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O aplicativo móvel CalcVAN foi desenvolvido para auxiliar os profissionais de saúde para otimizar as doses de vancomicina em pacientes hospitalizados. Porém, é imprescindível avaliar a sua usabilidade antes de disponibilizá-lo para prática clínica. Assim, o objetivo do estudo é avaliar a usabilidade do aplicativo móvel na perspectiva dos profissionais de saúde. Trata-se de um estudo descritivo, de avaliação heurística da usabilidade de um aplicativo móvel. Foram convidados profissionais da área de saúde com expertise no tema de gerenciamento de antimicrobianos e vancomicina. O instrumento validado Smartphone Usability questionnaiRE (SURE) foi utilizado para mensuração da usabilidade por meio de um questionário on-line. Vinte e um especialistas participaram do estudo, com média de idade de 32,6 anos, sendo a maioria de mulheres (n = 14, 66,7%), profissionais farmacêuticos (n = 13, 61,9%), com pós-graduação lato sensu (n = 10, 47,6%), que trabalhavam em hospitais públicos ou privados (n = 15, 71,4%) e com média de experiência em 9,7 anos. Com base na interpretação dos resultados obtidos pelo instrumento SURE, a média de usabilidade geral do CalcVAN foi de 83 pontos, com escore menor de 78 e maior de 90 pontos. O teste de usabilidade foi enquadrado nos dois últimos níveis, 70 e 80, onde os profissionais de saúde passaram a concordar fortemente e totalmente, indicando que o aplicativo móvel apresenta uma usabilidade satisfatória. O CalcVAN atingiu uma usabilidade satisfatória e atende as necessidades e exigências dos profissionais de saúde, mostrando--se eficiente para realizar as funções propostas.

The CalcVAN app was developed to assist healthcare professionals in optimizing vancomycin doses for hospitalized patients. However, the usability test before making it available for clinical practice is essential. Therefore, the study aims to evaluate the usability of the app from the perspective of health professionals. A descriptive study, a heuristic evaluation of the usability of a mobile application was conducted. Healthcare professionals with expertise in antimicrobial management and vancomycin were invited to participate. The validated Smartphone Usability questionnaiRE (SURE) was used to measure usability through an online questionnaire. Twenty-one experts participated in the study, with a mean age of 32.6 years, mostly of them women (n = 14, 66.7%), pharmacists (n = 13, 61.9%), with postgraduate education (n = 10, 47.6%), working in private or public hospitals (n = 15, 71.4%), and a mean experience of 9.7 years. Overall usability score for CalcVAN was 83 points, ranging from a minimum of 78 to a maximum of 90 points. The usability test registered within the last two levels, 70 and 80, with users expressing strongly and fully agreed, indicating that the app demonstrates satisfactory usability. CalcVAN achieved satisfactory usability, fulfilling the needs and requirements of health professionals, proving to be efficient in performing the intended functions.

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CONTEXT: Analytic exchange-correlation kernel formulations are of the outermost importance for density functional theory (DFT) perturbation calculations. In this paper, the working equation for the exchange-correlation kernel of the generalized gradient approximation (GGA) for perturbation dependent auxiliary functions is derived and discussed in the framework of auxiliary density functional theory (ADFT). The presented new formulation is extended to the unrestricted approach, too. A comprehensive discussion of the implementation of the GGA ADFT kernel, using either the native exchange-correlation functional implementations in deMon2k or the ones from the LibXC library, is given. Calculations with analytic exchange-correlation kernels are compared to their finite difference counterparts. The obtained results are in quantitative agreement. Nevertheless, analytic GGA ADFT kernel implementations show substantial improvement in the computational performance. Similar results are reported for analytic second derivatives of effective core potential (ECP) and model core potential (MCP) matrix elements when compared to their finite difference counterparts in molecular frequency analyses. METHOD: All calculations are performed in the framework of ADFT as implemented in deMon2k. In the ADFT analytic frequency calculations, auxiliary density perturbation theory was used. The underlying two-center exchange-correlation kernel matrix elements are calculated by numerical integration either with analytic or finite difference kernel expressions. Validation calculations are performed with the VWN and PBE functionals employing DFT-optimized DZVP basis sets in conjunction with automatically generated GEN-A2 auxiliary density function sets. In the (Pt3Cu)n cluster benchmark calculations, the RPBE functional was used. For Pt atoms, the quasi-relativistic LANL2DZ effective core potential with the corresponding valence basis set was employed, whereas for Cu atoms, the all-electron DFT-optimized TZVP basis was applied. The auxiliary density was expanded by the automatically generated GEN-A2* auxiliary function set. We run all benchmark calculations in parallel on 24 cores.

