Spatial and spin symmetry breaking in semidefinite-programming-based Hartree-Fock theory

The Hartree-Fock problem was recently recast as a semidefinite optimization over the space of rank-constrained two-body reduced-density matrices (RDMs) [Phys. Rev. A 89, 010502(R) (2014)]. This formulation of the problem transfers the non-convexity of the Hartree-Fock energy functional to the rank constraint on the two-body RDM. We consider an equivalent optimization over the space of positive semidefinite one-electron RDMs (1-RDMs) that retains the non-convexity of the Hartree-Fock energy expression. The optimized 1-RDM satisfies ensemble $N$-representability conditions, and ensemble spin-state conditions may be imposed as well. The spin-state conditions place additional linear and nonlinear constraints on the 1-RDM. We apply this RDM-based approach to several molecular systems and explore its spatial (point group) and spin ($S^2$ and $S_3$) symmetry breaking properties. When imposing $S^2$ and $S_3$ symmetry but relaxing point group symmetry, the procedure often locates spatial-symmetry-broken solutions that are difficult to identify using standard algorithms. For example, the RDM-based approach yields a smooth, spatial-symmetry-broken potential energy curve for the well-known Be--H$_2$ insertion pathway. We also demonstrate numerically that, upon relaxation of $S^2$ and $S_3$ symmetry constraints, the RDM-based approach is equivalent to real-valued generalized Hartree-Fock theory.Comment: 9 pages, 6 figure

Comparison of esters determination techniques in cachaça

An analytical comparison of three different techniques for quantitative profile of esters in cachaça is reported. The Ministério da Agricultura Pecuária e Abastecimento (MAPA) recommends the use of GC/FID or volumetry. Despite being laborious and lacking in chemical speciation, the volumetric technique for total ester content shows to be appropriate, reproducible, and accurate for the analysis of cachaça. However, the GC/FID suggested by MAPA, considering only ethyl acetate, shows inaccuracy, underestimating the total ester content by a median factor of 72%, mainly due to the absence of ethyl lactate analysis. On the other hand, the GC/MS technique that comprises the analysis and speciation of nine esters, including ethyl lactate, proved to be reproducible, simple, fast and accurate for the analysis of total ester content in cachaça. Thus, the total ester content results obtained using GC/FID must be considered with precaution.FAPESPCNP

A novel approach for micro-antenna fabrication on ZrO2 substrate assisted by laser printing for smart implants

The use of Yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) in medicine has rapidly expanded over the past decade, driven by its advantageous properties, showing potential to overcome titanium alloy in implant fabrication. The release of metal ions and the aesthetic problems of titanium alloy implants are the main reasons for this trend. In addition to meeting expectations regarding its properties, an implant must possess intrinsic capacities such as auto-diagnostic and auto-treatment. Thus, based on the concept of smart implants, this work proposes a hybrid approach for printing a part of the communication system of a zirconia implant by resorting to laser technology, aiming to endow the implant with intrinsic capacities. Therefore, the antenna was designed and then printed on the zirconia surface. The laser was applied as a versatile tool, whether for preparing the surface of the material in a subtractive way, by creating the micro-cavity, or for printing the silver-based antenna in an additive way through laser technology. The silver powder was used as the conductor material of the antenna. The results revealed that the antenna is capable of communicating from inside the body with the outside world without needing to have an exterior antenna attached to the skin.This work has been supported by the FCT (Fundação para a Ciência e Tecnologia -Portugal) in the scope of the projects UID/EEA/04436/2019; Magsense_POCI-01-0247-FEDER-033783, Add.Additive_Manufacturing to Portuguese Industry_POCI-01-0247-FEDER-024533, grant SFRH/BD/ 116554/2016 and the CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) for the grant 205791/2014-

Brief Report: Excitatory and Inhibitory Brain Metabolites as Targets of Motor Cortex Transcranial Direct Current Stimulation Therapy and Predictors of Its Efficacy in Fibromyalgia

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/110535/1/art38945.pd

Synergy of DNA intercalation and catalytic activity of a copper complex towards improved polymerase inhibition and cancer cell cytotoxicity

