Deprotection‐free preparation of propargyl ether‐containing phosphinated benzoxazine and the structure–property relationship of the resulting thermosets

Generally, protection and deprotection procedures of amino groups are required in preparing propargyl ether‐containing benzoxazines. In this study, we report a facile, deprotection‐free preparation of a propargyl ether‐containing phosphinated benzoxazine (2) from the nucleophilic substitution of a phenolic OH‐containing phosphinated benzoxazine (1) and propargyl bromide in the catalysis of potassium carbonate. The structure of (2) was characterized and confirmed by a high‐resolution mass spectrum, ¹H, ¹³C, ¹H‐¹H, ¹H‐¹³C nuclear magnetic resonance (NMR) spectra, and X‐ray single crystal diffractogram. infrared (IR) and differential scanning calorimetry were used to monitor the ring‐opening of benzoxazine and crosslinking of propargyl ether. The microstructure and the structure–property relationship of the resulting homopolymers and copolymers are discussed. The T_g of homopolymer of (2) is 208 °C by dynamic mechanical analysis, the coefficient of thermal expansion is 43 ppm/°C, and T_d 5% (N₂) is 393 °C, respectively, which are higher than those of the homopolymer of (1) . Similar trends were observed in the copolymerization system. The results demonstrate the beneficial effect of crosslinking afforded by the propargyl ether group is higher than that by the phenolic OH group. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly(2-hydroxyethyl acrylate) hydrogels containing hyper-branched poly(amidoamine) for sustained drug release

Hydrogels containing hyper-branched poly(amidoamine) (hb-PAMAM) microenvironments were suggested for the sustained release of ionizable drugs. For this purpose, a series of poly(2-hydroxyethyl acrylate) (PHEA) hydrogels containing hb-PAMAM (PHEA-hb-PAMAM) were prepared by copolymerization of 2-hydroxyethyl acrylate with acryl-terminated hb-PAMAM. The hb-PAMAM was synthesized by the Michael addition reaction of triacryloylhexahydro-1,3,5-triazine (TT) and piperzaine (PZ). By using nonionic Tegafur and ionizable salicylic acid (SA) as model drugs, the release mechanisms of drugs from PHEA-hb-PAMAM hydrogels were investigated. Compared with the release kinetic of Tegafur, the release rate of SA from the hydrogels was evidently slowed down. Moreover, the release rate of SA can be modulated by the addition of salt. This can be attributed to the ionic interaction of SA with hb-PAMAM microenvironments. By analyzing the release kinetics of SA from the hydrogels, it was found that the release of SA followed non-Fickian diffusion.     

Preparation and evaluation of <Superscript>131</Superscript>I-quercetin as a novel radiotherapy agent against dedifferentiated thyroid cancer

Here we reported the radiolabeling and evaluation of a novel ¹³¹I-radiolabeled quercetin for the treatment of dedifferentiated thyroid cancers. The human thyroid cancer cell lines (FTC-133, TT and DRO) experienced much higher uptake of ¹³¹I-quercetin as compared to the free ¹³¹I. And the proliferation inhibition rate of ¹³¹I-quercetin on in vitro DRO cell line was 86.87 ± 7.15%. Biodistribution and SPECT analysis demonstrated that the injected radioactivity mainly accumulated in tumors. The tumor volume in the treatment group was dramatically inhibited in comparison with the control group.     

Intermolecular Domino Reaction of Two Aryl Iodides Involving Two CH Functionalizations

A palladium‐catalyzed intermolecular cross‐coupling of two aryl iodides is reported, giving polycyclic ring systems with a high level of convergence and efficiency.     

Suppression of the Charge Density Wave State in Two-Dimensional 1T-TiSe2 by Atmospheric Oxidation

Two-dimensional (2D) metallic transition-metal dichalcogenides (TMDCs), such as 1T-TiSe₂, have recently emerged as unique platforms for exploring their exciting properties of superconductivity and the charge density wave (CDW). 2D 1T-TiSe₂ undergoes rapid oxidation under ambient conditions, significantly affecting its CDW phase-transition behavior. We comprehensively investigate the oxidation process of 2D TiSe₂ by tracking the evolution of the chemical composition and atomic structure with various microscopic and spectroscopic techniques and reveal its unique selenium-assisting oxidation mechanism. Our findings facilitate a better understanding of the chemistry of ultrathin TMDCs crystals, introduce an effective method to passivate their surfaces with capping layers, and thus open a way to further explore the functionality of these materials toward devices.     

Analysis of sialic acid levels in Chinese intravenous immunoglobulins by high‐performance liquid chromatography with fluorescence detection

Intravenous immunoglobulin (IVIg) is increasingly used for the treatment of autoimmune and systemic inflammatory diseases with both licensed and off‐label indications. Recent studies indicated that IVIg‐mediated immunomodulation and anti‐inflammation are closely associated with the IgG sialylation, especially with IgG crystallizable fragment (Fc) sialylation. The sialic acid levels of the IgG molecules and Fc fragments in 12 IVIg preparations from six Chinese manufacturers were evaluated. The Fc fragments were derived from the papain digestion of IVIg, followed by affinity and size exclusion chromatography. The sialic acid levels in Fc fragments and IVIg preparations were determined by high‐performance liquid chromatography with fluorescence detection, after the sialic acid residues were released from the proteins. The results showed that the sialic acid levels in Chinese IVIg preparations ranged from 0.875 (mol/mol IgG) to 1.085 (mol/mol IgG), and the sialic acid levels in Fc fragments were from 0.321 (mol/mol Fc) to 0.361 (mol/mol Fc). Furthermore, the sialic acid levels of IVIg preparations and Fc fragments from different Chinese manufactures were significantly different. These findings will contribute to an increased understanding of Chinese IVIg preparations and the relationship between the sialic acid levels in IVIg preparations and their clinical efficacy in future clinical studies.     

Radioanalysis of ultra-low level radionuclides for environmental tracer studies and decommissioning of nuclear facilities

Journal of Radioanalytical and Nuclear Chemistry - Determination of long-lived radionuclides is critical for environmental radioactivity investigation, environmental processes studies and...