Graphene as a diffusion barrier for isomorphous systems: Cu-Ni system

Electrochemical exfoliation technique using the pyrophosphate anion derived from tetra sodium pyrophosphate was employed to produce graphene. As-synthesized graphene was then drop dried over a cold rolled Cu sheet. Ni coating was then electrodeposited over bare Cu and graphene-Cu substrates. Both substrates were then isothermally annealed at 800 degrees C for 3 h. WDS analysis showed substantial atomic diffusion in annealed Ni-Cu sample. Cu-graphene-Ni sample, on the other hand, showed negligible diffusion illustrating the diffusion barrier property of the graphene coating. (C) 2016 Elsevier B.V. All rights reserved.

Sequence specific recognition and cleavage of DNA by synthetic molecules

DNA recognition is an essential biological process responsible for the regulation of cellular functions including protein synthesis and cell division and is implicated in the mechanism of action of some anticancer drugs. Studies directed towards defining the elements responsible for sequence specific DNA recognition through the study of the interactions of synthetic organic ligands with DNA are described.

DNA recognition by poly-N-methylpyrrolecarboxamides was studied by the synthesis and characterization of a series of molecules where the number of contiguous N-methylpyrrolecarboxamide units was increased from 2 to 9. The effect of this incremental change in structure on DNA recognition has been investigated at base pair resolution using affinity cleaving and MPE•Fe(II) footprinting techniques. These studies led to a quantitative relationship between the number of amides in the molecule and the DNA binding site size. This relationship is called the n + 1 rule and it states that a poly-N methylpyrrolecarboxamide molecule with n amides will bind n + 1 base pairs of DNA. This rule is consistent with a model where the carboxamides of these compounds form three center bridging hydrogen bonds between adjacent base pairs on opposite strands of the helix. The poly-N methylpyrrolecarboxamide recognition element was found to preferentially bind poly dA•poly dT stretches; however, both binding site selection and orientation were found to be affected by flanking sequences. Cleavage of large DNA is also described.

One approach towards the design of molecules that bind large sequences of double helical DNA sequence specifically is to couple DNA binding subunits of similar or diverse base pair specificity. Bis-EDTA-distamycin-fumaramide (BEDF) is an octaamide dimer of two tri-N methylpyrrolecarboxamide subunits linked by fumaramide. DNA recognition by BEDF was compared to P7E, an octaamide molecule containing seven consecutive pyrroles. These two compounds were found to recognize the same sites on pBR322 with approximately the same affinities demonstrating that fumaramide is an effective linking element for Nmethylpyrrolecarboxamide recognition subunits. Further studies involved the synthesis and characterization of a trimer of tetra-N-methylpyrrolecarboxamide subunits linked by β-alanine ((P4)_(3)E). This trimerization produced a molecule which is capable of recognizing 16 base pairs of A•T DNA, more than a turn and a half of the DNA helix.

DNA footprinting is a powerful direct method for determining the binding sites of proteins and small molecules on heterogeneous DNA. It was found that attachment of EDTA•Fe(II) to spermine creates a molecule, SE•Fe(II), which binds and cleaves DNA sequence neutrally. This lack of specificity provides evidence that at the nucleotide level polyamines recognize heterogeneous DNA independent of sequence and allows SE•Fe(II) to be used as a footprinting reagent. SE•Fe(II) was compared with two other small molecule footprinting reagents, EDTA•Fe(II) and MPE•Fe(II).

Theoretical studies of novel organic systems : biradicals, polyradicals, and conducting polymers

Chapter 1

Cyclobutanediyl has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C_(2h) and C_(2v) forms, which interconvert via a C_s transition state. For the singlet, only a C_(2h) form is found. It passes, via a C_s transition state, onto the C_(2v) surface on which bicyclobutane is the only minimum. The ring-flipping (inversion) process in bicyclobutane includes the singlet biradical as an intermediate, and involves a novel, nonleast motion pathway. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.