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In this study, a novel 3,3'-bipyrazolo [3,4-b]pyridine-type structure was synthesized from 5-acetylamino-3-methyl-1-phenylpyrazole using the Vilsmeier-Haack reaction as a key step. The spectroscopic properties and structural elucidation of the compound were determined with the use of FT-IR, HRMS, 1H NMR, and 13C NMR. Likewise, the theoretical analysis of the IR and NMR spectra allowed peaks to be assigned and a solid correlation was demonstrated between the experimental and theoretical results. Finally, ab initio calculations based on the density functional theory method at the B3LYP/6-311G (d,p) level of theory were used to determine the conformational energy barrier, facilitating the identification of the most probable conformers of the synthesized compound. Overall, our findings contribute to the understanding of bipyrazolo [3,4-b]pyridine derivatives.

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We introduce a Molecular Theory for Compressible Fluids (MOLT-CF) that enables us to compute free energies and other thermodynamic functions for nanoparticle superlattices with any solvent content, including the dry limit. Quantitative agreement is observed between MOLT-CF and united-atom molecular dynamics simulations performed to assess the reliability and precision of the theory. Among other predictions, MOLT-CF shows that the amount of solvent within the superlattice decreases approximately linearly with its vapor pressure and that in the late stages of drying, solvent-filled voids form at lattice interstitials. Applied to single-component superlattices, MOLT-CF predicts fcc-to-bcc Bain transitions for decreasing vapor pressure and for increasing ligand length, both in agreement with experimental results. We explore the stability of other single-component phases and show that the C14 Frank-Kasper phase, which has been reported in experiments, is not a global free-energy minimum. Implications for precise assembly and prediction of multicomponent nanoparticle systems are discussed.

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In this study, a novel Z-scheme heterojunction on bismuth vanadium/cadmium sulfide (BiVO4/0.6CdS) was developed and evaluated for simultaneous photocatalytic removal of combined tetracycline (TC) and hexavalent chromium Cr(Ⅵ) pollution under visible light. Based on the analysis of intermediate products and theoretical calculation, the property of the intermediate products of TC degradation and the effect of built-in electric field (IEF) of composite materials on photo-generated carrier separation were illustrated. According to the experiments and evaluation results, the performance of BiVO4/0.6CdS is higher than CdS 2.83 times and 4.82 times under the visible light conditions, with the aspect of simultaneous oxidizing TC and reducing Cr(Ⅵ), respectively. The catalyst has a faster removal rate in the binary composite pollution system than the single one. Therefore, the photocatalytic degradation of TC using BiVO4/0.6CdS can reduce the toxic effect of TC on the environment. The aforementioned evaluation provides a new design strategy for Z-scheme heterojunction to simultaneous photocatalytic degradation of composite organic and inorganic pollutants.