Improving the binding of metal complexes to DNA to boost cancer cell cytotoxicity requires fine tuning of their structural and chemical properties. Copper has been used as a metal center in compounds containing intercalating ligands due to its ability to catalytically generate reactive oxygen species (ROS), such as hydroxyl radicals (OH˙). We envision the synergy of DNA binding and ROS generation in proximity to target DNA as a powerful chemotherapy treatment. Here, we explore the use of [Cu(2CP-Bz-SMe)]2+(2CP-Bz-SMe = 1,3-bis(1,10-phenanthrolin-2-yloxy)-N-(4-(methylthio)benzylidene)propan-2-amine) for this purpose by characterizing its cytotoxicity, DNA binding, and ability to affect DNA replication through the polymerase chain reaction - PCR and nuclease assays. We determined the binding (Kb) and Stern-Volmer constants (KSV) for complex-DNA association of 5.8 ± 0.14 × 104and 1.64 (±0.08), respectively, through absorption titration and competitive fluorescence experiments. These values were superior to those of other Cu-complex intercalators. We hypothesize that the distorted trigonal bipyramidal geometry of [Cu(2CP-Bz-SMe)]2+allows the phenanthroline fragments to be better accommodated into the DNA double helix. Moreover, the aromaticity of these fragments increases the local hydrophobicity thus increasing the affinity for the hydrophobic domains of DNA. Nuclease assays in the presence of common reducing agents ascorbic acid, nicotinamide adenine dinucleotide, and glutathione showed the effective degradation of DNA due to thein situgeneration of OH˙. The [Cu(2CP-Bz-SMe)]2+complex showed cytotoxicity against the following human cancer cells lines A549, MCF-7, MDA-MB-231 and MG-63 with half maximal inhibitory concentration (IC50) values of 4.62 ± 0.48, 5.20 ± 0.76, 5.70 ± 0.42 and 2.88 ± 0.66 μM, respectively. These low values of IC50, which are promising if compared to that of cisplatin, are ascribed to the synergistic effect of ROS generation with the intercalation ability into the DNA minor grooves and blocking DNA replication. This study introduces new principles for synergizing the chemical and structural properties of intercalation compounds for improved drug-DNA interactions targeting cancer.Fil: Romo, Adolfo I. B.. University of Illinois. Urbana - Champaign; Estados Unidos. Universidade Federal do Ceara; BrasilFil: Carepo, Marta P.. Universidade Nova de Lisboa; PortugalFil: Levin, Pedro. Universidad de Santiago de Chile; ChileFil: Nascimento, Otaciro R.. Universidade Federal do São Carlos; BrasilFil: Díaz, Daniel E.. Universidad de Santiago de Chile; ChileFil: Rodriguez Lopez, Joaquin. University of Illinois. Urbana - Champaign; Estados UnidosFil: Leon, Ignacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Bezerra, Lucas F.. Universidade Federal do Ceara; BrasilFil: Lemus, Luis A.. Universidad de Santiago de Chile; ChileFil: Diógenes, Izaura C. N.. Universidade Federal do Ceara; Brasi

Methodology of geoarchaeological prospections in a fluvial basin (example of the Peruaçu river basin, Minas Gerais, Brazil).

Knowledge about the prehistoric occupancy of a region depends obviously on the method of data acquisition based on a systematic methodology. The recent introduction of the multidisciplinary approach in modem studies allows the elaboration of a systemic methodology of location of the archeological sites, based on the basic geomorphological unit, the hydrographical basin. The methodology elaborated and developed in the Rio Perua§u basin, in northern Minas Gerais, area studied since 1980, is founded on the morphogenesis and evolution of the landscape. Its goal is to help the understanding of the human colonization of a definite geomorphological unity.O conhecimento da ocupação pré-histórica de uma região depende dos métodos de aquisição de dados que devem se apoiar sobre uma metodologia sistemática. A introdução de uma abordagem interdisciplinar para as pesquisas modernas permite a elaboração de uma metodologia sistêmica de localização de sítios arqueológicos, a partir de uma unidade geomorfológica básica, a saber, a bacia hidrográfica. A metodologia elaborada e desenvolvida na bacia do rio Peruaçu, região norte do estado de Minas Gerais, estudada desde o início dos anos 1980, é fundada na análise morfogenética da paisagem. Ela tem por objetivo facilitar a compreensão da ocupação humana dentro de uma unidade geomorfológica definida

Pré-tratamento de resíduos agro-industriais e novas perspectivas na produção de bioprodutos

Visando contribuir para a melhoria das condições ambientais pela eliminação dos resíduos agrícolas/agroindustriais, bem como proporcionar a formação de uma linha de pesquisa com propósito de captar e disseminar informações técnicas e tecnológicas agregando maior valor nestes subprodutos ou resíduos é que o presente trabalho foi realizado. Deste modo, o sabugo de milho in natura foi submetido a dois diferentes processos de prétratamento para a extração das hemiceluloses, como etapa inicial de aplicação integral do resíduo, onde posteriormente estudos e aplicação do complexo celulose-lignina resultante seriam realizados. Dentro deste contexto, o objetivo deste trabalho foi determinar a eficiência de extração de frações de hemiceluloses de sabugo de milho por processos alcalinos (0,75 a 1,25 mol/L em 42,5ºC/180 min), e processos de autohidrólise (165 a 185ºC, razão líquida de 10:1p/p por 40 min). Este procedimento indicou o potencial de pré-tratamentos, em especial dos licores hemicelulosicos obtidos, como parte de um processo que conduza à utilização de materiais lignocelulósicos em diferentes processos biotecnológicos