Liquid chromatographic method for the analysis of two plant based insecticide synergists dillapiole and dihydrodillapiole

A reversed-phase LC method for the determination of two plant based insecticide synergists dillapiole (5-allyl 6,7-dimethoxy 1,3-benzodioxole) and dihydrodillapiole (5-n-propyl 6,7-dimethoxy-1,3-benzodioxole) is reported. The resolution of dillapiole and dihydrodillapiole has been achieved on RP-18 column using methanol-water (90:10, v/v) as mobile phase and a photodiode array detector at 207 nm. The response was linear in the range of 25-250 microg. The developed isocratic RP-LC method was validated for specificity, linearity, precision, and accuracy. It has been applied for individual or simultaneous detection, monitoring and quantification of dillapiole and dihydrodillapiole from treated French bean Phaseolus sp.     

Gas-sensing properties of armchair silicene nanoribbons towards carbon-based gases with single-molecule resolution

Structural Chemistry - Using non-equilibrium Green’s function (NEGF) formalism combined with first-principle density functional theory (DFT), we explore the nature of adsorption of...     

Glycerol acetylation considering competing dimerization

Glycerol acetylation is a very interesting reaction for studies of consecutive kinetics. In this short communication, we present a pseudo-homogeneous model for the synthesis of triacetyl glycerol from the reaction of glycerol and acetic acid over strongly acidic Amberlyst-15 and Amberlyst-70 catalysts, considering a dimerization of diacetyl glycerol (DAG) into diglycerol tetraacetate as a parallel reaction and compare the results with a model without side reactions. The best fits were obtained for apparent zeroth-order dimerization and first-order consecutive reactions in the presence of acetic acid in excess and with removal of water. An adaptation was made for DAG. The proposed model shows that the formation of DAG is faster than the consumption of glycerol, which could be an explanation for the occurrence of DAG dimerization instead of other parallel reactions in acetylation.     

On Scalable Attack Detection in the Network

Current intrusion detection and prevention systems seek to detect a wide class of network intrusions (e.g., DoS attacks, worms, port scans) at network vantage points. Unfortunately, even today, many IDS systems we know of keep per-connection or per-flow state to detect malicious TCP flows. Thus, it is hardly surprising that these IDS systems have not scaled to multi-gigabit speeds. By contrast, both router lookups and fair queuing have scaled to high speeds using aggregation via prefix lookups or DiffServ. Thus, in this paper, we initiate research into the question as to whether one can detect attacks without keeping per-flow state. We will show that such aggregation, while making fast implementations possible, immediately causes two problems. First, aggregation can cause behavioral aliasing where, for example, good behaviors can aggregate to look like bad behaviors. Second, aggregated schemes are susceptible to spoofing by which the intruder sends attacks that have appropriate aggregate behavior. We examine a wide variety of DoS and scanning attacks and show that several categories (bandwidth based, claim-and-hold, port-scanning) can be scalably detected. In addition to existing approaches for scalable attack detection, we propose a novel data structure called partial completion filters (PCFs) that can detect claim-and-hold attacks scalably in the network. We analyze PCFs both analytically and using experiments on real network traces to demonstrate how we can tune PCFs to achieve extremely low false positive and false negative probabilities     

Cyclopentanone thiosemicarbazone, a new complexing agent for copper determination in biological samples by adsorptive stripping voltammetry.

A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with cyclopentanone thiosemicarbazone (CPTSC) is presented. The method is based on the adsorptive accumulation of the resulting copper-CPTSC complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurements at the reduction current of the adsorbed complex at -0.37 V vs. Ag/AgCl. The optimal conditions for the stripping analysis of copper include pH 9.3, deposition time of 120 s, and a deposition potential of -0.1 V (vs. Ag/AgCl). The peak current is linearly proportional to the copper concentration over a range 3.14 x 10(-9) M to 1.57 x 10(-6) M with a limit of detection of 1.57 x 10(-9) M. The technique has been applied to the determination of copper in biological samples, like urine and whole blood.     