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PURPOSE: To present a reproducible method to calculate the toricity needed at the intraocular lens (IOL) plane with toric phakic IOLs (ICL, Staar Surgical) and compare its results with those obtained with the online calculator provided by the manufacturer. DESIGN: Retrospective case series. SETTING: Private practice, Buenos Aires, Argentina. METHODS: The formula originally described by Holladay to calculate the IOL power in phakic eyes was used to calculate the required spherical power along the less refractive meridian and along the more refractive meridian. Meridional analysis was applied to calculate the required toricity at the IOL plane and the surgically induced corneal astigmatism was incorporated into the calculations. The refractive cylinder predicted by this method and by the online calculator of the manufacturer were compared to the postoperative refractive cylinder by means of vector analysis. The possible changes in the ratio of toricity in patients with different amounts of astigmatism and anterior chamber depth are assessed in a theoretical section. RESULTS: In 35 eyes, the measured mean postoperative refractive cylinder was 0.09 D @ 99°, the mean predicted postoperative refractive astigmatism was 0.04 D @ 102° according to the manufacturer's online calculator and 0.09 D @100° according to our method. With both methods, 91.43% of eyes had an absolute cylinder prediction error within ±0.50 diopters. CONCLUSIONS: The method described in this article to calculate the toricity of phakic IOLs has a refractive accuracy similar to that of the original calculator developed by the manufacturer.

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Diketopiperazine alkaloids have proven the most abundant heterocyclic alkaloids up to now, which usually process diverse scaffolds and rich biological activities. In our search for bioactive diketopiperazine alkaloids from marine-derived fungi, two novel diketopiperazine alkaloids, penipiperazine A (1) and its biogenetically related new metabolite (2), together with a known analogue neofipiperzine C (3), were obtained from the strain Penicillium brasilianum. Their planar structures and absolute configurations were elucidated by extensive spectroscopic analyses, 13C NMR calculation, Marfey's, ECD, and ORD methods. Compound 1 featured a unique 6/5/6/6/5 indole-pyrazino-pyrazino-pyrrolo system, and its plausible biogenetic pathway was also proposed. Additionally, compounds 1-3 have been tested for their inflammatory activities. 1 and 2 significantly inhibited the release of NO and the expression of related pro-inflammatory cytokines on LPS-stimulated RAW264.7 cells, suggesting they could be attracting candidate for further development as anti-inflammatory agent. KEY POINTS: • A novel diketopiperazine alkaloid featuring a unique 6/5/6/6/5 indole-pyrazino-pyrazino-pyrrolo system was isolated from the marine fungus Penicillium brasilianum. • The structure of 1 was elucidated by detailed analysis of 2D NMR data, 13C NMR calculation, Marfey's, ECD, and ORD methods. • Compounds 1 and 2 significantly inhibited the release of NO and the expression of related pro-inflammatory cytokines on LPS-stimulated RAW264.7 cells.

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Simulation and rigorous design of industrial dryers combine a large number of models, which feed three fundamental balances: (1) mass; (2) energy; and (3) quantity of movement of the material through the dryer. Many of these models represent physical phenomena affecting the three balances at the same time, which makes these calculations extremely complex, hence, accurate models are essential. The hypothesis that the kinetic stage of drying of any material culminates in the thermodynamic moisture equilibrium between solid and drying gas has been in effect for many years. However, recent findings show that there is a transition stage between the kinetic stage and the thermodynamic equilibrium, which, experimentally, looks like an equilibrium. The beginning of this transition stage or dynamic pseudo-equilibrium stage would mark the end of the drying kinetics models, which has been named as the dynamic pseudo-equilibrium moisture contents (Xdpe). The non-observance of this phenomenon presupposes a model limited in its prediction capacity, especially in the last stages of drying and even more so at low drying temperatures. As a consequence, sizes of industrial dryers could be underestimated during the simulation and rigorous design process, or underestimate drying times, in batch dryers. On the other hand, the optimal conditions may never be found, during the optimization of existing industrial drying processes. The objective of this work is to present the procedure to determine Xdpe, during the experimental determination of drying curves of any material. Likewise, to propose the practical moisture ratio, which uses Xdpe, instead of the equilibrium moisture, to be used in the modeling of the drying kinetics.•The drying process is divided into three stages: kinetic, transition, and equilibrium.•The dynamic pseudo-equilibrium moisture content divides the kinetic and the transition stages.•The practical moisture ratio should be used in rigorous industrial dryer design calculations.