Chapter 2

The dimethylenepolycyclobutadienes (n) are the non-Kekulé analogues of the classical acenes. Application of a variety of theoretical methods reveals several novel features of such structures. Most interesting is the emergence of a parity rule. When n is even, n is predicted to be a singlet, with n disjoint NBMOs. When n is odd, theory predicts a triplet ground state with (n+1) NBMOs that are not fully disjoint.

Chapter 3

Bi(cyclobutadienyl) (2), the cyclobutadiene analogue of biphenyl, and its homologues tri- (3) and tetra(cyclobutadienyl) (4) have been studied using electronic structure theory. Ab initio calculations on 2 reveal that the central bond is a true double bond, and that the structure is best thought of as two allyl radicals plus an ethylene. The singlet and triplet states are essentially degenerate. Trimer 3 is two allyls plus a dimethylenecyclobutanediyl, while 4 is two coplanar bi(cyclobutadienyl) units connected by a single bond. For both 3 and 4, the quintet, triplet, and singlet states are essentially degenerate, indicating that they are tetraradicals. The infinite polymer, polycyclobutadiene, has been studied by HMO, EHCO, and VEH methods. Several geometries based on the structures of 3 and 4 have been studied, and the band structures are quite intriguing. A novel crossing between the valence and conduction bands produces a small band gap and a high density of states at the Fermi level.

Chapter 4

At the level of Hückel theory, polyfulvene has a HOCO-LUCO degeneracy much like that seen in polyacetylene. Higher levels of theory remove the degeneracy, but the band gap (E_g) is predicted to be significantly smaller than analogous structures such as polythiophene and polypyrrole at the fulvenoid geometry. An alternative geometry, which we have termed quinoid, is also conceivable for polyfulvene, and it is predicted to have a much larger E_g. The effects of benzannelation to produce analogues of polyisothianaphthene have been evaluated. We propose a new model for such structures based on conventional orbital mixing arguments. Several of the proposed structures have quite interesting properties, which suggest that they are excellent candidates for conducting polymers.

Chapter 5

Theoretical studies of polydimethylenecyclobutene and polydiisopropylidene- cyclobutene reveal that, because of steric crowding, they cannot achieve a planar, fully conjugated structure in either their undoped or doped states. Rather, the structure consists of essentially orthogonal hexatriene units. Such a structure is incompatible with conventional conduction mechanisms involving polarons and bipolarons.

The changes in various iron compounds in culture media for algae. [Translation from: Archiv fur Hydrobiologie Supplemente Band 38(1/2) 151-169, 1970.]

The purpose of this work is a contribution to the quantitative record of the use of iron by planktonic algae. Preliminary experiments with Chlorella to determine the rate of iron intake in the presence of inorganic sources of iron did not produce the desired result. The crucial point of this work is the investigation of the influence of various external factors on the stability of FeEDTA (FeEDTA = Ferric(III)-compound of ethylene-diamine tetra-acetic acid), since this compound appears to be particularly well-suited as a source of iron for planktonic algae (e.g. TAMIYA et al. 1953). Cultures of Chlorella fusca in a light thermostat were used in experimental research. Methods and results are discussed.

