Generalizing minimal supergravity

In Grand Unified Theories (GUTs), the Standard Model (SM) gauge couplings need not be unified at the GUT scale due to the high-dimensional operators. Considering gravity mediated supersymmetry breaking, we study for the first time the generic gauge coupling relations at the GUT scale, and the general gaugino mass relations which are valid from the GUT scale to the electroweak scale at one loop. We define the index k   for these relations, which can be calculated in GUTs and can be determined at the Large Hadron Collider and the future International Linear Collider. Thus, we give a concrete definition of the GUT scale in these theories, and suggest a new way to test general GUTs at future experiments. We also discuss five special scenarios with interesting possibilities. With our generic formulae, we present all the GUT-scale gauge coupling relations and all the gaugino mass relations in the SU(5)$\mathit{SU}(5)$ and SO(10)$\mathit{SO}(10)$ models, and calculate the corresponding indices k. Especially, the index k   is 5/3 in the traditional SU(5)$\mathit{SU}(5)$ and SO(10)$\mathit{SO}(10)$ models that have been studied extensively so far. Furthermore, we discuss the field theory realization of the U(1)$U(1)$ flux effects on the SM gauge kinetic functions in F-theory GUTs, and calculate their indices k as well.     

Tuning Local Coordination Environments of Manganese Single-Atom Nanozymes with Multi-Enzyme Properties for Selective Colorimetric Biosensing

Single-atom nanozymes (SAzymes) are promising in next-generation nanozymes, nevertheless, how to rationally modulate the microenvironment of SAzymes with controllable multi-enzyme properties is still challenging. Herein, we systematically investigate the relationship between atomic configuration and multi-enzymatic performances. The constructed Mn_SA−N₃-coordinated SAzymes (Mn_SA−N₃−C) exhibits much more remarkable oxidase-, peroxidase-, and glutathione oxidase-like activities than that of Mn_SA−N₄−C. Based on experimental and theoretical results, these multi-enzyme-like behaviors are highly dependent on the coordination number of single atomic Mn sites by local charge polarization. As a consequence, a series of colorimetric biosensing platforms based on Mn_SA−N₃−C SAzymes is successfully built for specific recognition of biological molecules. These findings provide atomic-level insight into the microenvironment of nanozymes, promoting rational design of other demanding biocatalysts.     

A new synthesis of lysophosphatidylcholines and related derivatives. Use of p-toluenesulfonate for hydroxyl group protection

A new stereoselective synthesis of lysophosphatidylcholines is reported. The synthesis is based upon (1) the use of 3-p-toluenesulfonyl-sn-glycerol to provide the stereocenter for construction of the optically active lysophospholipid molecule, (2) tetrahydropyranylation of the secondary alcohol function to achieve orthogonal protection of the sn-2- and sn-3-glycerol positions, and (3) elaboration of the phosphodiester headgroup using a 2-chloro-1,3,2-dioxaphospholane/trimethylamine sequence. In the course of developing the synthesis it has been discovered that methoxyacetate displacement of the sn-3-p-toluenesulfonate yields a reactive methoxyacetyl ester, which in turn can be selectively cleaved with methanol/tert-butylamine, while the ester group at the sn-1-position remains unaffected. The sequence has been shown to be suitable for preparation of spectroscopically labeled lysophosphatidylcholines. One of these compounds was readily converted to a double-labeled mixed-chain phosphatidylcholine applicable for real-time fluorescence resonance energy transfer (FRET) assay of lipolytic enzymes. In addition, the work led to new synthetic strategies based on chemoselective manipulation of the tosyl group in the presence of other base-labile groups such as FMOC derivatives that are often used for the protection of amino and hydroxyl groups in syntheses.     

Antiproliferative activity, antioxidant capacity and tannin content in plants of semi-arid northeastern Brazil

The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents.     

Carboxylate clays: A model study for polypropylene/clay nanocomposites

Sodium-montmorillonite was intercalated by carboxylate salts to prepare carboxylate clays. The intercalation of sodium acetate doubles the clay basal spacing and no degradation of the carboxylate clay is noticed in the extrusion temperature range. These carboxylate clays were used to synthesize polypropylene-graft-maleic anhydride (PP-g-MA)/clay nanocomposites. Nanocomposites were also produced by a one-pot process using in situ prepared carboxylate clay. The carboxylate salts within the clay layers partially neutralize the maleic anhydride groups of the PP-g-MA matrix, in situ during the melt compounding. The ionic groups of the partially neutralized polymer offer favourable interactions with the clay, hence reinforcing the interfacial bond between the polymer and the clay and improving the composite properties. The use of carboxylate clay clearly improves the clay dispersion into the PP-g-MA matrix and improves the nanocomposite’s thermal and rheological properties.     

