Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Dielectrics in a time-dependent electric field: a real-time approach based on density-polarization functional theory

In the presence of a (time-dependent) macroscopic electric field the electron dynamics of dielectrics cannot be described by the time-dependent density only. We present a real-time formalism that has the density and the macroscopic polarization P as key quantities. We show that a simple local function of P already captures long-range correlation in linear and nonlinear optical response functions. Specifically, after detailing the numerical implementation, we examine the optical absorption, the second- and third-harmonic generation of bulk Si, GaAs, AlAs and CdTe at different level of approximation. We highlight links with ultranonlocal exchange-correlation functional approximations proposed within linear response time-dependent density functional theory framework.

A functional genomics approach reveals novel quantitative trait loci associated with platelet signalling pathways

Platelet response to activation varies widely between individuals but shows interindividual consistency and strong heritability. The genetic basis of this variation has not been properly explored. We therefore systematically measured the effect on function of sequence variation in 97 candidate genes in the collagen and adenosine-diphosphate (ADP) signaling pathways. Resequencing of the genes in 48 European DNA samples nearly doubled the number of known single nucleotide polymorphisms (SNPs) and informed the selection of 1327 SNPs for genotyping in 500 healthy Northern European subjects with known platelet responses to collagen-related peptide (CRP-XL) and ADP. This identified 17 novel associations with platelet function (P < .005) accounting for approximately 46% of the variation in response. Further investigations with platelets of known genotype explored the mechanisms behind some of the associations. SNPs in PEAR1 associated with increased platelet response to CRP-XL and increased PEAR1 protein expression after platelet degranulation. The minor allele of a 3' untranslated region (UTR) SNP (rs2769668) in VAV3 was associated with higher protein expression (P = .03) and increased P-selectin exposure after ADP activation (P = .004). Furthermore the minor allele of the intronic SNP rs17786144 in ITPR1 modified Ca2+ levels after activation with ADP (P < .004). These data provide novel insights into key hubs within platelet signaling networks.

Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Three new Mn(III) complexes [MnL1(OOCH)(OH2)] (1), [MnL2(OH2)(2)][Mn2L22(NO2)(3)] (2) and [Mn2L21(NO2)(2)] (3) (where H2L1 = H(2)Me(2)Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene and H2L2 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta-1,6-diene) have been synthesized. X-ray crystal structure analysis reveals that 1 is a mononuclear species whereas 2 contains a mononuclear cationic and a dinuclear nitrite bridged (mu-1 kappa O:2 kappa O') anionic unit. Complex 3 is a phenoxido bridged dimer containing terminally coordinated nitrite. Complexes 1-3 show excellent catecholase-like activity with 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. Kinetic measurements suggest that the rate of catechol oxidation follows saturation kinetics with respect to the substrate and first order kinetics with respect to the catalyst. Formation of bis(mu-oxo)dimanganese(III,III) as an intermediate during the course of reaction is identified from ESI-MS spectra. The characteristic six line EPR spectra of complex 2 in the presence of 3,5-DTBC supports the formation of manganese(II)-semiquinonate as an intermediate species during the catalytic oxidation of 3,5-DTBC.

Numerical implementation of a functional observability algorithm : a singular value decomposition approach

The paper outlines a numerical algorithm to implement the concept of Functional Observability introduced in [6] based on a Singular Value Decomposition approach. The key feature of this algorithm is in outputting a minimum number of additional linear functions of the state vector when the system is Functional Observable, these additional functions are required to design the smallest possible order functional observer as stated in [6].

A system decomposition approach to the design of functional observers

This paper reports a system decomposition that allows the construction of a minimum-order functional observer using a state observer design approach. The system decomposition translates the functional observer design problem to that of a state observer for a smaller decomposed subsystem. Functional observability indices are introduced, and a closed-form expression for the minimum order required for a functional observer is derived in terms of those functional observability indices. © 2014 Taylor & Francis.

Approach to fault detection of time-delay systems using functional observers

A new methodology is reported for designing functional observers to detect actuator faults of a class of time-delay systems where the matrix pair (A, C) is not observable. First, a generalised state transformation is used to transform the system into new coordinates where the delay term associated with the state vector is injected into the system's output and input. Then, a minimum-order functional observer is designed to construct a residual function that can trigger system faults. The finding is significant as it is now possible to detect faults of time-delay systems where the pair (A, C) is not required to be observable. A numerical example is given to illustrate the effectiveness of the proposed design approach. © The Institution of Engineering and Technology 2014.