Estudo físico-químico de copoliéteres por viscosimetria

A viscosimetria é um procedimento experimental simples e pouco oneroso, que pode fornecer informações valiosas sobre o volume hidrodinâmico e a conformação de macromoléculas em solução, num determinado solvente, em uma dada temperatura. Os parâmetros viscosimétricos podem ser matematicamente calculados por extrapolação gráfica, cuja execução experimental é mais demorada. Em contrapartida, é possível que a determinação seja feita por um único ponto. Neste trabalho, os dois métodos de cálculo, empregando uma série de seis equações: Huggins, Kraemer e Schulz-Blaschke, por extrapolação gráfica, e Schulz-Blaschke, Solomon-Ciuta e Deb-Chanterjee por um único ponto, foram utilizados em soluções de poli(glicol propilênico) (PPG) e copolímeros em bloco à base de poli(glicol propilênico) e poli(glicol etilênico) (EG-b-PG), com diferentes teores de poli(glicol etilênico), tendo isopropanol, tetra-hidrofurano (THF) e tolueno como solventes puros, além das misturas em proporções iguais de THF/ isopropanol e THF/ tolueno, a 25C. Os valores de viscosidade intrínseca e de algumas constantes indicaram que os solventes puros e as misturas se apresentaram no limite entre o bom e o mau solvente. Verificou-se também que o método de cálculo por um único ponto foi válido, especialmente quando a equação de Schulz-Blaschke foi empregada, apresentando um baixo percentual de erro sendo possível assim reduzir o tempo de análise para a maioria dos sistemas estudados

Carbon-13 magnetic resonance spectroscopy

High-resolution, natural-abundance ¹³C spectra have been obtained from a wide variety of organic compounds; ¹³C chemical shifts and coupling constants have been correlated with other molecular properties.

Geminal and vicinal, carbon-proton couplings in benzene and the five- and six-membered aromatic heterocycles have been related to the corresponding proton-proton couplings in substituted ethylenes. The carbon-proton coupling constants in benzene are J_CCH = + 1.0, J_CCCH = +7.4 and J_CCCH = -1.1 Hz. Extended Hückel wavefunctions are uniformly poor in explaining the long-range, carbon-proton couplings in aromatic systems.

Couplings between carbon and elements other than hydrogen have been observed in proton decoupled ¹³C spectra. All of the carbons in fluorobenzene and 1-fluoronaphthalene, but only six of the carbons in 2-fluoronaphthalene are coupled to the fluorine. One-bond, carbon-phosphorus coupling in trialkylphosphines is negative, while one-bond, carbon-phosphorus coupling in tetra-alkylphosphonium ions is positive. Atoms which do not use hybrid orbitals to form bonds to carbon (F, P(III), Se, Te) may have negative, one-bond coupling constants because of the failure of the average energy approximation. One-bond couplings between carbon and carbon, silicon, tin, lead and mercury appear to be explainable in terms of an effective nuclear charge and the s-bond order of the metal. Couplings between carbon and nitrogen and phosphorus (IV) have significant negative contributions to the Fermi contact coupling expression, though, within one series, correlations with s-bond order may be valid. Carbon-carbon coupling in cyclopropane derivatives (10-15 Hz) is consistent with a high degree of p character in the interior orbitals. Some two- and three-bond carbon-carbon coupling constants have also been observed.

Substituent effects of hydroxyl groups on the ¹³C chemical shifts of continuous-chain alkanes depend both on steric and electronic factors. The hydroxyl substituent effects in the long-chain, primary alcohols are α = -48.3, β = -10.2, and γ = +6.0 ppm. The upfield γ effect is attributed to steric crowding in the gauche conformations. Additivity of the hydroxyl and carbonyl and alkyl substituent effects in alkyl-substituted cyclohexanols and cyclohexanones has been demonstrated.

MOFs basados en metaloporfirinas: diseño estructural orientado a la biomimetización de sus propiedades naturales