Synthetic talc as a solid base catalyst for condensation of aldehydes and ketones

Magnesium organo silicates (MOSs; synthetic talc) as such and with amine surface functionalities were synthesized by sol–gel method under non-hydrothermal conditions and characterized by spectroscopic techniques. The synthesized talc samples were observed to be thermally stable up to 200 °C in nitrogen atmosphere and used as catalysts for condensation of aldehydes and ketones. Application of synthetic talc as a solid base catalyst for condensation of aldehydes and ketones is being reported for the first time. The effect of solvent, solvent to reactant molar ratio, amount of catalyst and temperature was studied in detail for self-condensation of propanal. High conversion (86%) of propanal with 95% selectivity of 2-methylpentenal was achieved using dimethyl sulphoxide as a solvent. The kinetic study was carried out for the condensation of propanal catalyzed by amine functionalized MOS under optimum reaction conditions. Catalyst was re-used without significant loss in activity up to three cycles.     

Propagation characteristics of thermoelastic waves in piezoelectric (6 mm class) rotating plate

The propagation of Lamb waves in a homogeneous, transversely isotropic (6 mm class), piezothermoelastic plate rotating with uniform angular velocity about normal to its boundary has been investigated. The generalized (non-classical) theories of thermoelasticity in contrast to Sharma and Pal [Sharma, J.N., Pal, M., 2004. Lamb wave propagation in transversely isotropic piezothermoelastic plate. J. Sound Vib. 270, 587–610] have been used to investigate the problem. The surfaces of the plate are subjected to stress free, thermally insulated/isothermal and electrically shorted boundary conditions. Secular equations for wave propagation modes in the plate are derived from a coupled system of governing partial differential equations of linear piezothermoelasticity. After obtaining the complex characteristic roots with the help of Descartes' algorithm, the transcendental secular equations have been solved by functional iteration numerical technique to compute phase velocity and attenuation coefficient. Finally, in order to illustrate the analytical development, numerical solution of secular equations is carried out for PZT-5A piezo-thermoelastic material. The corresponding simulated results of various physical quantities such as phase velocity, attenuation coefficients, specific loss factor of energy dissipation, thermo-mechanical coupling factor and relative frequency shifts have been presented graphically for both rotating and non-rotating plates for comparison purpose. There is a scope for extension of the present work to other classes of piezo/pyroelectric crystals. The study will be useful in design and construction of gyroscope, rotation sensors, temperature sensors and other pyro/piezoelectric surface acoustic wave (SAW) devices.     

Copper-catalyzed rearrangement of oximes into primary amides

The atom-efficient and cost-effective rearrangement of oximes into primary amides is catalyzed by simple copper salts. The use of homogeneous Cu(OAc)₂ (1-2 mol %) was found to be effective for this transformation at 80 °C. The reaction was successful with either conventional or microwave heating. CuO and CuO/ZnO on activated carbon provided a competent reuseable heterogeneous catalyst which could be used in a batch process or in flow. Copper salts are much cheaper than the precious metals previously used for this rearrangement, and the reaction conditions are milder than those reported.     

Affinity Maturation of Macrocyclic Peptide Modulators of Lys48-Linked Diubiquitin by a Twofold Strategy

Messenger RNA display of peptides containing non-proteinogenic amino acids, referred to as RaPID system, has become one of the leading methods to express libraries consisting of more than trillion-members of macrocyclic peptides, which allows for discovering de novo bioactive ligands. Ideal macrocyclic peptides should have dissociation constants (K_D) as low as single-digit values in the nanomolar range towards a specific target of interest. Here, a twofold strategy to discover optimized macrocyclic peptides within this affinity regime is described. First, benzyl thioether cyclized peptide libraries were explored to identify tight binding hits. To obtain more insights into critical sequence information, sequence alignment was applied to guide rational mutagenesis for the improvement of their binding affinity. Using this twofold strategy, benzyl thioether macrocyclic peptide binders against Lys48-linked ubiquitin dimer (K48-Ub2) were successfully obtained that display K_D values in the range 0.3–1.2 nm , which indicate binding two orders of magnitude stronger than those of macrocyclic peptides recently reported. Most importantly, this macrocyclic peptide also showed an improved cellular inhibition of the K48-Ub2 recognition by deubiquitinating enzymes and the 26S proteasome, resulting in the promotion of apoptosis in cancer cells.