Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Modulation of trans-to-cis photoisomerization and photoluminescence of 1,2-bis(4-pyridyl)ethylene or 4-styrylpyridine coordinated to fac-tricarbonyl(5-chloro-1,10-phenathroline)rhenium(I)

Photochemical and photophysical properties of fac-[Re(CO)(3)(Clphen)(trans-L)](+) complexes, Clphen = 5-chloro-1,10-phenathroline and L = 1,2-bis(4-pyridyl)ethylene, bpe, or 4-styrylpyridine, stpy, were investigated to complement the understanding of intramolecular energy transfer process in tricarbonyl rhenium(I) complexes having an electron withdrawing group attached to polypyridyl ligands. These new compounds were synthesized, characterized and the photoisomerization quantum yields were accurately determined by (1)H NMR spectroscopy. The true quantum yields for fac-[Re(CO)(3)(Clphen) (trans-bpe)](+) were constant (Phi = 0.55) at all investigated irradiation wavelengths. However, for fac-[Re(CO)(3)(Clphen)(trans-stpy)](+), similar true quantum yields were observed only at higher energy irradiation (Phi(313 nm) = 0.53 and Phi(365 nm) = 0.57), but it decreased significantly at 404 nm (Phi = 0.41). These results indicated different deactivation pathways for the trans-stpy complex photoisomerization. Quantum yields decreased as the (3)IL(trans-L) and (3)MLCT(Re -> NN) excited states become closer and the behavior was discussed in terms of the excited state energy gaps. Additionally, luminescence properties of photoproducts, fac-[Re(CO)(3)(Clphen)(cis-L)](+), were also investigated in different environments to analyze the relative energy of the (3)MLCT(Re -> Clphen) excited state for each compound. (C) 2011 Elsevier B.V. All rights reserved.

Photoswitches and Luminescent Rigidity Sensors Based on fac-[Re(CO)(3)(Me(4)phen)(L)](+)

The fac-[Re(CO)(3)(Me(4)phen)(trans-L)](+) complexes, Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline and L = 4-styrylpyridine, stpy, or 1,2-bis(4-pyridyl)ethylene, bpe, were synthesized and characterized by their spectroscopic, photochemical, and photophysical properties. The complexes exhibit trans-to-cis isomerization upon 313, 334, 365, and 404 nm irradiation, and the true quantum yields can be efficiently determined by absorption changes combined with (1)H NMR data. For fac-[Re(CO)(3)(Me(4)phen)(trans-bpe)](+) similar quantum yields were determined at all wavelengths investigated. However, a lower value (phi(true) = 0.35) was determined for fac-[Re(CO)(3)(Me(4)phen)(trans-stpy)](+) at 404 nm irradiation, which indicates different pathways for the photoisomerization process. The photoproducts, fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+), exhibit luminescence at room temperature with two maxima ascribed to the (3)IL(Me4phen) and (3)MLCT(Re -> Me4phen) excited states. The luminescence properties were investigated in different media, and the behavior in glassy EPA at 77 K showed that the contribution of each emissive state is dependent on the excitation wavelength. The photochemical and photophysical behavior of the complexes were rationalized in terms of the energy gap of excited states and can be exploited in photoswitchable luminescent rigidity sensors.

2-Aminopurine non-radiative decay and emission in aqueous solution: A theoretical study

The minimum energy path along the lowest-lying pi pi* excited state of 2-aminopurine was calculated to elucidate the mechanisms of radiationless decay and emission in water. The sequential Monte Carlo quantum mechanics approach with a multiconfigurational and perturbative description of the wave function was employed to compute the minimum, transition state, and conical intersection. It was found that the barrier in the potential energy surface to access the conical intersection funnel increases in aqueous environment, making the system prone to enlarge the emission yield. These results rationalize the observed enhancement of emission in 2-aminopurine upon increasing of the solvent polarity. (c) 2008 Elsevier B.V. All rights reserved.

A theoretical study of the binding and electronic spectrum of the Mo-2 molecule

Multiconfigurational SCF and second-order perturbation theory have been employed to study seven low-lying singlet and triplet electronic states of the Mo-2 molecule. The bond order of the ground state has been analyzed based on the effective bond order (EBO), indicating that a fully developed sextuple bond is formed between the two Mo atoms. The experimentally observed excited states a(3)Sigma(+)(u) and A(1)Sigma(+)(u) have been determined and the so-called (3)Lambda excited state identified as the b(3)Sigma(+)(u) state, in agreement with experimental expectations. (C) 2007 Elsevier B.V. All rights reserved.