La Ciencia y Tecnología de Materiales tiene el reto permanente de desarrollar y mejorar materiales multifuncionales y respetuosos con el medio ambiente. En este sentido, los materiales de tipo MOF (Metal-Organic Framework) están siendo objeto de un gran interés, ya que las redes sólidas de coordinación (especialmente, las porosas) presentan aplicaciones en campos en los que la sociedad manifiesta una demanda creciente de ciencia y tecnología, como el almacenamiento y transporte de energía, la captura de gases con efecto invernadero, la catálisis heterogénea y la liberación controlada de fármacos, entre otros. En este contexto, el presente trabajo se planteó con el objetivo de desarrollar nuevos materiales de tipo MOF basados en metaloporfirinas, al objeto de mimetizar las funciones que desempeñan las mismas en los sistemas biológicos, con el fin de reproducirlas en el estado sólido. Para ello, se han escogido biometales como el hierro y el cobalto: característicos de estos sistemas, de bajo coste y medioambientalmente respetuosos. Por otra parte, las porfirinas seleccionadas han sido las siguientes: TPP (meso-tetra-4-fenilporfirina), TCPP (meso-tetra-4-carboxifenilporfirina) y TPPS (meso-tetra-4-sulfonatofenilporfirina). Estas tres moléculas conforman un conjunto de ligandos que difieren ligeramente en sus grupos funcionales. Asimismo, en ocasiones, se ha utilizado un ligando secundario dipiridínico (4,4´-bipiridina) que ha actuado como espaciador. El diseño de las síntesis se ha centrado tanto en las combinaciones adecuadas de metales y ligandos como en la selección de las técnicas de síntesis. Así, se han obtenido cinco nuevos compuestos, que se han sintetizado en condiciones solvotermales suaves o mediante radiación microondas. La caracterización preliminar de los mismos se ha llevado a cabo mediante análisis cuantitativo, espectroscopia infrarroja y Raman, difracción y fluorescencia de rayos X y medidas de densidad. El estudio estructural se ha realizado mediante difractometría de rayos X y el estudio térmico se ha llevado a cabo mediante termogravimetría y termodifractometría. En los casos en que ha resultado procedente, también se han caracterizado los compuestos mediante espectroscopia ultravioleta-visible (UV-Vis), Mössbauer y resonancia paramagnética electrónica (EPR) y mediante medidas de la susceptibilidad magnética. Asimismo, ocasionalmente, se han realizado cálculos mecano-cuánticos basados en la teoría del funcional de la densidad (DFT) y medidas catalíticas. El primero de los cinco compuestos obtenidos, de fórmula [FeTCPP], es quiral y destaca por ser la tercera estructura 2D publicada basada en esta porfirina. La formación de este compuesto está condicionada por la oxidación de los iones de hierro y por la existencia de grupos carboxílicos en la porfirina. Por otra parte, con la participación del espaciador 4,4´-bipiridina (bipy) se han obtenido tres redes 1D. Así, la estructura cristalina del compuesto ([FeTPPbipy]•)n se explica mediante la formación de radicales neutros que se estabilizan en un empaquetamiento que permite la formación de enlaces entre los grupos fenílicos de distintas cadenas. La formación de estos enlaces queda corroborada por la existencia de significativas interacciones antiferromagnéticas. Por otra parte, en el compuesto [CoTPP(bipy)]•([CoTPP])0.22•(TPP)0.78, la disposición de las cadenas deja grandes huecos en la red que se ocupan con porfirinas tanto coordinadas como sin coordinar. El tercero de estos compuestos 1D presenta la fórmula [CoTPPS0.5(bipy)(H2O)2]•6H2O y destaca porque la extensión de las cadenas se produce por la alternancia de dos tipos de octaedros de CoII. La naturaleza de los grupos sulfonato de la porfirina TPPS es determinante para comprender la intrincada red de enlaces de hidrógeno de este compuesto, que propician la formación de una red interpenetrada caracterizada por su gran estabilidad térmica (hasta los 370ºC). Finalmente, con la porfirina TCPP se ha obtenido un segundo compuesto de fórmula -O-[FeTCPP]2•nDMF (n≈ 16; DMF = dimetilformamida). El mismo presenta grandes cavidades (47% de porosidad) que diluyen la matriz magnética, caracterizada por fuertes interacciones antiferromagnéticas intradiméricas. Todo ello revela una inusual estructura superhiperfina, observada por espectroscopia EPR. El trabajo que se recoge en esta memoria constituye, por lo tanto, un “viaje” de mayor a menor dimensionalidad en las estructuras cristalinas. La guía de este viaje ha sido la búsqueda de propiedades catalíticas en sistemas heterogéneos. Así, el [CoTPP(bipy)]•([CoTPP])0.22•(TPP)0.78 obedece el enfoque de inmovilizar o anclar el catalizador en los huecos de la red. Sin embargo, la estrategia alternativa seguida para el compuesto m-O-[FeTCPP]2•nDMF (es decir, que el propio MOF actúe de catalizador) es la que ha aportado mejores y más prometedores resultados en lo que a catálisis heterogénea se refiere.

