NMR Chemical Shielding and Spin-Spin Coupling Constants of Liquid NH(3): A Systematic Investigation using the Sequential QM/MM Method

The NMR spin coupling parameters, (1)J(N,H) and (2)J(H,H), and the chemical shielding, sigma((15)N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functional theory calculations. Two different Lennard-Jones potentials are used in the liquid simulations. Electronic polarization is included in these two potentials via an iterative procedure with and without geometry relaxation, and the influence on the calculated properties are analyzed. B3LYP/aug-cc-pVTZ-J calculations were used to compute the V(N,H) constants in the interval of -67.8 to -63.9 Hz, depending on the theoretical model used. These can be compared with the experimental results of -61.6 Hz. For the (2)J(H,H) coupling the theoretical results vary between -10.6 to -13.01 Hz. The indirect experimental result derived from partially deuterated liquid is -11.1 Hz. Inclusion of explicit hydrogen bonded molecules gives a small but important contribution. The vapor-to-liquid shifts are also considered. This shift is calculated to be negligible for (1)J(N,H) in agreement with experiment. This is rationalized as a cancellation of the geometry relaxation and pure solvent effects. For the chemical shielding, U(15 N) Calculations at the B3LYP/aug-pcS-3 show that the vapor-to-liquid chemical shift requires the explicit use of solvent molecules. Considering only one ammonia molecule in an electrostatic embedding gives a wrong sign for the chemical shift that is corrected only with the use of explicit additional molecules. The best result calculated for the vapor to liquid chemical shift Delta sigma((15)N) is -25.2 ppm, in good agreement with the experimental value of -22.6 ppm.

Polarization and Spectral Shift of Benzophenone in Supercritical Water

Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and that the inclusion of this polarization is important for a reliable description of the spectral shifts considered here.

Polarization and solvatochromic shift of ortho-betaine in water

Betaine dyes are known to show very large transition energy shifts in different solvents. The ortho-betaine molecule - a simple two-ring prototype of the E-T(30) Reichardt dye - has been investigated theoretically from a combined statistical and quantum mechanics approach. Using sequential Monte Carlo (MC) simulations and MP2/cc-pVDZ calculations the in-water dipole moment of ortho-betaine is obtained as 12.30 +/- 0.05 D. This result shows a considerable increase of 75% compared to the in-vacuum dipole moment. For comparison, the use of a polarizable continuum model using the same MP2/cc-pVDZ leads to an in-water dipole moment of 11.6 D, in good agreement. This large polarization is incorporated in the classical potential for another MC simulation to generate solute-solvent configurations and to obtain the contribution of the polarization effect in the solvatochromic shift. Using statistically uncorrelated configurations and supermolecular INDO/CIS calculations, including the solute and, explicitly, 230 solvent water molecules, the statistically converged calculated shift is obtained here as 6360 cm(-1), in good agreement with the experimental result of 7550 cm(-1). (c) 2007 Elsevier B.V. All rights reserved.

Crossed products by twisted partial actions and graded algebras

For a twisted partial action e of a group G on an (associative non-necessarily unital) algebra A over a commutative unital ring k, the crossed product A x(Theta) G is proved to be associative. Given a G-graded k-algebra B = circle plus(g is an element of G) B-g with the mild restriction of homogeneous non-degeneracy, a criteria is established for B to be isomorphic to the crossed product B-1 x(Theta) G for some twisted partial action of G on B-1. The equality BgBg-1 B-g = B-g (for all g is an element of G) is one of the ingredients of the criteria, and if it holds and, moreover, B has enough local units, then it is shown that B is stably isomorphic to a crossed product by a twisted partial action of G. (c) 2008 Elsevier Inc. All rights reserved.

Partial projective representations and partial actions

The concept of a partial projective representation of a group is introduced and studied. The interaction with partial actions is explored. It is shown that the factor sets of partial projective representations over a field K are exactly the K-valued twistings of crossed products by partial actions. (C) 2009 Elsevier B.V. All rights reserved.