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The PI3K class I is composed of four PI3K isoforms that serve as regulatory enzymes governing cellular metabolism, proliferation, and survival. The hyperactivation of PI3Kα is observed in various types of cancer and is linked to poor prognosis. Unfortunately, the development inhibitors selectively targeting one of the isoforms remains challenging, with only few agents in clinical use. The main difficulty arises from the high conservation among residues at the ATP-binding pocket across isoforms, which also serves as target pocket for inhibitors. In this work, molecular dynamics and quantum calculations were performed to investigate the molecular features guiding the binding of selective inhibitors, alpelisib and GDC-0326, into the ATP-binding pocket of PI3Kα. While molecular dynamics allowed crystallographic coordinates to relax, the interaction eergy between each amino acid residues and inhibitors was obtained by combining the Molecular Fractionation with Conjugated Caps scheme with Density Functional Theory calculations. In addition, the atomic charge of ligands in the bound and unbound (free) was calculated. Results indicated that the most relevant residues for the binding of alpelisib are Ile932, Glu859, Val851, Val850, Tyr836, Met922, Ile800, and Ile848, while the most important residues for the binding of GDC-0326 are Ile848, Ile800, Ile932, Gln859, Glu849, and Met922. In addition, residues Trp780, Ile800, Tyr836, Ile848, Gln859 Val850, Val851, Ile932 and Met922 are common hotspots for both inhibitors. Overall, the results from this work contribute to improving the understanding of the molecular mechanisms controlling selectivity and highlight important interactions to be considered during the rational design of new agents.Communicated by Ramaswamy H. Sarma.

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In this work, the characterization and analysis of the physics of a GaAs quantum well with AlGaAs barriers were carried out, according to an interior doped layer. An analysis of the probability density, the energy spectrum, and the electronic density was performed using the self-consistent method to solve the Schrödinger, Poisson, and charge-neutrality equations. Based on the characterizations, the system response to geometric changes in the well width and to non-geometric changes, such as the position and with of the doped layer as well as the donor density, were reviewed. All second-order differential equations were solved using the finite difference method. Finally, with the obtained wave functions and energies, the optical absorption coefficient and the electromagnetically induced transparency between the first three confined states were calculated. The results showed the possibility of tuning the optical absorption coefficient and the electromagnetically induced transparency via changes to the system geometry and the doped-layer characteristics.

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A copper-containing nitrite reductase catalyzes the reduction of nitrite to nitric oxide in the denitrifier Sinorhizobium meliloti 2011 (SmNirK), a microorganism used as bioinoculant in alfalfa seeds. Wild type SmNirK is a homotrimer that contains two copper centers per monomer, one of type 1 (T1) and other of type 2 (T2). T2 is at the interface of two monomers in a distorted square pyramidal coordination bonded to a water molecule and three histidine side chains, H171 and H136 from one monomer and H342 from the other. We report the molecular, catalytic, and spectroscopic properties of the SmNirK variant H342G, in which the interfacial H342 T2 ligand is substituted for glycine. The molecular properties of H342G are similar to those of wild type SmNirK. Fluorescence-based thermal shift assays and FTIR studies showed that the structural effect of the mutation is only marginal. However, the kinetic reaction with the physiological electron donor was significantly affected, which showed a âˆ¼ 100-fold lower turnover number compared to the wild type enzyme. UV-Vis, EPR and FTIR studies complemented with computational calculations indicated that the drop in enzyme activity are mainly due to the void generated in the protein substrate channel by the point mutation. The main structural changes involve the filling of the void with water molecules, the direct coordination to T2 copper ion of the second sphere aspartic acid ligand, a key residue in catalysis and nitrite sensing in NirK, and to the loss of the 3 N-O coordination of T2.