Auto-ensamblaje de unidades porfirínicas para la obtención de dispositivos supramoleculares

40 p. : il.

Auto-ensamblaje de unidades porfirínicas para la obtención de dispositivos supramoleculares

Comunicación presentada en: II Reunión de Jóvenes Cristalógrafos, 29 Sept-1 Oct de 2010, Bilbao, España

Temperature characteristics of optical parameters of phthalocyanine LB films and spin-coated films

The LB films and spin-coated films of tetra-neopentoxy phthalocyanine zinc (TNPPcZn) were prepared and annealed at different temperatures. Their refractive index (n) and extinction coefficient (k) were measured by p-polarized reflectance. The similar value of n and k, as well as similar changing tendency of it and k at varied annealing temperatures, was found between LB films and spin-coated films. In addition, the absorption curves of TNPPcZn LB films and spin-coated films in visible range at different annealing temperature were investigated. The results indicate that the changing tendency of the extinction coefficient of two kinds of TNPPcZn films obtained from two methods mentioned above were coincident. When the annealing temperature increased to 150 degrees C, the monomers of TNPPcZn films transformed to aggregates, n(f) and k(f) of the films increased. Further, n(f) and k(f) decreased as aggregates changed back to monomers again at the annealing temperature of 300 degrees C. The experimental results coincide well with the theoretical analysis. (C) 2004 Elsevier B.V. All rights reserved.

V^3＋：YAG晶体的生长、色心与光谱性能研究

采用石墨电阻加热的温梯法生长了V：YAG晶体，晶体的不同部位呈现两种不同的颜色：浅绿色和黄褐色．通过对比分析不同颜色V：YAG晶体的室温吸收光谱，推断出石墨发热体高温下扩散出来的C可以起到还原作用，提高晶体中V^3＋tetra离子的浓度，同时诱导了F心的形成．在1300℃下，对不同颜色的V：YAG晶体进行真空退火处理，发现处于八面体格位中的V^3＋离子在热激发作用下与近邻的四面体格位Al^3＋离子存在置换反应，由此产生一定浓度的四面体格位V^3＋离子．同时，F心在退火过程中被完全消除，释放出来的自由电子被

Characteristics and optical spectra of V : YAG crystal grown in reducing atmosphere

A V:YAG single crystal was grown by the temperature gradient technique (TGT) with graphite-heating elements. The as-grown crystal has different colorations of light green and yellow brown in different parts. Distribution of vanadium in three samples with different colorations was determined by inductively coupled plasma-mass spectrometry. From the absorption spectrum of the yellow-brown part with peaks at 370, 820 and 1320nm, we can deduce that the reducing atmosphere of carbon diffused from the heating elements can increase the concentration of tetrahedral V3+ ions and induce F color centers. All three samples exhibited light-green color after annealing in vacuum or H-2 atmospheres. In the vacuum annealing process, the V3+ ions in tetrahedral positions were enhanced through two methods: one method is the exchanging of octahedral V3+ and tetrahedral Al3+ ions in neighboring sites under thermal excitation, the other is that F color centers were thoroughly eliminated and the escaped free electrons could be captured by V ions with higher valance states to further improve the concentration of tetrahedral V3+ ions. Besides the two mechanisms, the H-2 annealing process greatly improved the V-tetra(3+) ions through the reduction effect of H-2. (c) 2006 Elsevier B.V. All rights reserved.