Registro periodontal simplificado em gestantes

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

Simplified periodontal record for pregnant women

The assessment using the PSR (Periodontal Screening and Recording) of the prevalence and severity of and the basic treatment needs for periodontal disease in a group of pregnant women who attended the Preventive Dentistry Clinic at the School of Dentistry of Araraquara--UNESP. Forty-one pregnant women of 16 to 37 years of age, were examined. The PSR index was evaluated with a suitable periodontal probe (Trinity-model 621-WHO) with index codes scores of from 0 to 4, capable of indicating the presence of the following conditions: periodontal health, bleeding on probing, calculus, shallow and deep pockets. These codes were attributed to each sextant and could be marked with an asterisk (*) to indicate the presence of gingival recession, furcation lesions, mobility or any other mucogingival alterations. It is shown that 100% of the pregnant women had some kind of gingival alteration, represented mainly by PSR code 2 (56.1%) and * (19.5%). The women in the youngest age groups, 15-19 and 20-24 years, had code 2 as their highest score with no sextant excluded. In the 25-29 age group, the PSR code 2 still prevailed (54.5%) although codes 3 and 4 were already appearing. The code * and the occurrence of excluded sextants tended to increase in the oldest age group (30-37). In general, the affected sextants showed codes 1 and 2 more frequently, corresponding to 41.6% and 39.8% respectively, which represented a mean of 2.49 and 2.39 sextants affected in each pregnant woman. Regarding the treatment needs, 90.2% of the women needed some treatment beyond the preventive measures begun, including scaling and root planning and/or corrections of defective restorative margins (61%), and more complex treatment (29.2%). The meeting of the treatment needs during pregnancy must include special efforts to increase motivation and promote oral health, minimizing the possibility of vertical transmission of pathogenic microrganisms to the child, and thus contributing to the primary prevention of the main oral diseases.

Kleiner's theorem for unitary representations of posets

A subspace representation of a poset S = {s(1), ..., S-t} is given by a system (V; V-1, ..., V-t) consisting of a vector space V and its sub-spaces V-i such that V-i subset of V-j if s(i) (sic) S-j. For each real-valued vector chi = (chi(1), ..., chi(t)) with positive components, we define a unitary chi-representation of S as a system (U: U-1, ..., U-t) that consists of a unitary space U and its subspaces U-i such that U-i subset of U-j if S-i (sic) S-j and satisfies chi 1 P-1 + ... + chi P-t(t) = 1, in which P-i is the orthogonal projection onto U-i. We prove that S has a finite number of unitarily nonequivalent indecomposable chi-representations for each weight chi if and only if S has a finite number of nonequivalent indecomposable subspace representations; that is, if and only if S contains any of Kleiner's critical posets. (c) 2012 Elsevier Inc. All rights reserved.

CYP3A5 and NAT2 gene polymorphisms: role in childhood acute lymphoblastic leukemia risk and treatment outcome

Susceptibility to acute lymphoblastic leukemia can be highly influenced by genetic polymorphisms in metabolizing enzyme genes of environmental carcinogens. This study aimed to evaluate the impact of the CYP3A5 and NAT2 metabolizing enzyme polymorphisms on the risk of childhood acute lymphoblastic leukemia. The analysis was conducted on 204 ALL patients and in 364 controls from a Brazilian population, using PCR-RFLP. The CYP3A5*3 polymorphic homozygous genotype was more frequent among ALL patients and the *3 allele variant was significantly associated with increased risk of childhood ALL (OR = 0.29; 95% CI, 0.14-0.60). The homozygous polymorphic genotype for the *6 allele variant was extremely rare and found in only two individuals. The heterozygous frequencies were similar for the ALL group and the control group. No significant differences were observed between the groups analyzed regarding NAT2 variant polymorphisms. None of the polymorphisms analyzed was related to treatment outcome. The results suggest that CYP3A5*3 polymorphism may play an important role in the risk of childhood ALL.

SLCO1B1 haplotypes are not associated with atorvastatin-induced myalgia in Brazilian patients with familial hypercholesterolemia

Purpose Recent studies reported the association of SLCO1B1 haplotypes with the development of musculoskeletal side effects during simvastatin use. The aim was to evaluate the pharmacogenetic association of SLCO1B1 haplotypes with atorvastatin-induced myalgia in a sample of individuals on high-dose atorvastatin regimens. Methods One hundred and forty-three patients with familial hypercholesterolemia were followed for at least 12 months while receiving atorvastatin. Genotypes for the rs2306283 (c.A388G) and rs4149056 (c.T521C) polymorphisms were detected by high-resolution melting analysis. These markers form four distinct haplotypes (*1A, *1B, *5 and *15). Results During the follow-up period, 14 (9.8%) patients developed myalgia and 16 (11.2%) presented CK levels more than 3 times the upper limit of the normal range. No association of the SLCO1B1 rs2306283 and rs4149056 genotypes or haplotypes with the presence of myalgia or creatine kinase (CK) values was found. Presence of rs2306283 AG+GG genotypes was not associated with increased risks of myalgia or abnormal CK values (OR 2.08, 95% CI 0.62-7.00, p=0.24 and OR 0.51, 95% CI 0.21-1.26, p=0.15 respectively). The presence of rs4149056 TC+CC genotypes was also not associated with increased risk of myalgia or abnormal CK values (OR 2.24, 95% CI 0.47-10.72, p=0.31 and OR 1.51, 95% CI 0.57-3.96, p=0.41 respectively). Conclusions Our findings reaffirm that the SLCO1B1 genetic risk appears to be greater in those patients receiving simvastatin compared with those receiving atorvastatin. This suggests that the importance of SLCO1B1 haplotypes depends on the specific statin that has been used.

