, Fabio Bellotti - São Paulo Anjos, Juliano Graff- Master Minds, Oren Pinsky - Grupo Stratus, Renato Marques - Finep - Mediadora: Elisabeth Lerner - Tripod Investments

Mudanças climáticas: uma realidade (trailer parte 1, 2, 3)

Secas extremas, inundações, furacões, pessoas que perderam suas casas, suas plantações, seus animais, sua fé. Essa é a realidade enfrentada por brasileiros em diversas regiões do País. A causa? As mudanças do clima. Apesar de muita gente ainda achar que aquecimento global é coisa de cinema ou que só acontecerá daqui a muitas gerações, o documentário do Greenpeace "Mudanças do Clima, Mudanças de Vidas" mostra que tudo isso já é, infelizmente, uma realidade. Confira ao lado o filme e clique no menu acima para adquirir a sua cópia

Radar Rio+20: Cecília Ferraz no Debate Rio+20: cidades sustentáveis (parte 1, 2 e 3)

Na época coordenadora do programa Desenvolvimento Local (GVces), Cecília Ferraz participou do debate cidades sustentáveis, promovido em março de 2012 pelo Radar Rio +20, uma iniciativa Centro de Estudos em Sustentabilidade da FGV/EAESP (GVces), Instituto Socioambiental e Vitae Civilis, em parceria de mídia com a Rádio Estadão ESPN

Valoração de serviços ecossistêmicos (parte 1, 2 e 3)

Natalia Lutti Hummel apresenta a iniciativa Tendências em Serviços Ecossistêmicos (TeSE) e os métodos de valoração

3º Debate "Bode na sala" (parte 1, 2 e 3)

Nesta edição, especialistas e público foram convidados a refletir sobre o desafio da economia de baixo carbono no contexto da atual crise econômica na qual vive o Brasil neste ano