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The processing of coal tar pitch (CTP) to produce clean fuel gas and carbon black (CB) is studied in a plasma reactor equipped with a direct-current plasma torch. The composition of the gas produced and energy costs were estimated theoretically for the CTP pyrolysis and gasification processes by two oxidants, namely oxygen and water vapor. We have found that the main gaseous compounds obtained in the pyrolysis and gasification processes are hydrogen (H2), carbon monoxide (CO), and very often carbon dioxide (CO2). For the pyrolysis case, the mean value of the synthesis gas concentration reaches a major value of 98 vol.% (H2 - 81 vol.%, CO - 17. vol.%). However, only 23% of the initial CTP is transformed into gas phase at 1100 K and its content increases up to 37.4% at a temperature of 3000 K. For oxygen gasification, the syngas quantity is little less compared to the pyrolysis case and attains 96.6 vol.% (H2 - 26.5 vol.%, CO - 70.1 vol.%) for T > 1100 K. An intermediate syngas content for the water steam gasification is 97.8 vol.% (with H2 - 55.8 vol.% and CO - 42.0 vol.%). The CB produced was composed of well-defined spherical particles of 30-nm size. Furthermore, it is composed of carbon (98.2%), and followed by oxygen (1.8%) with a surface area of 97 m2 g-1. The thermal plasma system shows high efficiency in conversion of CTP into high-value-added products.

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Proteins equipped with flavin adenine dinucleotides (FAD) or flavin mononucleotides (FMN) are named flavoproteins and constitute about 1% of all existing proteins. They catalyze redox, acid-base and photochemical reactions in a variety of biochemical phenomena that goes from energy metabolism to DNA repair and light sensing. The versatility observed in flavoproteins is ultimately a balance of flavin intrinsic properties modulated by a protein environment. This thesis aims to investigate how flavoproteins work by systematic evaluating flavin properties and reactivity. In particular, the mechanism of fumarate reduction by the flavoenzyme fumarate reductase Fcc3 was determined. Electronic-structure calculations were used for this task based on rigorous calibration with experimental data and error assessment. Flavin properties at chemical accuracy were obtained with single reference coupled-cluster CCSD(T) calculations at the complete basis set limit. Density functional theory was demonstrated an excellent alternative with lower computational costs and slightly less accuracy. Flavin protonation and tautomerism were shown to be important modulators of flavin properties and reactivity, with the possibility of various tautomers existing at neutral pH. Regarding flavin redox properties, an analysis based on multiconfigurational wave function weights was proposed for categorizing flavin redox reactions as hydride or hydrogen-atom transfers. This analysis is an upgrade over traditional partial charges methods and can be applied not only to flavin reactions but to any protoncoupled electron transfer. In the investigation of the enzymatic mechanism of fumarate reduction, the reaction was determined as a nucleophilic addition by hydride transfer with carbanion formation. Fumarate reductase employs electrostatic catalysis in contrast to previous proposals of substrate straining and general-acid catalysis. Also, hydride transfer was shown to be vibronically adiabatic with low tunneling contribution. These findings give new insights into the mechanisms of fumarate reductases and provide a framework for future computational studies of flavoproteins in general. The analyses and benchmark studies presented can be used to build better models of properties and reactivity of flavins and flavoproteins

