Chiral dienamides-substrates for asymmetric synthesis of amido cyclohexenes

Chiral dienamides, derived from chiral amines and oxazolidinones, react with electron deficient dienophiles Eo give amino-cyclohexanes with good to excellent de's.

Site symmetry dependence of repulsive interactions between chemisorbed oxygen atoms on Pt{100}-(1x1)

Ab initio total energy calculations using density functional theory with the generalized gradient approximation have been performed for the chemisorption of oxygen atoms on a Pt{100}-(1 x 1) slab. Binding energies for the adsorption of oxygen on different high-symmetry sites are presented. The bridge site is the most stable at a coverage of 0.5 ML, followed by the fourfold hollow site. The atop site is the least stable. This finding is rationalized by analyzing the ''local structures'' formed upon oxygen chemisorption. The binding energies and heats of adsorption at different oxygen coverages show that pairwise repulsive interactions are considerably stronger between oxygen atoms occupying fourfold sites than those occupying bridge sites. Analysis of the partial charge densities associated with Bloch states demonstrates that the O-Pt bond is considerably more localized at the bridge site. These effects cause a sharp drop in the heats of adsorption for oxygen on hollow sites when the coverage is increased from 0.25 to 0.5 ML. Mixing between oxygen p orbitals and Pt d orbitals can be observed over the whole metal d-band energy range.

Nonclassicality and criticality in symmetry protected magnetic phases

Quantum and global discord in a spin-1 Heisenberg chain subject to single-ion anisotropy (uniaxial field) are studied using exact diagonalisation and the density matrix renormalisation group (DMRG). We find that these measures of quantum non-classicality are able to detect the quantum phase transitions confining the symmetry protected Haldane phase and show critical scaling with universal exponents. Moreover, in the case of thermal states, we find that quantum discord can increase with increasing temperature.

Scaled Heavy-Ball Acceleration of the Richardson-Lucy Algorithm for 3D Microscopy Image Restoration

The Richardson–Lucy algorithm is one of the most important in image deconvolution. However, a drawback is its slow convergence. A significant acceleration was obtained using the technique proposed by Biggs and Andrews (BA), which is implemented in the deconvlucy function of the image processing MATLAB toolbox. The BA method was developed heuristically with no proof of convergence. In this paper, we introduce the heavy-ball (H-B) method for Poisson data optimization and extend it to a scaled H-B method, which includes the BA method as a special case. The method has a proof of the convergence rateof O(K^2), where k is the number of iterations. We demonstrate the superior convergence performance, by a speedup factor off ive, of the scaled H-B method on both synthetic and real 3D images.

Enzyme-catalysed oxidation of 1,2-disulfides to yield chiral thiosulfinate, sulfoxide and cis-dihydrodiol metabolites

Enantioenriched and enantiopure thiosulfinates were obtained by asymmetric sulfoxidation of cyclic 1,2-disulfides, using chemical and enzymatic (peroxidase, monooxygenase, dioxygenase) oxidation methods and chiral stationary phase HPLC resolution of racemic thiosulfinates. Enantiomeric excess values, absolute configurations and configurational stabilities of chiral thiosulfinates were determined. Methyl phenyl sulfoxide, benzo[c]thiophene cis-4,5-dihydrodiol and 1,3-dihydrobenzo[c]thiophene derivatives were among unexpected types of metabolites isolated, when acyclic and cyclic 1,2-disulfide were used as substrates for Pseudomonas putida strains. Possible biosynthetic pathways are presented for the production of metabolites from 1,4-dihydrobenzo-2,3-dithiane, including a novel cis-dihydrodiol metabolite that was also derived from benzo[c]thiophene and 1,3-dihydrobenzo[c]thiophene.

