A novel silane coupling agent with peroxy groups used as an initiator in the graft polymerization of AN or MMA on nano-TiO<Subscript>2</Subscript>

A novel peroxy group-containing silane coupling agent was synthesized and anchored on the surface of titanium dioxide nanoparticles (nano-TiO₂) to form an immobilized-initiator-modified nano-TiO₂ species. In this study, the kinetic parameters of the peroxy group-containing silane were tested and assessed using DSC. The pre-exponential factor (A_d) was 8.973?×?10⁸ and the activation energy (E_a) was 80.736 kJ mol^?1. Moreover, the empirical Arrhenius equation was determined to be ln K_d?=???80.736/RT?+?ln(8.973?×?10⁸). To obtain continuous polymers, acrylonitrile (AN) and methyl methacrylate (MMA) were polymerized using the novel peroxy group-containing silane and FeSO₄ as an initiator system. The number average molecular weights (M_n of PAN?=?3×10⁴ and M_n of PMMA?=?1.4?×?10⁵) and polydispersity indexes (PDI of PAN?=?2.76 and PDI of PMMA?=?1.65) were determined by GPC. It was suggested that the redox initiation system can generate highly reactive species on the surfaces of inorganic nanoparticles. The nano-TiO₂-grafted polymers were successfully obtained.     

γ-Hydroxyphosphonate inducing single-chain antibodies capable of catalyzing soman hydrolysis

A γ-hydroxyphosphonate P6 (O1-methyl-O2-(1, 2, 2-trimethylpropyl)-2-hydroxy-5-nitrophenyl methylphosphonic acid) which is proposed to be an analog of the transition state in hydrolysis of soman was synthesized. Artificial antigens were obtained by conjugating P6 to the carrier proteins BSA (bovine serum albumin) and LPH (Limulus polyphenus hemocyanin). Mice were immunized with P6-LPH and recombinant single-chain antibody phage display library was constructed. After 4 rounds of panning against P6-BSA and competitive inhibition enzyme immunoassay, more than 70 strains of phage antibodies capable of binding soman were obtained and 11 of them can accelerate the hydrolysis reaction of soman. One of them (EP6) was studied further. Soluble single-chain antibody was prepared and purification was performed by gel filtration and ion exchange chromatography. The kinetic experiment was carried out showing that the turnover number kcat = 198 minγ1 and the rate enhancement kcat/kuncat = 122 419. When 0.16 mg·mLγ1 EP6 was preincubated in vitro with 0.132 mmol·Lγ1 (220 g·kgγ1 = 1.1×LD95) of soman prior to the administration to mice by subcutaneous route, all animals (19 mice) survived whereas all the control mice (14) treated with PBS and soman died within 30 min. Furthermore, EP6 could prolong the latent time of spasm and death when mice were passively immunized with EP6 intravenously 15 min before 1×LD95 of soman challenge. These results demonstrate that EP6 is able to increase the rate of soman degradation and protect against soman's toxicity, especially in vitro.     

Determination of SYUIQ-F5, a Novel Telomerase Inhibitor and Anti-tumor Lead-Compound, in Tissues and Plasma Samples by LC�CMS�CMS: Application to a Tissue Distribution Study in Rat

A sensitive assay for determining SYUIQ-F5, a novel telomerase inhibitor and anti-tumor drug, in rat tissues and plasma was developed and validated by using liquid chromatography/tandem mass spectrometry (LC?CMS?CMS). After a single step liquid?Cliquid extraction with ethyl acetate-dichloromethane, SYUIQ-F5 and SUCL (internal standard) were subjected to LC?CMS?CMS analysis using positive electro-spray ionization under selected reaction monitoring mode. Chromatographic separation of SYUIQ-F5 and SUCL was achieved on a Zorbax Eclipse Plus C18 column (I.D. 4.6 mm × 150 mm, 3.5 ??m) with a mobile phase consisting of acetonitrile-2 mM ammonium formate (90:10, v/v) at a flow rate of 0.6 mL min^?1. The intra- and inter-batch precision of the method were <12.2 and 8.7%, respectively. The intra- and inter-batch accuracies ranged from 100.2 to 107.3%. The lowest limit of quantification for SYUIQ-F5 was 0.5 ng mL^?1. The method was applied to a SYUIQ-F5 tissue distribution study after an oral dose of 30 mg kg^?1 to rats. SYUIQ-F5 tissue concentrations decreased in the order of small intestine> liver> lung> spleen> stomach> kidneys> heart> brain> muscle> fat> testes> plasma. SYUIQ-F5 could still be detected in most of the tissues at 48-h post-dosing. These results indicated that the LC?CMS?CMS method was sensitive, reliable, and specific to quantify SYUIQ-F5 in different rat tissues.     

Determination of Six Analgesics by CE with an Improved Electromagnetic Induction Detector

A novel, rapid and validated capillary electrophoretic method with an improved electromagnetic induction detector has been developed for the determination of ibuprofen, acetaminophen, amantadine hydrochloride, aminopyrine, diclofenac sodium and codeine phosphate in three kinds of analgesic pharmaceutical preparations. Fabrication of the electromagnetic inductor was the same as previously described, but a brand new electric circuit was designed for the detector to lower the background noise and improve the detection sensitivity. Important factors which might influence the response of the detector, including the value of the adjustable inductor and resistor, excitation frequency and voltage, were examined. Electrophoretic parameters affecting separation efficiency, such as variety of buffer, buffer pH, buffer concentration and electroosmotic flow modifier, were also deliberately investigated. Under the optimal conditions, highly linear response was obtained for these six compounds over three orders of magnitude with detection limits ranging from 0.1 to 1.0 μg mL⁻¹ (S/N = 3). The average recovery and RSD were within the range of 97.5–101.5 and 1.1–2.3%, respectively. This simple, convenient, effective and stable method held great promise in quality control of pharmaceutical preparations.