Studies on the Thermodynamic and Kinetic Properties of the Reactions of Ti+ with Sulfur Transfer Reagent SCO Along the C═S Bond Activation Branch at 200–1200K

Theoretical studies on the thermodynamic and kinetic properties of the reactions of Ti⁺ with sulfur transfer reagent SCO via the C═S bond activation pathway have been carried on using DFT/B3LYP method, general statistical thermodynamics, and Eyring transition state theory with Wigner correction. The relevant reactions include reaction 1 ⁴ Ti⁺+¹SCO → ⁴ IM ₁ → ⁴ TS ₁ → ⁴ IM ₂ → ⁴ TiS⁺+ ¹ CO, and reaction 2 ⁴Ti⁺+¹SCO →⁴IM₁→ CP →²IM₂→²TiS⁺+¹CO in which the spin multiplicity changes from the quartet state to the doublet state in the crossing region. It is concluded that the increase of the temperature is favored to the reaction 1 process, since the equilibrium constants (K) rises from 0.566 × 10[P]-9 at 200 K to 0.109 × 10⁰ at 1200 K, and the reaction rate constant (k) from 0.222 × 10⁰ s[P]-1 at 200 K to 0.540 × 10 ¹¹ s[P]-1 at 1200 K. Moreover, reaction 1 is endothermic, and non-spontaneous in the way the entropy increases, while reaction 2 is exothermic and spontaneous in the way their entropy decreases. The reaction path 2 is the energetically favorable channel, and its thermodynamic data change not largely with the rise of temperature.     

Efficient Synthesis and Fungicidal Activities of 2-Alkylthiobenzofuro[3,2-d]Pyrimidinones

2-Alkylthiobenzofuro[3,2-d]pyrimidinones 5 and 6 were synthesized by S-alkylation of 2,3-dihydro-2-thioxobenzofuro[3,2-d]pyrimidin-4(1H)-ones 4, which were obtained via aza-Wittig reaction of iminophosphorane 2 with CS₂ and further reaction of the product with various amines. Compounds 5 and 6 exhibited fungicidal activity. For example, compound 6a, which has a small N-substituted methyl group, showed the best inhibitive activity (91%) against Dothiorella gregaria at 50 mg/L.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Injectable Graphene Oxide/Graphene Composite Supramolecular Hydrogel for Delivery of Anti-Cancer Drugs

Injectable hydrogels have attracted a lot of attention in drug delivery, however, their capacity to deliver water-insoluble or hydrophobic anti-cancer drugs is limited. Here, we developed injectable graphene oxide/graphene composite supramolecular hydrogels to deliver anti-cancer drugs. Pluronic F-127 was used to stabilize graphene oxide (GO) and reduced graphene oxide (RGO) in solution, which was mixed with α-cyclodextrin (α-CD) solution to form hydrogels. Native hydrogel was used as control. GO or RGO slightly shortened gelation time. The storage and loss moduli of the hydrogels were tracked by dynamic force measurement. The storage modulus of GO or RGO composite hydrogels was larger than that of the native hydrogel. Hydrogels were unstable in solution and eroded gradually. GO or RGO in Pluronic F-127 solution could potentially improve the solubility of the water-insoluble anti-cancer drug camptothecin (CPT), especially with large drug-loaded CPT amount. Drug release behaviors from solutions and hydrogels were characterized. The nanocomponents (GO or RGO) were able to bind more drug molecules either for CPT or for doxorubicin hydrochloride (DXR) in solution. Therefore, GO or RGO composite hydrogel could potentially enable better controlled and gentler drug release (for both CPT and DXR) than native hydrogel.     

Chemical-Modified Nylon 4 Membrane for Pervaporation

Abstract

A hydrophilic polymer membrane was synthesized with 2-hydroxyethyl methacrylate (HEMA) onto a Nylon 4 polymer backbone, PHEMA-g-N4. The membranes were water permselective because of the hydrophilicity, and the water permselectivity increased with increasing the degree of grafting. Permseparation of water was investigated with respect to the feed aqueous alcohol concentration, feed temperature, size of the alcohols, and degree of grafting. The separation factors of this PHEMA-g-N4 membrane were higher than those of the unmodified Nylon 4 membrane for pervaporation of aqueous ethanol solution, while the permeation rate was slightly lower. A separation factor of 98 and a 194 g/m²·h permeation rate could be obtained. Compared with an unmodified Nylon 4 membrane, the PHEMA-g-N4 membrane effectively increased the pervaporation separation index for the water-ethanol mixtures on pervaporation separation.     