A CASSCF/MRCI Study of the Low-Lying Electronic States of the BeS Molecule

Accurate potential energy curves, dipole moment functions, dissociation energies, and molecular constants for several low-lying singlet and triplet electronic states of BeS were investigated using the CASSCF/MRCI methodology, and the cc-pV5Z basis set for beryllium, and the aug-cc-pV(5+d) Z set for sulfur. Besides presenting improved results for the three lowest lying states, this study presents the first theoretical characterization of another set of nine excited states so far unknown experimentally. Our results are sufficiently accurate to reliably guide the experimental search and characterization of these states, and also to confirm the experimental assignment of the B(1)Sigma(+) excited state. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1694-1700, 2011

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Fjärrvärmedrivna vitvaror : Erfarenheter från utveckling, installationer och kostnadsberäkningar

Värmedrivna vitvaror eller HWC-maskiner som de kallas av tillverkaren värms med varmt vatten från en cirkulerande krets via en värmeväxlare inbyggd i maskinen, till skillnad från konventionella maskiner som värms med el. Denna teknik skall inte förväxlas med maskiner som är anslutna till varmvattenledningen och fylls på med varmt vatten och som därmed begränsas till disk- och tvätt. Syftet med fjärrvärmedrivna vitvaror är alltså att använda fjärrvärme, som har lägre kvalitet och pris än elenergi för uppvärmning och torkning och på så sätt spara el och utöka fjärrvärmeunderlaget. En jämförelse av koldioxidutsläpp och primärenergianvändning mellan konventionella vitvaror och fjärrvärmedrivna vitvaror visar att både koldioxidutsläpp och primärenergianvändning blir lägre för fjärrvärmedrivna vitvaror om biobränsle anses koldioxidneutralt och den el som ersätts är producerad i kolkraftverk eller gaskombikraftverk.   Denna rapport beskriver utveckling och kommersialisering av värmedrivna vitvaror (disk- och tvättmaskiner samt torktumlare och torkskåp) och hur de kan anslutas mot fjärrvärmesystem i olika systemlösningar. Dessutom har de energimässiga och ekonomiska förutsättningarna för tekniken undersökts. Erfarenheterna från fältprovning är dock mycket begränsade, eftersom de byggen där fälttesterna skulle ske försenades. Under 2013 färdigställs ett flerbostadshus med värmedrivna vitvaror i 160 lägenheter i Västerås.   De utvecklade maskinernas värmeanvändning som andel av total energianvändning vid 60 graders framledningstemperatur har uppmätts till ca 50 % för diskmaskinen, 67 % för tvättmaskinen, 80 % för torktumlaren och 93 % för torkskåpet. I det studerade flerbostadshuset av passivhusstandard uppgår lasten från värmedrivna vitvaror komfortgolvvärme och handdukstorkar till upp mot 30 % av husets totala värmeanvändning. För småhus är motsvarande siffra upp mot 20 %. Att använda fjärrvärme istället för elvärme till dessa installationer som normalt är elvärmda kan allts minska elbehovet betydligt i lågenergibebyggelse vilket också minskar både koldioxidutsläppen och primärenergianvändningen.   Ekonomiska analyser har genomförts för två olika systemkoncept (separat vitvarukrets och Västeråsmodellen) för nybyggda småhusområden och flerfamiljshus där fjärrvärme inte bara används till vitvaror utan också till handdukstorkar och komfortgolvvärme. De ekonomiska analyserna visar att Västeråsmodellen är den mest ekonomiskt intressanta systemlösningen med värmedrivna vitvaror, handdukstork och komfortgolvvärme. I flerfamiljshus kan den vara konkurrenskraftig mot de elvärmda alternativen (konventionellt system med eldrivna vitvaror, komfortgolvvärme och handdukstorkar) om prisskillnaden mellan el och fjärrvärme är större än 0,7 kr/kWh. En parameterstudie visar att kapitalkostnaden blir ganska hög jämfört med energikostnaden, vilket betyder att lång livslängd och många cykler är viktigt för att förbättra de ekonomiska förutsättningarna för värmedrivna vitvaror. För passiva småhus blir kostnaden för Västeråsmodellen med värmedrivna vitvaror, handdukstork och komfortgolvvärme likvärdig med de elvärmda alternativen vid energiprisskillnader på 0,7 kr/kWh inklusive moms, medan det krävs prisskillnader på 0,9 kr/kWh inklusive moms för normalisolerade småhusområden.   Sammanfattningsvis kan sägas att i kommuner med ett konkurrenskraftigt fjärrvärmepris finns det viss lönsamhet för hela konceptet enligt Västeråsmodellen med värmedrivna vitvaror, komfortgolvvärme, och handdukstorkar. Om man däremot ser på konkurrensen för enskilda vitvaror är det främst torktumlaren som är konkurrenskraftig i bostäder. Målpriset på 1000 kr extra för värmedrift har inte kunnat uppnås inom projektet för diskmaskiner och tvättmaskiner. Det krävs lägre priser och låga anslutningskostnader för att räkna hem diskmaskinen och tvättmaskinen som enskilda komponenter.   Värmedrivna tvättmaskiner och torktumlare är konkurrenskraftiga i flerfamiljstvättstugor. Speciellt i de fall där beläggningen är god och flera maskiner delar på anslutningskostnaden till fjärrvärmecentralen kan värmedrift bli riktigt lönsam. Torkskåpens konkurrenskraft har inte kunnat utvärderas, då priset ännu inte fastställts. Att använda VVC-systemet för värmedistribution till värmedrivna vitvaror kan vara mycket intressant, men det kräver att legionellaproblematiken kan lösas. I nuläget finns ingen lösning som uppfyller formuleringarna i boverkets byggregler. Ett annat distributionssätt som kan vara intressant, men som inte undersökts i studien är att använda VVC för varmvattendistribution och en gemensam radiator- och vitvarukrets med konstant framledningstemperatur. Den aktör som förväntas ha störst ekonomiskt intresse av att tekniken implementeras är sannolikt fjärrvärmebolagen som får sälja mer värme och det ligger därmed främst på deras ansvar att marknadsföra tekniken i mötet med sina kunder.

