Silica Aerogel: Synthesis,Characterization, Applications,and Recent Advancements

Silica aerogels have drawn considerable attention due to their low density (almost 95% of the total volume is composed of air), hydrophobicity, optical transparency, low conductivity of heat, and large surface to volume ratio. Sol–gel processing is used to prepare aerogels from molecular precursors. To replace the pore fluid with air while retaining the solid network, a supercritical drying process (the most frequent approach) is used. However, recent technologies use atmospheric pressure to allow for liquid removal followed by chemical alteration of the gel's internal layer, which leaves only a silica network with a porous structure filled with air. This study discusses the sol–gel method for preparing silica aerogels and their various drying processes. Furthermore, various areas of applications of silica aerogels, including electronics, construction, aerospace, purification of water and air, sensing, catalyst, biomedical, absorbent, food packing, textile, etc., are also discussed. Lastly, this review provides a perception of the recent scientific progress along with the futuristic development of silica aerogel.     

PtCl2-mediated cycloisomerization of unsaturated propargylic carboxylates

The PtCl₂-mediated cycloisomerization of unsaturated propargylic carboxylates yields differently functionalized bicyclo[4.1.0]heptane enol esters from moderate to good yield, in a very diastereoselective manner. We have prepared and submitted to PtCl₂-catalyzed cycloisomerization a series of differently substituted hept-1-en-6-ynes with different O-acyl (acetyl, trichloroacetyl, 3,4,5-trimethoxybenzoyl, etc.) protecting groups at propargylic positions, investigating also the effect of the geometry at the double bond, as well as the effect of the number of substituents at the alkene moiety. As a result, we have found that the O-acetyl migrating group is the best one in terms of simplicity and chemical yields. In this reaction we have isolated mixtures of compounds formed by minor 1-acetoxy-allenes and major bicyclo[4.1.0]heptane derivatives. Major products are the result of a sequential process involving steps of cycloisomerization plus cyclopropanation, followed by acyl migration. The basic methanolysis (K₂CO₃, MeOH) of these intermediates gave mixtures of cis and trans-caran-2-ones. This two-step protocol (cycloisomerization plus basic methanolysis) for the syntheses of α,β-unsaturated cyclopropyl ketones constitutes a synthetic alternative to the usual unfriendly, intramolecular cyclopropanation of unsaturated α-diazocarbonyl derivatives. The formation of these bicyclo[4.1.0]heptane derivatives is a simple, but efficient entry into the skeleton of the ‘carane’ family of natural products.     

An alternative to the use of delta-lactam urethanes in the "ring switch" approach to higher homologues of AMPA-type glutamate antagonists

In an alternative strategy to the use of delta-lactam urethanes for the preparation of homologues of AMPA-type glutamate antagonists, we have used 5-exomethylene derivatives of pyroglutamate esters. The homochiral pyrazole amino acid derivatives 18 and 19 have been prepared in this way. Although this synthesis yields products with a glycine residue separated from a heterocyclic ring by two carbon atoms, the substitution of the heterocyclic ring is different from that in compounds prepared from delta-lactam urethanes. The branched chain compounds 32 and 33 have also been prepared in this way but the second chiral centre is epimerised during the synthesis. An interesting reaction, giving the pyridone 27 from the imino ether 24 and tert-butyl acetoacetate, is also reported.     

Temperature dependence of gamma-ray-induced luminescence of xylene-based liquid scintillator between 200 and 242 K

The luminescence response of xylene-based liquid scintillator (scintillation grade), xylene + 1 g/l PPO + 0.1 g/l BBOT, has been studied as a function of temperature in the range 200 to 242 K. It has been observed that under gamma-ray excitation the light output increases with the decrease of temperature. The data are well described by the Arrhenius relation,I _low−I=I ₀ exp(−E/kT), whereI is the count rate at temperatureT.I _low is a constant equal to 5600 counts per min, theI ₀ factor is 3.3 × 10⁶ counts/min,k is the Boltzmann constant. The activation energyE was found to be equal to 0.20 eV. It is typical for thermally activated diffusion controlled process.     

Management of Parthenium hysterophorus (Asteraceae) by Withania somnifera (Solanaceae)

This study was designed to evaluate the herbicidal activity of Withania somnifera (L.) Dunal against the noxious weed parthenium (Parthenium hysterophorus L.). In a laboratory bioassay, the effect of aqueous, methanol and n-hexane shoot and root extracts of 5%, 10%, 15% and 20% w/v concentrations (on a fresh weight basis) of W. somnifera were tested against the germination and seedling growth of parthenium. In general, aqueous and methanol extracts markedly suppressed the germination, root and shoot growth of parthenium. The shoot extracts were more inhibitory than the root extracts. In a foliar spray bioassay, the aqueous and methanol shoot extracts of 10% w/v (on a dry weight basis) concentration were sprayed on 1-week and 2-week-old pot-grown parthenium seedlings. Two subsequent sprays were carried out 5 and 10 days after the first spray. The aqueous and methanol extracts significantly reduced the length and biomass of parthenium shoots. In a soil amendment bioassay, the crushed shoots of W. somnifera were incorporated in the soil at 1-5% w/w. Parthenium seeds were sown one week after the residue incorporation and plants were harvested 40 days after sowing. All the soil amendment treatments significantly reduced seed germination by 43-89%. The highest dosages of 4% and 5% significantly suppressed the root and shoot biomasses of parthenium. This study concludes that foliar spray of aqueous and methanol extracts, and soil amendment with leaf residue of W. somnifera, can control the germination and growth of parthenium, one of the world's worst weeds.     

Analysis of polyethyleneoxide macromonomers by liquid chromatography along the critical adsorption line

Polyoxyethylene macromonomers are analyzed by one-dimensional liquid chromatography under different conditions, depending on the required information. These samples may contain polyethylene glycol (PEG) and the corresponding di(meth)acrylate besides the desired mono(meth)acrylate. The molar mass distribution (MMD) of the PEG and the monoester can be obtained by liquid adsorption chromatography (LAC) on a reversed-phase column in acetone–water with a gradient from 10% to 20% acetone. The MMD of the diesters can be obtained with isocratic elution by liquid chromatography at critical conditions (LCCC) on a reversed-phase column in 31% acetone, or using size-exclusion conditions for PEG and LAC conditions for the end groups, which is the case in 40–55% acetone. The absolute amount of the series with different functionality can be obtained by LCCC in ternary mobile phases consisting of acetone, methanol, and water along the critical adsorption line. Under such conditions, all series elute as narrow peaks (regardless their MMD), which can easily be integrated and quantified.     

Optimum Allocation in Two-Stage Stratified Randomized Response Model

In the present paper a two-stage stratified Warner’s randomized response model is used to determine the optimum allocation in the presence of non-response. The problem is formulated as a Nonlinear Programming Problem. A complete method of solution of the formulated problem is proposed. Two numerical examples are worked out to illustrate the computational details of the proposed method.