Proteínas equipadas com dinucleotídeos de flavina-adenina (FAD) e mononucleotídeos de flavina (FMN) são chamadas flavoproteínas e constituem cerca de 1% de todas as proteínas existentes. Elas catalisam reações redox, ácido-base e fotoquímicas numa variedade de fenômenos bioquímicos que vão desde o metabolismo energético até reparo de DNA e captação de luz. A versatilidade observada em flavoproteínas é em última instância um balanço das propriedades intrínsecas de flavinas moduladas por um ambiente proteico. Esta tese busca investigar como flavoproteínas funcionam através de avaliações sistemáticas de propriedades e reatividade de flavinas. Em particular, o mecanismo de redução de fumarato pela flavoenzima fumarato redutase Fcc3 foi determinado. Cálculos de estrutura eletrônica foram usados para esta tarefa com base em rigorosa calibração com dados experimentais e avaliação de erros. As propriedades de flavinas foram determinadas com acurácia química com cálculos monoconfiguracionais de coupled-cluster CCSD(T) no limite de conjunto base completo. A teoria do funcional da densidade mostrou-se uma alternativa excelente com menor custo computacional e um pouco menos de acurácia. Protonação e tautomerismo de flavinas mostraram-se moduladores importantes de suas propriedades e reatividade, com a possibilidade de vários tautômeros existirem em pH neutro. Em relação às propriedades redox de flavinas, uma análise baseada nos pesos de funções de onda multiconfiguracionais foi proposta para categorizar as reações redox de flavinas como transferências de hidreto ou hidrogênio. Esta análise é uma melhoria em relação aos métodos tradicionais de cargas parciais e pode ser aplicada não apenas para reações de flavinas mas para qualquer transferência de próton acoplada a elétrons. Na investigação do mecanismo enzimático de redução de fumarato, a reação foi designada como uma adição nucleofílica por transferência de hidreto e formação de carbânion. A fumarato redutase usa catálise eletrostática diferentemente de prospostas anteriores envolvendo distorção do substrato e catálise ácida geral. Além disso, a transferência de hidreto mostrou-se vibronicamente adiabática com pouca contribuição de tunelamento. Estas descobertas abrem novas perspectivas sobre os mecanismos de fumarato redutases e fornecem uma base para estudos computacionais futuros sobre flavoproteínas em geral. As análises e estudos comparativos apresentados podem ser usados para construir melhores modelos para propriedades e reatividade de flavinas e flavoproteínas

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Two new relativistic adapted Gaussian basis sets of small and medium size are presented for all elements from Hydrogen through Xenon. These sets are free of variational prolapse and were developed with the polynomial generator coordinate Dirac-Fock method to be used with two finite nuclear models, uniform sphere and Gaussian. The largest basis set errors for electronic configurations from the Aufbau principle are around 10.0 and 4.7 mHartree for the small- and medium-size sets, respectively, which is in accordance with the accuracy level expected in each case. Hence, to our knowledge, these are the smallest prolapse free basis sets developed for these elements.

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Objetivo: Determinar los resultados refractivos con las fórmulas Holladay 2 y Barret Universal 2 a partir del cálculo de la lente intraocular en pacientes operados de catarata. Métodos: Se realizó un estudio descriptivo prospectivo y longitudinal con 60 ojos de 50 pacientes operados de catarata mediante la técnica de facoemulsificación. Se empleó para el cálculo de la lente el IOL Master 700 y el Pentacam AXL con la fórmula Holladay 2 y Barret Universal 2, respectivamente. Resultados: Predominó el sexo femenino y el grupo etario mayor de 60 años. Los ojos mayores de 26 mm mostraron la mayor diferencia entre el poder dióptrico de la lente intraocular que se implantó según Holladay y en menores de 22 mm según Barret Universal. Ambos grupos presentaron una disminución del equivalente esférico, siendo superior a 7 y 5 dioptrías en ojos mayores de 26 mm en el posoperatorio de ambas fórmulas. Posterior a la cirugía se observó una mejoría en la agudeza visual sin corrección y corregida de más de 4 líneas en la cartilla de Snellen, independiente de la longitud axial, para ambos grupos en estudio. Sin cambios significativos en el cilindro queratométrico. En el 70,0 por ciento de los casos, el resultado refractivo final estuvo en rango de la emetropía para el grupo Holladay 2 y el 66,7 por ciento para el grupo Barret Universal 2. Conclusiones: Ambas fórmulas resultan útiles para el cálculo de la lente intraocular en todos los rangos de longitud axial(AU)