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

Flares and variability from Sagittarius A(star): five nights of simultaneous multi-wavelength observations

Aims. We report on simultaneous observations and modeling of mid-infrared (MIR), near-infrared (NIR), and submillimeter (sub-mm) emission of the source Sgr A * associated with the supermassive black hole at the center of our Galaxy. Our goal was to monitor the activity of Sgr A* at different wavelengths in order to constrain the emitting processes and gain insight into the nature of the close environment of Sgr A*. Methods. We used the MIR instrument VISIR in the BURST imaging mode, the adaptive optics assisted NIR camera NACO, and the sub-mm antenna APEX to monitor Sgr A* over several nights in July 2007. Results. The observations reveal remarkable variability in the NIR and sub-mm during the five nights of observation. No source was detected in the MIR, but we derived the lowest upper limit for a flare at 8.59 mu m (22.4 mJy with A(8.59 mu m) = 1.6 +/- 0.5). This observational constraint makes us discard the observed NIR emission as coming from a thermal component emitting at sub-mm frequencies. Moreover, comparison of the sub-mm and NIR variability shows that the highest NIR fluxes (flares) are coincident with the lowest sub-mm levels of our five-night campaign involving three flares. We explain this behavior by a loss of electrons to the system and/or by a decrease in the magnetic field, as might conceivably occur in scenarios involving fast outflows and/or magnetic reconnection.

Eocene calcareous nannofossils in DSDP Holes 95-612 and 95-613

Lower Eocene calcareous nannofossil limestone cored at DSDP Site 612 on the middle slope off New Jersey represents an almost complete biostratigraphic sequence; only the lowest biozone (CP9a; NP10*) was not recovered. The thickness of the strata (198 m), the good preservation of the nannofossils, and the lack of long hiatuses justify the acceptance of this section as a lower Eocene reference for the western North Atlantic margin. The widely recognized and very similar nannofossil zonations of Martini (NP zones) and Bukry-Okada (CP zones) are emended slightly to make their lower Eocene biozones coeval; in addition, five new subzones are erected that subdivide zones CP10 and CPU (NP12 and NP13). Established biozone names are retained as they are altered little in concept, but alphanumeric code systems are changed somewhat by appending an asterisk (*) to identify zones that are emended. Zone CP10* (NP12*) is divided into two parts, the Lophodolithus nascens Subzone (CP10*a; NP12*a) and the Helicosphaera seminulum Subzone (CP10*b; NP12*b). Zone CPU* (NP13*) is divided into three parts, the Helicosphaera lophota Subzone (CP11*a; NP13*a), the Cyclicargolithuspseudogammation Subzone (CP11*b; NP13*b), and the Rhabdosphaera tenuis Subzone (CP11*c; NP13*c). At Site 612, a time-depth curve based on nannofossil datums dated in previous studies reveals a smoothly declining sediment accumulation rate, from 4.9 cm/10**3yr in CP10* (NP12*) to 2.8 cm/103 yr. in CP12* (NP14*). The ages of first-occurrence datums not previously dated are approximated by projection onto this timedepth curve and are as follows: Helicosphaera seminulum, 55.0 Ma; Helicosphaera lophota, 54.5 Ma; Cyclicargolithus pseudogammation, 53.7 Ma; Rhabdosphaera tenuis, 52.6 Ma; and Rhabdosphaera inflata, 50.2 Ma. At nearby Site 613 on the upper rise, strata of similar age, 139 m thick, contain an unconformity representing Subzone CPll*b (NP13*b) and a hiatus of approximately 1.1 m.y. duration. The sediment accumulation rate in the lower part of this section (9.7 cm/10**3yr.) is twice that observed for equivalent strata at Site 612. The hiatus and the heightened sediment accumulation rate at Site 613 probably represent the effects of episodic mass wasting on the early Eocene continental slope and rise.

