Development and application of a new solid-phase microextraction fiber by sol–gel technology on titanium wire

Novel solid-phase microextraction fibers were prepared based on sol–gel technique. Commonly used fused silica substrate was replaced by titanium wire which provided high strength and longer fiber life cycle. Titanium isopropoxide was employed as the precursor which provides a sol solution containing Ti–OH groups and shows more tendencies to the molecularly similar group on the substrate. Three different polymers, poly (dimethylsiloxane) (PDMS), poly(ethylenepropyleneglycol)-monobutyl ether (Ucon) and polyethylene glycol (PEG) were employed as coating polymer in preparing three different fibers. The applicability of these fibers was assessed for the headspace SPME (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water sample followed by gas chromatography–mass spectrometry (GC–MS). Effects of different parameters such as fiber coating type, extraction condition, desorption condition were investigated and optimized. Under the optimized conditions, LODs and LOQs of 0.75–10 μg L⁻¹ (S/N = 3) and 1–20 μg L⁻¹ (S/N = 10) were respectively obtained. The method showed linearity in the range of 10–25,000 μg L⁻¹ with correlation coefficient of >0.99. The relative standard deviation was less than 8%.     

Reaction kinetics of a novel thermoset nanocomposite: the glycerol diglycidyl ether/3,3-dimethylglutaric anhydride/nano-Al2O3 system

Abstract  

The curing behavior of the glycerol diglycidyl ether/3,3-dimethylglutaric anhydride/nano-alumina system was examined using a dynamic differential scanning calorimetry technique. The activation energy of the system was calculated using the Kissinger, Ozawa, Barrett, and two-parameter Sestak–Berggren models. Under the assumption of a constant activation energy and an autocatalytic mechanism, the activation energy, frequency factor, and total order of reaction were computed. The theoretical reaction rate was also calculated and compared to the experimental results. Good agreement was seen between the experimental and calculated data confirming the autocatalytic mechanism. The effect of triethylamine concentration on the reaction rate was clarified using the Barrett method. Fourier transform infrared spectroscopy (FT-IR) spectroscopy was used to verify the formation of internal ester groups. Scanning electron microscopy (SEM) and X-ray mapping analyses revealed that the nanofiller was homogeneously distributed in the continuous phase.     

PEG-mediated catalyst-free expeditious synthesis of polysubstituted anilines and benzenes via the reaction of malononitrile and β-ketoester derivatives in the presence of activated acetylenes

Poly(ethylene glycol) (PEG) has been used as a sustainable, non-volatile, and environmentally friendly reaction solvent for synthesis of functionalized anilines and benzenes via the reaction of malononitrile and β-ketoester derivatives in the presence of activated acetylenes at 80° C. No additional solvent and catalyst are required.     

硅胶键合的N-丙基三亚乙基四胺氨基磺酸作为可回收固体酸催化剂催化合成2-氨基-4,6-二芳基烟腈(英文)

A simple and efficient procedure for the preparation of silica-bound N-propyl triethylenetetramine sulfamic acid(SBPTETSA) by the reaction of silica-bound N-propyl triethylenetetramine(SBPTET) with chlorosulfonic acid in chloroform is described.Silica-bound N-propyl triethylenetetramine sulfamic acid was employed as a recyclable catalyst for the synthesis of 2-amino-4,6-diarylnicotinonitriles from the multi-component reaction of an acetophenone derivative,an aromatic aldehyde,malononitrile,and ammonium acetate under solvent-free conditions at 100 °C.The heterogeneous catalyst was recycled for five consecutive runs in the optimized multi-component reaction of 4-chloroacetophenone,4-chloroenzaldehyde,malononitrile,and ammonium acetate without significant loses to its catalytic activity.     

Isomeric pyridylcarbenes and their Si and Ge heavier analogues at DFT: stabilization through π–p or n–p interaction

To realize the effects of the pyridyl group on the stability, multiplicity, and geometry of isomeric pyridylcarbenes and their heavier Si and Ge analogues, a theoretical study was performed at B3LYP/6-311++G(d,p)//B3LYP/6-31G(d). The behavior of nitrogen atom was totally different in each multiplicity (singlet and triplet), structural isomer (ortho-, meta-, and para-), and divalent center (C, Si, and Ge). All pyridylcarbenes have triplet ground states, while the stable silylene and germylene analogues are singlet. The pyridyl group stabilizes both singlet and triplet states divalent centers with more pronounced effects on the singlet states in the order: carbene>germylene>silylene. While all planar species benefit from common π–p conjugative interaction of the pyridyl ring, in the ortho-isomers of 2-pyridylsilylene and 2-pyridylgermylene there is another interaction, n–p, that leads to two stable non-planar conformers. This finding is confirmed by NBO charges, calculated UV–vis spectra, philicity indices (N and ω), and isodesmic reactions.     