Objective: To determine refractive outcomes with the Holladay 2 and Barret Universal 2 formulas from intraocular lens calculation in cataract surgery patients. Methods: A prospective and longitudinal descriptive study was performed with 60 eyes of 50 patients who underwent cataract surgery by phacoemulsification. The IOL Master 700 and Pentacam AXL with the Holladay 2 and Barret Universal 2 formula, respectively, were used to calculate the lens. Results: Female gender and age group older than 60 years predominated. Eyes larger than 26 mm showed the greatest difference between the dioptric power of the intraocular lens implanted according to Holladay and those smaller than 22 mm according to Barret Universal. Both groups presented a decrease of the spherical equivalent, being higher than 7 and 5 diopters in eyes larger than 26 mm postoperatively in both formulas. Postoperatively, there was an improvement in uncorrected and corrected visual acuity of more than 4 lines in the Snellen chart, independent of axial length, for both groups under study. No significant changes in keratometric cylinder. In 70.0 percent of the cases, the final refractive result was in the emmetropia range for the Holladay 2 group and 66.7 percent for the Barret Universal 2 group. Conclusions: Both formulas are useful for the calculation of the intraocular lens in all axial length ranges(AU)

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The development of conjugated polymer-based nanocomposites by adding metallic particles into the polymerization medium allows the proposition of novel materials presenting improved electrical and optical properties. Polyaniline Emeraldine-salt form (ES-PANI) has been extensively studied due to its controllable electrical conductivity and oxidation states. On the other hand, tungsten oxide (WO3) and its di-hydrated phases, such as WO3·2H2O, have been reported as important materials in photocatalysis and sensors. Herein, the WO3·2H2O phase was directly obtained during the in-situ polymerization of aniline hydrochloride from metallic tungsten (W), allowing the formation of hybrid nanocomposites based on its full oxidation into WO3·2H2O. The developed ES-PANI-WO3·2H2O nanocomposites were successfully characterized using experimental techniques combined with Density Functional Theory (DFT). The formation of WO3·2H2O was clearly verified after two hours of synthesis (PW2 nanocomposite), allowing the confirmation of purely physical interaction between matrix and reinforcement. As a result, increased electrical conductivity was verified in the PW2 nanocomposite: the DFT calculations revealed a charge transfer from the p-orbitals of the polymeric phase to the d-orbitals of the oxide phase, resulting in higher conductivity when compared to the pure ES-PANI.

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Objetivo: Optimizar las constantes utilizadas por las fórmulas SRK/T, SRK/T2, Holladay 1 y Hoffer Q para cinco modelos de lentes intraoculares (LIO), implantados durante la cirugía de catarata en el Instituto Cubano de Oftalmología (enero/2006-octubre/2019). Método: Se estudiaron retrospectivamente 47341 pacientes. Las constantes se optimizaron ajustando a cero el error de predicción promedio (EPm) y obteniendo el valor que arrojó el máximo número de ojos con error de predicción absoluto -EP- ≤; 0,25, tanto para la biometría ultrasónica como para la óptica. La eficacia de las constantes optimizadas se verificó mediante el análisis de los errores absolutos medio y mediano (EAM/EAMed) más bajos y el porcentaje de ojos en un intervalo determinado de error de predicción en función del valor de las constantes. También se analizaron el índice de rendimiento de la fórmula de Haigis y un nuevo índice introducido. Resultados: Las constantes optimizadas fueron significativamente diferentes de los valores del fabricante. Los valores obtenidos para EPm = 0 fueron diferentes a los mínimos de EAM y EAMed. El porcentaje de ojos con -EP- ≤ 0,25 y 0,50 D difirió cuando los criterios de optimización fueron diferentes. SRK/T y SRK/T2 mostraron los mejores rendimientos, según ambos índices. Conclusiones: Las constantes optimizadas mejoran los resultados postoperatorios para cada combinación LIO-fórmula. Diferentes criterios de optimización conducen a diferentes resultados. El EAM, el EAMed y el porcentaje de ojos con -EP- ≤; 0,50 D son parámetros válidos para comprobar el rendimiento de las fórmulas, hasta disponer de un índice único, fiable y consensuado(AU)