Os extremos do ciclo de vida: trabalho infantil e aposentadoria precoce

Este trabalho procura analisar dois problemas bastante graves que afligem a sociedade brasileira. De um lado, a entrada precoce na força de trabalho, que tem sua face mais perversa no trabalho infantil; de outro, a saída também precoce da força de trabalho de adultos em idade ainda produtiva. Ambos fenômenos são empobrecedores para a sociedade e atuam como mecanismo de geração e perpetuação de pobreza. O trabalho infantil, discutido na primeira parte do trabalho, prejudica a educação. A saída precoce da força de trabalho, analisado na segunda parte do trabalho, é um desperdício de recursos. Na terceira parte é desenvolvida uma análise formal que procura mostrar o quanto um sistema de aposentadorias como o sistema previdenciário brasileiro, que garante uma renda por vida às pessoas após um certo anos de trabalho, pode induzir escolhas que embora ótimas do ponto de vista privado são bastante custosas do ponto vista social. Especificamente, procura-se mostrar como esta legislação pode incentivar tanto a entrada quanto a saída precoce do mercado de trabalho.

Escolaridade e o diferencial de rendimentos entre o setor privado e o setor público no Brasil

We study the determinants of the public-private earning gap for different levels of schooling of Brazilian workers. First, using the current earnings as the variable of interest, it is estimated an earnings gap favorable to the less educated workers from the public sector. On the other hand, for workers with higher qualification the earnings gap disappears or becomes favorable to the private sector. Further, we considerate the different regimes of retirement in Brazil by creating the variable Present Value of Work Contract (PVWC). This variable is a measure of the life time earnings for each individual of our database. Different from the results of the current earnings, we found that the PVWC gap is favorable to the public sector even for the most schooling group of workers.

The macroeconomic effects of infrequent information with adjustment costs

We extend the macroeconomic literature on Sstype rules by introducing infrequent information in a kinked ad justment cost model. We first show that optimal individual decision rules are both state-and -time dependent. We then develop an aggregation framework to study the macroeconomic implications of such optimal individual decision rules. In our model, a vast number of agents act together, and more so when uncertainty is large.The average effect of an aggregate shock is inversely related to its size and to aggregate uncertainty. These results are in contrast with those obtained with full information ad justment cost models.