Outcomes and projected impact on vision restoration of the China million cataract surgeries program

Purpose: The recently completed Chinese "Million Cataract Surgeries Program" (MCSP) is among the largest such campaigns ever, providing 1.05 million operations. We report MCSP outcomes for the first time, in Jiangxi, the province with the greatest program output. Methods: Ten county hospitals participating in MCSP were selected in Jiangxi (range of gross domestic product per capita US$743-2998). Each hospital sought to enroll 75 consecutive MCSP patients aged ≥50 years. Data recorded included type of cataract procedure, bilateral uncorrected visual acuity (UCVA) and best-corrected visual acuity (BCVA), and refractive error pre- and ≥50 days postoperatively. Results: Among 715 patients (mean age 72.3±9.1 years, 55.5% female), preoperative UCVA was <3/60 (legally blind) bilaterally in 13.3% and unilaterally in the operated eye in 50.9%. No subjects had UCVA >6/18 preoperatively. Small incision cataract surgery was performed in 92.3% patients. Among 662 patients (92.6%) completing follow-up was ≥ 40 days after surgery, BCVA was ≥6/18 in 80.1%, UCVA was ≥6/18 in 57.1% and UCVA was <3/60 in 2.1%. Older age (p<0.001), female sex (p=0.04), worse refractive error (p=0.02) and presence of intra- (p=0.002) and postoperative surgical complications (p<0.001), were independently associated with worse postoperative UCVA. Based on these results, the MCSP cured an estimated 124,950 cases (13.3%×[100-2.1%]×1.05 million) of bilateral and 502,500 (50.9%×[100-2.1%]×1.05 million) of unilateral blindness. Conclusions: Due to relatively good outcomes and the large number of surgeries performed on blind persons, the sight-restoring impact of the MCSP was probably substantial. © Informa Healthcare USA, Inc.

Assessment of higher plant species suitability for ecological restoration following major disturbance

O presente trabalho é constituído por uma revisão bibliográfica e uma série de estudos científicos experimentais visando a melhoria do conhecimento da ecologia de germinação e resposta ao estresse hídrico em arbustos autóctones. Estes estudos pretendem contribuir para o conhecimento da ecologia de espécies autóctones na fase de germinação e estabelecimento inicial das plântulas através da comparação da resposta de sementes de diferentes proveniências. Os primeiros três capítulos focam-se no estudo dos efeitos de pré-tratamentos na germinação de espécies arbustivas com diferentes estratégias de regeneração e dormência da semente, enquanto os dois últimos capítulos incidem sobre o efeito de diferentes condições de disponibilidade de água na germinação e estabelecimento inicial de plântulas com potencial para restauro ecológico. Este estudo procura abordar aspetos importantes para o estudo e validação do uso de espécies alvo para o restauro ecológico em zonas Mediterrânicas, contribuindo deste modo para a melhoria do conhecimento da ecologia destas espécies. A germinação foi estimulada por pré-tratamentos de calor em quatro das cinco espécies cuja época de dispersão da semente na primavera-verão. As sementes provenientes do sul tenderam a germinar melhor, sendo ao mesmo tempo mais pequenas. Por outro lado, a germinação em espécies cuja dispersão da semente ocorre no outono-inverno variou de acordo com o tipo de dormência da semente. A germinação foi em geral favorecida pela estratificação a frio na espécie apresentando dormência fisiológica mas foi negativamente afetada na espécie que não apresenta dormência. Esta resposta não foi, no entanto, inequívoca pois foi dependente da proveniência estudada. O efeito da estratificação a frio teve em geral um efeito mais positivo ou menos negativo nas sementes provenientes do norte em comparação com as outras proveniências. O stress-osmótico teve um efeito negativo consistente na germinação de Pistacia lentiscus e outro fator que também afetou significativamente a germinação foi a variabilidade intra-populacional entre plantas mãe. As duas proveniências apresentaram diferentes graus de associação entre a germinação e/ou caracteres morfológicos da semente ou planta mãe. Quanto à fase de estabelecimento inicial, o baixo conteúdo em água teve um claro efeito negativo no investimento relativo em biomassa acima do solo e um efeito positivo no investimento relativo em biomassa abaixo do solo em Arbutus unedo. Esta resposta não foi inequívoca, uma vez que as proveniências diferiram em adaptações morfológicas ao baixo conteúdo em água. As plântulas da proveniência mais húmida revelaram uma taxa de crescimento relativo superior mas, ao mesmo tempo, uma fraca adaptação às condições de baixa disponibilidade de água, quando comparadas com as outras proveniências. Ao contrário, as plântulas da proveniência seca com verão mais quente apresentaram semelhantes diâmetro do colo da raiz, peso seco de folhas e performance fisiológica sob os dois regimes de irrigação. Os resultados obtidos revelam diferenças significativas na germinação e desenvolvimento inicial entre as distintas proveniências que poderão estar relacionadas com adaptações ao clima dos locais de origem. Os desenvolvimentos futuros do estudo dos mecanismos subjacentes às adaptações observadas poderiam contribuir para a melhoria das previsões de sucesso do estabelecimento inicial em diferentes populações de plantas, permitindo aumentar a confiança e efetividade de custos nas decisões relacionadas com ações de restauro ecológico em cenários de alterações climáticas.