Highly cis‐Diastereoselective Synthesis of Coumarin‐Based 2,3‐Disubstituted Dihydrobenzothiazines by Organocatalysis

An efficient and organocatalyzed asymmetric reaction of phenacyl halides with coumarin‐based dihydrobenzothiazoles was developed to afford cis‐2,3‐disubstituted 3,4‐dihydro‐2H‐benzothiazines. This method provides a one‐step and highly diastereoselective route to a wide variety of coumarin‐based 3,4‐dihydro‐2H‐benzothiazines using the cheap and commercially available Cinchona alkaloid quinine hydrochloride.     

Extraordinarily water permeable sol-gel formed nanocomposite nanofibrous membranes

Electrospun nanofibrous membranes (ENMs) are considered as a state of the art in water filtration technology mainly owing to their high interconnected porosity and tunable pore size assumed to offer a very high permeability also selectivity. However, the extremely high surface area makes the ENMs prone to mechanical breakdown and lack of wettability lowering the filtration efficiency. Hence, any attempt to enhance both the mechanical properties and hydrophilicity of the ENMs is highly recommended. In the current study, the structural and transport properties of polyethersulfone (PES) ENMs were modified through incorporation of titania (TiO(2)) nanoparticles via a sol-gel approach. Presence of titania precursor increased the conductivity of the electrospun solution thereby optimized the structural features of the electrospun mat in terms of formation of very thin beadless nanofibers, a higher porosity and smaller pore size. Moreover, a significant rise in mechanical properties, thermal stability and switching from a highly hydrophobic membrane to a superhydrophilic one occur simultaneously. The combination of a more optimum porosity, very high mechanical properties and hydrophilicity leads to a significantly higher water permeability in the TiO(2)/PES ENMs encouraging us to propose it as a water filtration membrane with longer life span and lower energy consumption.     

Antioxidant activity and cytotoxic effect of aviprin and aviprin-3″-O-D-glucopyranoside on LNCaP and HeLa cell lines

Many researchers have shown that plant-derived polyphenolic compounds are helpful nutraceuticals in restraining various disorders such as neoplastic diseases. In this study two linear furanocoumarins, aviprin and aviprin-3″-O-D-glucopyranoside (A3G), were isolated from methanol extract of Prangos uloptera roots. The evaluation of free radical scavenging capacity of the compounds showed that aviprin is a more effective antioxidant than A3G with RC50 of 0.54?mg?mL?1. The biological and antiproliferative activities of the furanocoumarins were examined using human cervical carcinoma HeLa cell line and LNCaP prostatic cell line. Cell membrane integrity and cell viability were evaluated by measuring trypan blue exclusion assay and reduction of the tetrazolium blue compound, respectively. Treating the LNCaP cell line with various concentrations of the furanocoumarins showed that IC?? of aviprin and A3G were 0.4 and 6.6?mg?mL?1, whereas their CC50 values were 0.7 and 11?mg?mL?1, respectively. These results indicated that 42.7% of LNCaP cells were not dead by necrosis. Treating the HeLa cells by the furanocoumarins showed the greater sensitivity of the HeLa cell line than the LNCaP cell line. A morphological analysis and the study of DNA fragmentation provided further some evidence for the inhibition of the LNCaP cell line via apoptosis induction.     

Molecular structure and theoretical studies of new stable phosphorus ylides derived from trialkyl phosphites

The reaction between dialkyl acetylenedicarboxylates and NH heterocyclic compounds in the presence of trialkyl phosphite leads to stable phosphorus ylide derivatives in good yields. The x‐ray crystallographic data and theoretical study show that there is a resonance between two bonds of C₉P₁ and C₉₁O₉₁ in phosphorous ylide 4c . This compound crystallizes in the triclinic system, space group ( ), with the following unit cell parameters: a = 8.7522(3)Å, b = 8.8513(5)Å, c = 18.3469(5)Å, α = 99.1220(10)°, β = 90.954(2)°, γ = 118.792(2)°, Z = 2, and V = 1222.72(9)ų. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 22:36–43, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20653     

Decoration of carbon nanotube with size-controlled L10-FePt nanoparticles for storage media

In this work, first multi-wall carbon nanotubes (MWCNTs) with outer diameter about 20–30 nm are synthesized by a CVD method; they have been purified and functionalized with a two-step process. The approach consists of thermal oxidation and subsequent chemical oxidation. Then, monosize FePt nanoparticles along carbon nanotubes surface are synthesized by a Polyol process. The synthesized FePt nanoparticles are about 2.5 nm in size and they have superparamagnetic behavior with fcc structure. The CNTs surfaces as a substrate prevent the coalescence of particles during thermal annealing. Annealing at the temperature higher than 600 ^°C for 2 h under a reducing atmosphere (90 % Ar + 10 % H₂) leads to phase transition from fcc to fct-L1₀ structure. So, the magnetic behavior changes from the superparamagnetic to the ferromagnetic. Furthermore, after the phase transition, the FePt nanoparticles have finite size with an average of about 3.5 nm and the coercivity of particles reaches 5.1 kOe.