Self-assembled films based on polypyrrole and carbon nanotubes composites for the determination of Diuron pesticide

In this work, polypyrrole (PPy) and its respective composite with functionalized multi-walled carbon nanotubes (MWCNT) were obtained by chemical polymerization of the monomer pyrrole in aqueous solution. The obtained PPy as well as its composite (PPy-MWCNT) were characterized by Fourier transform infrared spectroscopy (FTIR) and were used to produce nanostructured self-assembled (SA) films deposited onto glass substrates covered with indium tin oxide (ITO). The SA films were produced with alternated layers of polystyrene sulphonated (PSS) and were characterized by UV-visible, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) analyses. The applicability of the SA films was evaluated by square wave voltammetry (SWV) with standard additions of aliquots of Diuron pesticide in Britton-Robinson buffer solutions (pH = 2.0). The results showed an oxidation peak at 0.23 V which increases in function of the Diuron concentration for both the SA films. It was also observed that the SA film based on the composite (PPy-MWCNT/PSS) showed a peak current intensity about ten times higher in comparison with its unmodified counterpart (PPy/PSS) for a Diuron concentration of 4.29 × 10^?5 mol L^?1, indicating a synergic effect between PPy and MWCNT in the composite. The limits of quantification (LOQ) and limits of detection (LOD) were respectively 8.6 × 10^?7 mol L^?1 and 2.6 × 10^?7 mol L^?1.     

Synthesis and characterization of thiosemicarbazone derivatives of 2-ethoxy-3-methoxy-benzaldehyde and their rhenium(I) complexes

The ligands (HL¹, HL² and HL³) have been prepared and their reaction with fac-[ReX(CO)₃(CH₃CN)₂] (X = Br, Cl) in chloroform gave the adducts [ReX(CO)₃(HL)] (1a X = Cl, R = H; 1a′ X = Br, R = H; 1b X = Cl, R = CH₃; 1b′ X = Br, R = CH₃; 1c X = Cl, R = Ph; 1c′ X = Br, R = Ph) in good yield. All the compounds have been characterized by elemental analysis, mass spectrometry (FAB), IR and ¹H NMR spectroscopic methods, and the structures of the ligands have been elucidated by X-ray diffraction. In the case of HL¹, we have tried the reaction with [ReX(CO)₅] (X = Br, Cl) in toluene and we proved the formation of the adduct also by this way by the isolation of single crystals of 1a′ · ½C₇H_8.     

Comparative study of the oxidative and thermal stability of vegetable oils to be used as lubricant bases

Demand for lubricating oils is increasing in the growing Brazilian economy. The use of vegetable bases in exchange of minerals can bring socio-economic and environmental benefits for Brazil. The purpose of this study is to compare the thermal and oxidative stability of vegetable oils related to the bases commonly used as lubricants. In this study, thermogravimetric analysis of castor oil, cotton oil, macauba’s almond oil, passion oil, paraffinic mineral oil, naphthenic oil (NH-140) and synthetic oil (Etro) was performed in inert and oxidative atmosphere to study the thermal and oxidative degradation of the vegetable oils related to the most common lubricants’ oils base. These oils’ oxidation stability were determined by standard procedures (ISO 6886). The use of mineral oil’s additives in these vegetable oils was tested to verify the viability of these additives to improve the oxidative stability of the vegetable oils. The castor oil and the cotton oil presented results of thermal analysis similar to the mineral and synthetic bases values. The castor oil was the only vegetable oil that showed a great oxidative stability. All other vegetable oils had their oxidative stability significantly increased by the additives.     

A linear semi-infinite programming strategy for constructing optimal wavelet transforms in multivariate calibration problems

A novel strategy for the optimization of wavelet transforms with respect to the statistics of the data set in multivariate calibration problems is proposed. The optimization follows a linear semi-infinite programming formulation, which does not display local maxima problems and can be reproducibly solved with modest computational effort. After the optimization, a variable selection algorithm is employed to choose a subset of wavelet coefficients with minimal collinearity. The selection allows the building of a calibration model by direct multiple linear regression on the wavelet coefficients. In an illustrative application involving the simultaneous determination of Mn, Mo, Cr, Ni, and Fe in steel samples by ICP-AES, the proposed strategy yielded more accurate predictions than PCR, PLS, and nonoptimized wavelet regression.