MOFS metaloporfirínicos 1D y 2D: Estudio cristaloquímico

Comunicación a congreso (póster): XXIV Simposio del Grupo Especializado de Cristalografía y Crecimiento Cristalino, GE3C. 23-26 de junio de 2014, Bilbao

Comparação interlaboratorial entre metodologias e estabilidade da amostra na dosagem do perfil lipídico e PCR-US

Segundo O`Kane et al, em 2008, foi demonstrado que 88,9% dos erros laboratoriais são realizados na fase pré-analítica. No laboratório de análises clínicas, o sistema de controle da qualidade pode ser definido como toda a ação sistemática necessária para dar confiança e segurança em todos os exames e prevenir a ocorrência de erros. O tempo de armazenamento pode variar de dias a meses ou mesmo anos, influenciando na definição da temperatura de estocagem. O armazenamento de longo prazo pode resultar na criopreservação inadequada para determinados analitos e pode desnaturar as lipoproteínas. Objetivos: Este trabalho teve como objetivo avaliar a fase pré-analítica, controle da qualidade interno e também avaliar o efeito do congelamento (- 80C) quanto ao tempo de armazenamento do soro e plasma de sangue colhido com ácido etilenodiamino tetra-acético (EDTA). As dosagens foram realizadas no Laboratório de Lípides LabLip, e estocadas em - 80 C por três anos, as mesmas foram redosadas no Serviço de Patologia Clínica da Policlínica Piquet Carneiro da UERJ com metodologias iguais e realizada a comparabilidade dos resultados. Foram analisados o perfil lipídico (CT, HDLc e TG) e PCR-US de 103 amostras, 73 no soro e 30 no plasma em dois laboratórios altamente qualificados. Discussão: Após redosagem foram encontrados nas dosagens de HDLc e CT resultados diminuídos respectivamente (correlação coeficiente no soro 0,48 e 0,62) teste t pareado no soro (CT p 0,0012 e HDLc p 0,0001). Conclusões: Os dados obtidos nas avaliações dos resultados de diferentes laboratórios e tempo de estocagem revelaram que as amostras quando armazenadas por um longo período após redosagem no soro, apresentaram diferenças em certos analitos, tais como CT e HDLc, no qual obteve-se resultados significativamente diminuídos, diferentemente no plasma, que após três anos de estocagem a -80C foram redosados e aplicados no teste t pareado, os analitos CT e PCR-US mantiveram a estabilidade.

Role of transglutaminase-mediated cross-linking of protein in the temperature-dependent setting of Alaska pollack surimi

During the low temperature setting of fish paste, myosin heavy chain (MHC) is polymerized to cross-linked myosin heavy chain (CMHC), which is considered to occur by the action of endogenous transglutaminase (TGase). In this study the contribution of TGase on the setting of Alaska pollack surimi at different temperatures was studied. Alaska pollack surimi was ground with 3% NaCl, 30% h2o and with or without ethylene glycol bis (β-aminoethylether) N, N, N¹,N¹- tetra acetic acid (EGTA), an inhibitor of TGase. Among the pastes without EGTA, highest TGase activity was observed at 25°C but breaking force of the gel set at 25°C was lower than that set at 30°, 35°, and 40°C. Addition of EGTA (5m mol/kg) to the paste suppressed TGase activity at all setting temperatures from 20° to 40°C. Gelation of the pastes and cross-linking of MHC on addition of EGTA were suppressed completely at 20° and 25°C, partially at 30° and 35°C, and not at all at 40°C. The findings suggested that during the setting of Alaska pollack surimi TGase mediated cross-linking of MHC was strong at around 25°C but the thermal aggregation of MHC by non-covalent bonds was strong at above 35°C. Setting of surimi at 40°C and cross-linking of its MHC did not involve TGase.