High-throughput preparation of radioprotective polymers via Hantzsch's reaction for in vivo X-ray damage determination.

Radioprotectors for acute injuries caused by large doses of ionizing radiation are vital to national security, public health and future development of humankind. Here, we develop a strategy to explore safe and efficient radioprotectors by combining Hantzsch's reaction, high-throughput methods and polymer chemistry. A water-soluble polymer with low-cytotoxicity and an excellent anti-radiation capability has been achieved. In in vivo experiments, this polymer is even better than amifostine, which is the only approved radioprotector for clinical applications, in effectively protecting zebrafish embryos from fatally large doses of ionizing radiation (80 Gy X-ray). A mechanistic study also reveals that the radioprotective ability of this polymer originates from its ability to efficiently prevent DNA damage due to high doses of radiation. This is an initial attempt to explore polymer radioprotectors via a multi-component reaction. It allows exploiting functional polymers and provides the underlying insights to guide the design of radioprotective polymers.

Ferrocene-Containing Polymer via the Biginelli Reaction for In Vivo Treatment of Oxidative Stress Damage.

Small molecule antioxidants have little impact on oxidative stress in vivo because of their poor bioavailability. To explore an antioxidant for in vivo applications, a polymeric antioxidant containing a ferrocene moiety was developed. The ferrocene-containing monomer was synthesized through the robust tricomponent Biginelli reaction with a high yield. The corresponding water-soluble copolymer was conveniently prepared via radical polymerization. Both the ferrocene moiety and the Biginelli structure (dihydropyrimidin-2(H)-one) contributed to the remarkable radical scavenging ability of this highly biocompatible copolymer. It was more efficient than traditional small molecule antioxidants at protecting cells against fatal oxidative stress. This copolymer also showed clear therapeutic activity in counteracting oxidation-induced acute liver damage in a live mouse model. Our study into functional organometallic polymers resulted in a promising polymeric biomaterial that may find therapeutic applications and have important implications in the fields of organic chemistry and polymer chemistry.

Multicomponent Reactions for Surface Modification.

Modification of material surfaces with polymers is an effective method to develop applicable polymer-material composites. Recently, multicomponent reactions (MCRs) have found their roles in advanced polymer chemistry and applied in surface modification. In this mini review, recent results of MCRs for surface modification are summarized, including the utilization of MCRs as coupling tools to link polymers on material surfaces, and polymers containing multicomponent structures for surface modification. The unique properties of these polymer-material composites stemming from MCRs are introduced, and the preliminary applications of these composites are also discussed.

High Throughput Preparation of UV-Protective Polymers from Essential Oil Extracts via the Biginelli Reaction.

A high throughput (HTP) system has been developed to exploit new functional polymers. We synthesized 25 monomers in a mini-HTP manner through the tricomponent Biginelli reaction with high yields. The starting materials were five aldehydes extracted from essential oils. The 25 corresponding polymers were conveniently prepared via mini-HTP radical polymerization initially realizing the benefit of HTP methods to quickly fabricate sample libraries. The distinct radical scavenging ability of these Biginelli polymers was evaluated through a HTP measurement to choose the three best radical scavengers. This confirms the superiority of the HTP strategy to rapidly collect and analyze data. The selected polymers have been upgraded and screened according to different requirements for biomaterials and offer water-soluble and biocompatible copolymers that effectively protect cells from the fatal UV damage. This research is a straightforward way to establish new libraries of monomers with abundant diversity. It offers polymers with interesting functionalities. This suggests that a broader study of multicomponent reactions and HTP methods might be useful in many interdisciplinary fields. To the best of our knowledge, this is the first report of a HTP study of the Biginelli reaction to develop a promising polymeric biomaterial, which might have important implications for the organic chemistry and polymer communities.

Electrospun interconnected Fe-N/C nanofiber networks as efficient electrocatalysts for oxygen reduction reaction in acidic media.