Influência da adição de cálcio nas propriedades de pastas geopoliméricas destinadas a cimentação de poços de petróleo

Nowadays, the search for new technologies that are able to follow the upcoming challenges in oil industry is a constant. Always trying properties improvements of the used materials, looking for the best performance and greater life time. Besides the search for technologies that show an improvement of performance, the search for materials environmentally correct along the whole production process. In Oil well cementing, this search for new technologies passes through the development of slurry systems that support these requests and that are also environmentally friendly. In this context, the use of geopolymer slurries is a great alternative route to cementing oil wells. Besides having good properties, comparable to Portland cement slurries, this alternative material releases much less CO2 gas in the production of their root materials when compared the production of Portland cement, which releases tons of CO2. In order to improve the properties of geopolymer slurries has been added Calcium Oxide, as observed in other studies that slurries where the Calcium is present the values of compressive strength is greater. The addition has been realized based in the CaO/SiO2 molar ratio of 0.05, 0.10 and 0.15. Have been performed compressive strength tests, thickening time, rheology and fliud loss control test of the slurries, following NBR 9831, as well as the physical chemical characterization of XRD, SEM and TG. Has been observed in most of the tests the slurries follow a tendency until the ratio of 0.10, which inverses in the ratio 0.15. This behavior can be explained by two phenomena that occur simultaneously, the first one is the break of the polymer chains and a consequent increase in molucules mobility, which prevails until the ratio of 0.1, and the second is possible approach of the chains due to the capacity of the calcium ions stabilize the charges of two different aluminum. There is only one linearity in the mechanical behavior that can be attributed to the appereance of the C-S-H phase. Based on this, it is concluded that the phenomenon of breaking the polymer chains predominates until the ratio of 0.1, causing an increase of the filtrate volume, lower rheological parameters and increasing thickening time. From the ratio of 0.15 the approach of the chains predominates, and the behavior is reversed

O direito à saúde: a medida do dever do estado de fornecer Medicamentos de dispensação excepcional à sociedade sob a ótica do desenvolvimento

It is a fact that the fundamental rights of citizens are being recognized and guaranteed by the state over time, regardless of the belief that if these rights has always been part of the heritage of subjective individuals, or whether they will be aggregated during the course of human history. In that, emerged the rights of freedom of men and, subsequently, the rights to create a situation of equality between the humans, the so-called social rights. In turn, as these rights known as social, to be implemented, need a positive action by the state, more precisely by the state power whose function is to manage public money and create policies for implementation of fundamental rights. Given this, pay attention to the right to health, was created the Programa de Medicamentos de Dispensação Excepcional, which aims to provide high-cost medicines to citizens Brazilian carriers of serious diseases, such as Alzheimer's and Mal Hepatitis C. Also on the program, it provides a way which will be mandatory that the drugs will be offered in such situations, and does not include a means of updating the list predicted able to monitor the progress of medicine that have been in the interest of the program. Given that, at present it is necessary to mention the recognition of another fundamental right: the right to development, which is the right of access to positive actions being implemented by the State, which are nothing more than public policy, gender which the Programa de Medicamentos de Dispensação Excepcional is kind. Thus, through the search in legislation and doctrine in relation to the theme, this work has the aim to examine the extent of the state to provide exceptional dispensing of medicines. Specifically, if the State in attention to the right to development and the implementation of the right to health, can really list exhaustively the drugs to be provided by the State, and what are the elements guiding this choice and how to control the same

Decomposição e liberação de nitrogênio de resíduos culturais de plantas de cobertura em um solo de cerrado

A produção de massa seca, a taxa de decomposição e a liberação de nitrogênio (N) foram avaliadas em um experimento com sete tipos de cobertura vegetal: milheto pérola (Pennisetum americanum sin. tiphoydes), braquiária (Brachiaria brizantha), sorgo forrageiro (Sorghum bicolor L. Moench), guandu (Cajanus cajan (L.) Millsp), crotalária juncea (Crotalarea juncea) e aveia-preta (Avena strigosa Schreb), em pousio e em área de cultivo convencional (testemunha), em solo de cerrado, em Uberaba, região do Triângulo Mineiro. Dentre as coberturas avaliadas, o milheto e a crotalária foram as que apresentaram a maior produção de massa seca, maior acúmulo e a maior liberação de N. A braquiária foi a cobertura que apresentou a maior taxa de decomposição. Todas as coberturas apresentaram a maior taxa de liberação de N até 42 dias após dessecação.

Laurdan Spectrum Decomposition as a Tool for the Analysis of Surface Bilayer Structure and Polarity: a Study with DMPG, Peptides and Cholesterol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)