Minimal multi-functional observers for linear systems using a direct approach

The direct approach in designing functional observers was first presented in [1] for estimating a single function of the states of a Linear Time-Invariant (LTI) system. One of the benefits of the direct scheme is that it does not require solving the interconnected Sylvester equations that appear in the other observer design approaches. In the present paper, the direct approach is extended to reconstruct multiple functions of the states in such a way that the minimum possible order of the observer is achieved. The observer is designed so that an asymptotic functional observer can be obtained with arbitrary convergence rate. In the proposed methodology, it is not necessary that a reduced order observer exists for the desired functions to be estimated. To release this limitation, an algorithm is employed to find some auxiliary functions in the minimum required number to be appended to the desired functions. This method assumes that the system is functional observable. This assumption however is less restrictive than the observability and detectability conditions of the system. A numerical example and simulation results explain the efficacy and the benefits of the proposed algorithm.

Casimir effect for the scalar field under Robin boundary conditions: a functional integral approach

In this work we show how to define the action of a scalar field such that the Robin boundary condition is implemented dynamically, i.e. as a consequence of the stationary action principle. We discuss the quantization of that system via functional integration. Using this formalism, we derive an expression for the Casimir energy of a massless scalar field under Robin boundary conditions on a pair of parallel plates, characterized by constants c(1) and c(2). Some special cases are discussed; in particular, we show that for some values of cl and c(2) the Casimir energy as a function of the distance between the plates presents a minimum. We also discuss the renormalization at one-loop order of the two-point Green function in the philambda(4) theory subject to the Robin boundary condition on a plate.

Functional and esthetic rehabilitation with In-Ceram alumina and zirconia system: A multidisciplinary approach

The development of all-ceramic systems following metalceramics restorations allowed simulation of natural dentition due to favorable esthetics and resistance. In-Ceram is an alternative when esthetics is primordial as well as resistance required in rehabilitation. However, an ideal smile is associated to not only shape, color, texture and translucency but also harmony with gingival tissue. So, the aim of this study is to report a clinical case based on periodontal and fixed partial dentures principles to perform periodontal plastic surgery followed by esthetic rehabilitation. A female patient, 40-year-old, presented complaint about dental esthetics. After clinical and radiographic exams, metal-ceramics crowns (teeth 11, 12, 13, 21, 22 and 23) were considered unsatisfactory due to marginal leakage, color change in gingival tissue associated to metallic margin, and gummy smile. So, a crown lengthening surgery of anterior teeth was performed followed by rehabilitation of superior teeth with In-Ceram single crowns. Clinical significance: The interaction between periodontics and fixed prosthodontic area is the key of an adequated treatment planning which involves gingival smile to provide function and an esthetic condition in association with an esthetic, resistant and predictable material.

Noninvasive and multidisciplinary approach to the functional and esthetic rehabilitation of amelogenesis imperfecta: a pediatric case report

Case Report. An 8-year-old girl with amelogenesis imperfecta (AI) reported unsatisfactory aesthetics, difficulty in mastication, and dental hypersensitivity. The intraoral examination observed mixed dentition, malocclusion in anteroposterior relationships, anterior open bite, and dental asymmetry. A hypoplastic form of AI was diagnosed in the permanent dentition. A multidisciplinary planning was performed and divided into preventive, orthopedic, and rehabilitation stages. Initially, preventive treatment was implemented, with fluoride varnish applications, in order to protect the fragile enamel and reduce the dental sensitivity. In the second stage, the patient received an interceptive orthopedic treatment to improve cross-relationship of the arches during six months. Finally, the rehabilitation treatment was executed to establish the vertical dimension. In the posterior teeth, indirect composite resin crowns were performed with minimally invasive dental preparation. Direct composite resin restorations were used to improve the appearance of anterior teeth. Follow-Up. The follow-up was carried out after 3, 6, 12, and 18 months. After 18 months of follow-up, The restoration of integrity, oral hygiene, and patient satisfaction were observed . Conclusion. Successful reduction of the dental hypersensitivity and improvement of the aesthetic and functional aspects as well as quality of life were observed.