Aprendizaje, simulación y desarrollo sobre las tecnologías de voz y datos

El objetivo del Proyecto Fin de Carrera (PFC) es el de conocer, simular y crear una red VoIP sobre una red de datos en un entorno docente, más concretamente, en la asignatura Redes y Servicios de telecomunicación en Grado en Ingeniería de Telecomunicaciones en la Universidad Politécnica de Madrid (UPM). Una vez se adquieran los conocimientos necesarios, se propondrán una serie de prácticas para que los alumnos se vayan familiarizando con el software y hardware utilizados, de manera que, se irá subiendo el grado de dificultad hasta que puedan realizar una auténtica red VoIP por sí mismos. A parte de la realización de las prácticas, los alumnos deberán pasar una prueba de los conocimientos adquiridos al final de cada práctica mediante preguntas tipo test. Los sistemas elegidos para la implantación de una red VoIP en los módulos de laboratorio son: 3CX System Phone y Asteisk-Trixbox. Los cuales, son capaces de trabajar mediante gestores gráficos para simplificar el nivel de dificultad de la configuración. 3CX es una PBX que trabaja sobre Windows y se basa exclusivamente en el protocolo SIP. Esto facilita el manejo para usuarios que solo han usado Windows sin quitar funcionalidades que tienen otras centralitas en otros sistemas operativos. La versión demo activa todas las opciones para poder familiarizarse con este sistema. Por otro lado, Asterisk trabaja en todas las plataformas, aunque se ha seleccionado trabajar sobre Linux. Esta selección se ha realizado porque el resto de plataformas limitan la configuración de la IP PBX, esta es de código abierto y permite realizar todo tipo de configuraciones. Además, es un software gratuito, esto es una ventaja a la hora de configurar novedades o resolver problemas, ya que hay muchos especialistas que dan soporte y ayudan de forma gratuita. La voz sobre Internet es habitualmente conocida como VoIP (Voice Over IP), debido a que IP (Internet Protocol) es el protocolo de red de Internet. Como tecnología, la VoIP no es solo un paso más en el crecimiento de las comunicaciones por voz, sino que supone integrar las comunicaciones de datos y las de voz en una misma red, y en concreto, en la red con mayor cobertura mundial: Internet. La mayor importancia y motivación de este Proyecto Fin de Carrera es que el alumno sea capaz de llegar a un entorno laboral y pueda tener unos conocimientos capaces de afrontar esta tecnología que esta tan a la orden del día. La importancia que estas redes tienen y tendrán en un futuro muy próximo en el mundo de la informática y las comunicaciones. Cabe decir, que se observa que estas disciplinas tecnológicas evolucionan a pasos agigantados y se requieren conocimientos más sólidos. ABSTRACT. The objective of my final project during my studies in university was, to simulate and create a VoIP network over a data network in a teaching environment, more specifically on the subject of telecommunications networks and services in Telecommunication Engineering Degree in Polytechnic University of Madrid (UPM). Once acquiring the necessary knowledge a number of practices were proposed to the students to become familiar with the software and hardware used, so that it would rise to the level of difficulty that they could make a real VoIP network for themselves. Parts of the experimental practices were that students must pass a test of knowledge acquired at the end of each practice by choice questions. The systems chosen for the implementation of a VoIP network in the laboratory modules are: 3CX Phone System and Asteisk - Trixbox. Which were able to work with graphics operators to simplify the difficulty level of the configuration. 3CX is a PBX that works on Windows and is based solely on the SIP protocol. This facilitates handling for users who have only used Windows without removing functionality with other exchanges in other operating systems. Active demo version all options to get to grips with this system. Moreover, Asterisk works on all platforms, but has been selected to work on Linux. This selection was made because other platforms limit the IP PBX configuration, as this is open source and allows all kinds of configurations. Also, Linux is a free software and an advantage when configuring new or solve problems, as there are many specialists that support and help for free. Voice over Internet is commonly known as VoIP (Voice Over IP), because IP (Internet Protocol) is the Internet protocol network. As technology, VoIP is not just another step in the growth of voice communications, but communications of integrating data and voice on a single network, and in particular, in the network with the largest global coverage: Internet. The increased importance and motivation of this Thesis is that the student is able to reach a working environment and may have some knowledge to deal with these technologies that is so much the order of the day. The importances of these networks have and will be of essences in the very near future in the world of computing and communications. It must be said it is observed that these technological disciplines evolve by leaps and bounds stronger knowledge required.

Index of Harvard graduates in the classes of 1642-1772, (manuscript notebook), ca. 1772-1791

Notebook containing an alphabetical index of Harvard graduates from 1642 to 1772. The author is unidentified, but the handwriting appears to be that of Harvard President Samuel Langdon (president from 1774 - 1780). The names are arranged alphabetically by surname. Each entry includes the graduate's name, additional degrees (Master, STD, MD, etc.), the year of graduation, and an asterisk if the individual was deceased. The asterisks are included for some graduates who died in 1791, indicating the work was created and updated between 1772 and 1791.