Eremostachiin: a new furanolabdane diterpene glycoside from Eremostachys glabra

The reversed-phase preparative HPLC analysis of the methanol extract of the rhizomes of Eremostachys glabra (Lamiaceae) led to the isolation of two furanolabdane diterpene glycosides, phlomisoside II, and beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl ester of phlomisoic acid (named eremostachiin), the latter being a novel natural product. The structure of the new compound has been elucidated unambiguously by HRMS and a series of 1D- and 2D-NMR spectroscopic techniques. The free radical scavenging activity of these compounds was assessed using the DPPH assay.     

Identification and quantification of protein carbonylation using light and heavy isotope labeled Girard's P reagent

Protein carbonyls are one of the most widely studied markers of oxidative stress. Determining increases in the concentration of protein carbonyls known to be associated with neurodegenerative diseases, heart disease, cancer and ageing. Identification of carbonylation sites in oxidized proteins has been a challenge. Even though recent advances in proteomics has facilitate the identification of carbonylation sites in oxidized proteins, confident identification remains a challenge due to the complicated nature of oxidative damage and the wide range of oxidative modifications. Here, we report the development of a multiplexing strategy that facilitates confident carbonylated peptide identification through a combination of heavy and light isotope coding and a multi-step filtering process. This procedure involves (1) labeling aliquots of oxidized proteins with heavy and light forms of Girard's reagent P (GPR) and combining them in a 1:1 ratio along with (2) LC/MS and MALDI-MS/MS analysis. The filtering process uses LC/MS and MALDI-MS/MS data to rule out false positives by rejecting peptide doublets that do not appear with the correct concentration ratio, retention time, tag number, or resolution. This strategy was used for the identification of heavily oxidized transferrin peptides and resulted in identification 13 distinct peptides. The competency of the method was validated in a complex mixture using oxidized transferrin in a yeast lysate as well as oxidized yeast. Twenty-five percent of the peptides identified in a pure oxidized sample of transferrin were successfully identified from the complex mixture. Analysis of yeast proteome stressed with hydrogen peroxide using this multiplexing strategy resulted in identification of 41 carbonylated peptides from 36 distinct proteins. Differential isotope coding of model peptides at different concentrations followed by mixing at different ratios was used to establish the linear dynamic range for quantification of carbonylated peptides using light and heavy forms of GPR.     

Impact of localized surface preheating on the microstructure and crack formation in laser direct deposition of Stellite 1 on AISI 4340 steel

Crack formation in laser cladding of the hardfacing alloy Stellite 1 on AISI-SAE 4340 steel was prevented through locally preheating the substrate prior to the deposition process. Numerical analysis showed that the preheating process helps developing a relatively steadier melt temperature as well as decreasing the cooling rates and consequently the thermal stresses during the subsequent deposition process. Microstructural analysis revealed a thicker cross-section with smoother surface profile, more uniform surface hardness and even distribution of a dendritic morphology in the preheated sample. This confirmed the presence of a well-developed melt pool with a homogeneous composition at solidification. The microstructure of non-preheated sample was, however, considerably non-uniform consisting of macro-scale colonies of dendritic and lamellar (eutectic) structures. The experimental observations, as implied through the numerical results, showed that the preheated sample, in general, reveals more uniform structure and properties making it less prone to cracking during the deposition process.     

Design of ionic liquid 3-methyl-1-sulfonic acid imidazolium nitrate as reagent for the nitration of aromatic compounds by in situ generation of NO(2) in acidic media

3-Methyl-1-sulfonic acid imidazolium nitrate ([Msim]NO(3)) as a new Br?nsted acidic ionic liquid and nitrating agent was prepared and used for the efficient nitration of aromatic compounds (even aniline derivatives). The dramatic effect of this reagent by in situ generation of nitrogen dioxide as a radical on aromatic compounds to give nitroarenes has been studied.     

Solvent-free and three-component synthesis of 1H,6H-6λ5-[1,2]benzoxaphospholo[2,3-b][1,2]benzoxaphosphol-1-ones

A concise and facile synthesis of a new class of P,O-heterocycles is described. Knoevenagel condensation reaction of a salicylaldehyde and a cyclohexane-1,3-dione forms an α,β-unsaturated intermediate, which undergoes nucleophilic addition of a trialkyl phosphite under solvent-free conditions to afford the title compounds in good to excellent yields.     