Training control centers' operators in incident diagnosis and power restoration using intelligent tutoring systems

The activity of Control Center operators is important to guarantee the effective performance of Power Systems. Operators’ actions are crucial to deal with incidents, especially severe faults like blackouts. In this paper, we present an Intelligent Tutoring approach for training Portuguese Control Center operators in tasks like incident analysis and diagnosis, and service restoration of Power Systems. Intelligent Tutoring System (ITS) approach is used in the training of the operators, having into account context awareness and the unobtrusive integration in the working environment. Several Artificial Intelligence techniques were criteriously used and combined together to obtain an effective Intelligent Tutoring environment, namely Multiagent Systems, Neural Networks, Constraint-based Modeling, Intelligent Planning, Knowledge Representation, Expert Systems, User Modeling, and Intelligent User Interfaces.

Inexact restoration approaches to solve mathematical program with complementarity constraints

Mathematical Program with Complementarity Constraints (MPCC) finds applica- tion in many fields. As the complementarity constraints fail the standard Linear In- dependence Constraint Qualification (LICQ) or the Mangasarian-Fromovitz constraint qualification (MFCQ), at any feasible point, the nonlinear programming theory may not be directly applied to MPCC. However, the MPCC can be reformulated as NLP problem and solved by nonlinear programming techniques. One of them, the Inexact Restoration (IR) approach, performs two independent phases in each iteration - the feasibility and the optimality phases. This work presents two versions of an IR algorithm to solve MPCC. In the feasibility phase two strategies were implemented, depending on the constraints features. One gives more importance to the complementarity constraints, while the other considers the priority of equality and inequality constraints neglecting the complementarity ones. The optimality phase uses the same approach for both algorithm versions. The algorithms were implemented in MATLAB and the test problems are from MACMPEC collection.

Oxo-molybdenum(VI) complexes containing chiral ligands: catalytic applications in selective epoxidations

Dissertation presented to obtain the Ph.D. degree in Chemistry

A New ROV Design: Issues on Low Drag and Mechanical Symmetry

This paper reports the design of a new remotely operated underwater vehicle (ROV), which has been developed at the Underwater Systems and Technology Laboratory (USTL) - University of Porto. This design is contextualized on the KOS project (Kits for underwater operations). The main issues addressed here concern directional drag minimization, symmetry, optimized thruster positioning, stability and layout of ROV components. This design is aimed at optimizing ROV performance for a set of different operational scenarios. This is achieved through modular configurations which are optimized for each different scenario.

Is mental practice an effective adjunct therapeutic strategy for upper limb motor restoration after stroke? A systematic review and meta- analysis

Stroke is one of the most common conditions requiring rehabilitation, and its motor impairments are a major cause of permanent disability. Hemiparesis is observed by 80% of the patients after acute stroke. Neuroimaging studies showed that real and imagined movements have similarities regarding brain activation, supplying evidence that those similarities are based on the same process. Within this context, the combination of mental practice (MP) with physical and occupational therapy appears to be a natural complement based on neurorehabilitation concepts. Our study seeks to investigate if MP for stroke rehabilitation of upper limbs is an effective adjunct therapy. PubMed (Medline), ISI knowledge (Institute for Scientific Information) and SciELO (Scientific Electronic Library) were terminated on 20 February 2015. Data were collected on variables as follows: sample size, type of supervision, configuration of mental practice, setting the physical practice (intensity, number of sets and repetitions, duration of contractions, rest interval between sets, weekly and total duration), measures of sensorimotor deficits used in the main studies and significant results. Random effects models were used that take into account the variance within and between studies. Seven articles were selected. As there was no statistically significant difference between the two groups (MP vs control), showed a - 0.6 (95% CI: -1.27 to 0.04), for upper limb motor restoration after stroke. The present meta-analysis concluded that MP is not effective as adjunct therapeutic strategy for upper limb motor restoration after stroke.