One-dimensional electrospun nanofibers have emerged as a potential candidate for high-performance oxygen reduction reaction (ORR) catalysts. However, contact resistance among the neighbouring nanofibers hinders the electron transport. Here, we report the preparation of interconnected Fe-N/C nanofiber networks (Fe-N/C NNs) with low electrical resistance via electrospinning followed by maturing and pyrolysis. The Fe-N/C NNs show excellent ORR activity with onset and half-wave potential of 55 and 108 mV less than those of Pt/C catalyst in 0.5 M H2SO4. Intriguingly, the resulting Fe-N/C NNs exhibit 34% higher peak current density and superior durability than generic Fe-N/C ones with similar microstructure and chemical compositions. Additionally, it also displays much better durability and methanol tolerance than Pt/C catalyst. The higher electroactivity is mainly due to the more effective electron transport between the interconnected nanofibers. Thus, our findings provide a novel insight into the design of functional electrospun nanofibers for the application in energy storage and conversion fields.

A Detailed Study on Understanding Glycopolymer Library and Con A Interactions.

Synthetic glycopolymers are important natural oligosaccharides mimics for many biological applications. To develop glycopolymeric drugs and therapeutic agents, factors that control the receptor-ligand interaction need to be investigated. A library of well-defined glycopolymers has been prepared by the combination of copper mediated living radical polymerization and CuAAC click reaction via post-functionalization of alkyne-containing precursor polymers with different sugar azides. Employing Concanavalin A as the model receptor, we explored the influence of the nature and densities of different sugars residues (mannose, galactose, and glucose) on the stoichiometry of the cluster, the rate of the cluster formation, the inhibitory potency of the glycopolymers, and the stability of the turbidity through quantitative precipitation assays, turbidimetry assays, inhibitory potency assays, and reversal aggregation assays. The diversities of binding properties contributed by different clustering parameters will make it possible to define the structures of the multivalent ligands and densities of binding epitopes tailor-made for specific functions in the lectin-ligand interaction. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2588-2597.

Controlled Alternate Layer-by-Layer Assembly of Lectins and Glycopolymers Using QCM-D.

Layer-by-layer (LBL) assembly of concanavalin A (Con A), peanut agglutinin (PNA) plant lectins, and well-defined synthetic glycopolymers via their biological affinities have been prepared using a quartz crystal microbalance with dissipation monitoring (QCM-D). We demonstrate the use of mannose/galactose glycopolymers as lectin binders due to their selective binding to Con A/PNA, respectively. A detailed analysis of the adsorption processes and the adsorbed layer are provided and tuning the composition of multilayers using a series of well-defined glycopolymers differing only in the pendant sugar ratio is discussed.

Pathogens of spontaneous bacterial peritonitis change in northern China.

OBJECTIVE: To determine the identity of microorganisms isolated from patients diagnosed with spontaneous bacterial peritonitis (SBP). METHODS: We reviewed cases diagnosed with SBP over a 14-year period. The medical records of 780 SBP-diagnosed patients with decompensated cirrhosis and ascites admitted to Tangdu Hospital, Xian, Shaanxi Province, China were retrospectively reviewed between January 1996 and December 2009. The patients were placed into 2 groups, and the clinical data were compared between the 2 groups. Ascitic fluid was collected from these patients and cultured for bacteria using the MicroScan WalkAway 40 system. RESULTS: There was a significant difference in the ratio of pathogens between group A (48 patients, from January 1996 to December 2002) and group B (50 patients, from January 2003 to December 2009) (χ²=9.630, p=0.002). The SBP patients with gram-positive bacteria needed significantly more antibiotics within 30 days compared to those with gram-negative bacteria (χ²=12.285, p=0.000). CONCLUSION: In recent years, the types of isolated pathogens have significantly changed in northern China. Such changes have also been observed in other countries and have been attributed to long-term antibiotic therapy and invasive procedures. Changes in the epidemiology of pathogens that cause SBP must be monitored for optimal treatment.