A nonmonotone trust-region line search method for large-scale unconstrained optimization

We consider an efficient trust-region framework which employs a new nonmonotone line search technique for unconstrained optimization problems. Unlike the traditional nonmonotone trust-region method, our proposed algorithm avoids resolving the subproblem whenever a trial step is rejected. Instead, it performs a nonmonotone Armijo-type line search in direction of the rejected trial step to construct a new point. Theoretical analysis indicates that the new approach preserves the global convergence to the first-order critical points under classical assumptions. Moreover, superlinear and quadratic convergence are established under suitable conditions. Numerical experiments show the efficiency and effectiveness of the proposed approach for solving unconstrained optimization problems.     

A chemometrics approach for simultaneous determination of cyanazine and propazine based on a carbon paste electrode modified by a molecularly imprinted polymer

In a completely rational and designed approach, simultaneous determination of cyanazine and propazine in environmental and food samples was performed using a molecularly imprinted polymer modified carbon paste electrode (MIP-CPE) and partial least squares. The MIP-CPE designed is based on the theoretical studies functioned as a selective recognition element and pre-concentrator agent for cyanazine and propazine. Fractional factorial and central composite designs were performed to recognize, and subsequently optimize, the variables affecting the cathodic stripping voltammetric currents for the analytes. The important variables were identified to be accumulation potential with optimum values of -0.45 and -0.44 V and pH with optimum values of 2.40 and 2.34 for cyanazine and propazine, respectively. Exploration of the overall optimum conditions for simultaneous determination of cyanazine and propazine resulted in accumulation potential of -0.44 V and pH of 2.4. Dynamic linear ranges of 0.05-9.00 μmol L(-1) and 0.01-1.00 μmol L(-1) and detection limits of 0.010 and 0.001 μmol L(-1) were obtained for cyanazine and propazine, respectively. The results of the application of the proposed method on the simultaneous determination of cyanazine and propazine in foodstuffs and environmental samples were satisfactory.     

Morphologies and magnetic properties of FeCo nanoparticles modulated by changing the types of ligands of Co

A new way of preparing FeCo nanoparticles has been developed using the co-precipitation technique based on the appropriate Co precursors of different types of ligands. These new precursors have been prepared by the reaction of cobalt acetate with three various coordination compositions for forming cobalt complex types. This technique provides proper control on nanoparticle size distribution after annealing to 500 °C. The variation of the magnetic properties with the type of ligands of Co can arise from the changes of the microstructures and crystalline anisotropies. Maximum coercivity values of 480 Oe were obtained. It is found that the precursors with special structures can prevent from agglomeration without presence of any surfactants.     

Control of the supercontinuum spectrum bandwidth and emission efficiency for intense-isolated sub 40-as pulse generation by using a coherent superposition of states

We present a systematic study for generation of intense and short single as pulse in pre-excited He-ionic medium with the use of a same-frequency laser field synthesis. By preparing He+ ions in a coherent superposition of the ground and excited states, a depth of spectral modulation efficiently decreases and the efficiency of harmonic plateau increases. By means of optimizing the laser parameters, the broadband XUV supercontinuum achieve by the superposition state scheme. It shows that by increasing the harmonic order of the supercontinuum, emission efficiency increases. The detailed view shows that the short-trajectory contributes to each supercontinuous harmonic and long-trajectory fully suppresses. Finally, by superposing some properly selected harmonics from optimal spectrum, an intense and almost transform-limited isolated 38-as pulse can be generated without phase compensation. A single isolated 5-as pulse can be achieved after phase compensation. These results are explained by using classical and quantum time-frequency analyses.     

Silicon carbide nanocones: Computational analysis of chemical shieldings for pristine and boron/nitrogen decorated models

Density functional theory (DFT) calculations were performed to investigate the electronic and structural properties of pristine and boron/nitrogen (B/N) decorated models of a representative silicon carbide nanocone (SiCNC). The atoms of apexes and tips were differently decorated by B/N atoms to make all possible decorations of the investigated SiCNC. The evaluated parameters by the optimization processes and nuclear magnetic resonance (NMR) calculations indicated that the overall and atomic scale properties of the investigated SiCNCs are significantly dependent on the ways of decorations of Si/C atoms by B/N atoms. The Si/C atoms close to the decorated regions also exhibited notable changes in comparison to the pristine model.