Cationic Lanthanide Luminescent Copolymer: Design,Synthesis and Interaction with DNA

Polymerizable rare earth complex Eu(AA)₃Phen was synthesized by complexion of europium ion, acrylic acid (AA), and 1,10-phenanthroline (Phen). The structure and fluorescence properties of the complex were studied by elemental analysis, ¹H-NMR spectroscopy, and fluorescence spectroscopy. Eu-containing copolymer poly(PEGMA-co-MMA-co-METAC-co-Eu(AA)₃Phen) (PPMMEu) was then synthesized by free radical copolymerization of Eu(AA)₃Phen and other functional monomers including poly(ethylene glycol) methyl ether methacrylate (PEGMA) and [2-(Methacryloyloxy) ethyl] trimethylammonium chloride (METAC). ¹H-NMR spectroscopy and fluorescence spectroscopy were used to characterize the copolymer and the interactions between the copolymer and DNA was investigated by TEM, fluorescence spectroscopy, and agarose gel electrophoresis. The desired luminescent cationic copolymer was successfully obtained. The copolymer can form micelles in water solution and can efficiently bind to DNA molecules through electrostatic interaction. The results suggest the potential use of PPMMEu in bioprobes and gene vectors.     

Further Studies on the Anionic Copolymerization of Styrene and Glycidyl Methacrylate in Toluene

Sequential anionic copolymerization of styrene and glycidyl methacrylate (GMA) was performed with the protection of argon under normal pressure, where styrene, GMA, toluene, THF, n-butyllithium and a small amount of lithium chloride (LiCl) were used as first monomer, second monomer, solvent, polar reagent, initiator and additive, respectively. Polystyrene-b-poly(glycidyl methacrylate) diblock copolymers (PS-b-PGMA) with well-defined structure and narrow molecular weight distribution were prepared by the copolymerization reaction of poly(styryl)lithium with GMA under certain temperatures. The copolymers were characterized using gel permeation chromatography (GPC), ¹H-NMR, ¹³C-NMR, thin layer chromatography (TLC) and hydrochloric acid-dioxane argentimetric methods. The effects of additives, copolymerization temperature and THF dosage on the copolymerization were studied. No chain transfer reaction of anionic polymerization of styrene in toluene was observed. Slightly broader molecular weight distribution of PS-b-PGMA was observed with the increase the GMA repeat units. Using THF/toluene blend solvent could reduce the polydispersity index (M _w /M _n ) and dissolve the copolymer better than toluene alone. Lower temperature (< -40°C) and LiCl are required to prepare PS-b-PGMA with narrower molecular weight distribution.     

Voltammetric determination of theophylline in pharmaceutical formulations using aligned carbon nanotubes (ACNTs) film modified electrode

A novel rapid, convenient and sensitive electrochemical method has been described for the determination of theophylline in pharmaceutical formulations, based on the extraordinary properties of an aligned carbon nanotubes (ACNTs) thin film. The voltammetric results suggest that the ACNTs-coated glass carbon electrode can exhibit excellent electrochemical activity for direct electrochemical oxidation of theophylline. Various experimental parameters such as solution pH value, amount of ACNTs suspension, accumulation conditions and scan rate were optimized for the determination of theophylline. Furthermore, it was found that the peak current increased linearly with the concentration of theophylline in the range of 8.0 × 10^?8?1.0 × 10^?5 M and the detection limit was 1.6 × 10^?8 M using differential pulse voltammetry. This newly proposed method has been applied successfully to the determination of theophylline in drugs.     

Catalytic effect analysis of metallic additives on light crude oil by TG and DSC tests

This research aimed at the investigation of the effect of different metallic additive on the combustion and kinetic behavior of crude oil. For this purpose, the thermal behavior of the oil-only and oil–metallic salts mixtures were studies by the thermogravimetry (TG)/derivative thermogravimetry and differential scanning calorimetry (DSC) on heating rate at 10 °C min^?1. The result shows that Dagang crude oil exhibited apparent low temperature oxidation (LTO), fuel deposition, and high temperature oxidation processes. With the addition of metallic salts, the LTO process has been shortened and samples added CuSO₄, CrCl₃·6H₂O, and AlCl₃·6H₂O achieved a much lower peak temperature than that of oil. Based on the Arrhenius model, metallic additives were proven to have obvious influence on the combustion activation energy. And, by comprehensive analysis of TG/DSC profile and activation energy, ZnSO₄ exhibited a positive influence on light crude oil combustion during the high pressure air injection process.