Objective: To optimize the constants used by the SRK/T, SRK/T2, Holladay 1 and Hoffer Q formulas for five intraocular lens (IOL) models implanted during cataract surgery at the Cuban Institute of Ophthalmology (January/2006-October/2019). Methods: 47341 patients were retrospectively studied. The constants were optimized by adjusting the average prediction error (EPm) to zero and obtaining the value that showed the maximum number of eyes with absolute prediction error -EP- ≤ 0.25, for both ultrasonic and optical biometry. The effectiveness of the optimized constants was verified by analyzing the lowest average and median absolute errors (EAM/EAMed) and the percentage of eyes in a given range of prediction error as a function of the value of the constants. The Haigis formula performance index and a newly introduced index were also analyzed. Results: The optimized constants were significantly different from the manufacturer's values. The values obtained for EPm = 0 were different from the EAM and EAMed minima. The percentage of eyes with -EP- ≤ 0.25 and 0.50 D differed when the optimization criteria were different. SRK/T and SRK/T2 showed the best performances, according to both indexes. Conclusions: Optimized constants improve postoperative outcomes for each IOL-formula combination. Different optimization criteria lead to different results. The EAM, the EAMed and the percentage of eyes with -EP- ≤ 0.50 D are valid parameters to check the performance of the formulas, until a single, reliable and consensual index is available(AU)

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The reactivity of the fluoride ion towards alkyl halides is highly dependent on the solvating environment. In polar aprotic solvents with large counter-ions is highly reactive and produces substantial E2 product, whereas in polar protic solvents leads to slow kinetics and high selectivity for SN2 reactions. The use of a more complex environment with stoichiometric addition of tert-butanol to acetonitrile solvent is able to module the reactivity and selectivity of tetrabutylammonium fluoride (TBAF). In the present work, we have performed a detailed theoretical analysis of this complex reaction system by density functional theory, continuum solvation model, and including explicit tert-butanol molecules. A kinetic model based on the free energy profile was also used to predict the reactivity and selectivity. The results indicated that the TBAF(tert-butanol) complex plays the key role to increase the SN2 selectivity, whereas higher aggregates are not relevant. The E2 product is formed exclusively via free TBAF, because the solvating tert-butanol in the TBAF(tert-butanol) complex inhibits the E2 pathway. Our analysis suggests that diols or tetraols could produce an improved selectivity.

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Background: Mobile applications (app) provide many benefits for healthcare professionals, making them a useful support clinical decision system. Objectives: To describe the development of a mobile app, CalcVAN, to calculate vancomycin dosage regimens for adult and pediatric patients. Methods: This study is a technological production research to develop a mobile app through the rapid prototyping type for the Android system in the Brazilian context. The mobile app structure was developed in four steps: 1) conception, including the needs assessment, the target audience, the literature search, and the definition of contents; 2) prototype planning, including the definition of topics and writing of modules, the selection of media, and the layout; 3) production of the mobile app, including the selection of multimedia tools, the navigation structure, and planning of environment configuration; and 4) make the mobile app available. Results: The CalcVAN has six screens, containing the vancomycin dosing calculator for adult and pediatric patients based on weight and estimated creatinine clearance parameters. Moreover, the mobile app is free and can be used without internet connection. Conclusions: A free mobile app was developed to calculate vancomycin dosage regimens for inpatients. This tool assists to optimize the vancomycin dosing, contributing to the antimicrobial stewardship.

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A rare dihydoxyflavan-epicatechin proanthocyanidin, entcassiflavan-(4ß→8)-epicatechin, was isolated from Dalbergia monetaria, a plant widely used by traditional people from the Amazon to treat urinary tract infections. The constitution and relative configuration of the compound were elucidated by HR-MS and detailed 1D- and 2D-NMR measurements. By comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD spectra of all 16 possible isomers, the absolute configuration, the interflavan linkage, and the atropisomers could be determined.

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