Phosphorus-Containing Polymers as Sensitive Biocompatible Probes for 31P Magnetic Resonance.

The visualization of organs and tissues using 31P magnetic resonance (MR) imaging represents an immense challenge. This is largely due to the lack of sensitive biocompatible probes required to deliver a high-intensity MR signal that can be distinguished from the natural biological background. Synthetic water-soluble phosphorus-containing polymers appear to be suitable materials for this purpose due to their adjustable chain architecture, low toxicity, and favorable pharmacokinetics. In this work, we carried out a controlled synthesis, and compared the MR properties, of several probes consisting of highly hydrophilic phosphopolymers differing in composition, structure, and molecular weight. Based on our phantom experiments, all probes with a molecular weight of ~3-400 kg·mol-1, including linear polymers based on poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), poly(ethyl ethylenephosphate) (PEEP), and poly[bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)]phosphazene (PMEEEP) as well as star-shaped copolymers composed of PMPC arms grafted onto poly(amidoamine) dendrimer (PAMAM-g-PMPC) or cyclotriphosphazene-derived cores (CTP-g-PMPC), were readily detected using a 4.7 T MR scanner. The highest signal-to-noise ratio was achieved by the linear polymers PMPC (210) and PMEEEP (62) followed by the star polymers CTP-g-PMPC (56) and PAMAM-g-PMPC (44). The 31P T1 and T2 relaxation times for these phosphopolymers were also favorable, ranging between 1078 and 2368 and 30 and 171 ms, respectively. We contend that select phosphopolymers are suitable for use as sensitive 31P MR probes for biomedical applications.

Synthesis and Characterization of Phosphorus-Containing Sorbent for Basic Dye Removal.

A new phosphorus-containing sorbent was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) and trimethylvinyl silane (TMVS) with diphenylvinylphoshine oxide (DPVO). It was characterized and applied in the removal of cationic dyes such as C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) and C.I. Basic Red 46 (BR46) using the batch method. Spectroscopic analysis indicated that the phosphinoyl group was introduced into the sorbent structure. Equilibrium adsorption data were fitted to the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. The Freundlich model is the most suitable to describe the adsorption of BB3 (the Freundlich constant kF = 32.3 mg1-1/nL1/n/g) and BY2 on the sorbent (13.8 mg1-1/nL1/n/g), while the Langmuir model is the most adequate to describe the adsorption of BR46 (the monolayer capacity Q0 = 2.7 mg/g). The kinetics of the dye adsorption follows the assumptions of the pseudo-second-order (the rate constants k2 = 0.087 ÷ 0.738 g/mg min) model rather than pseudo-first-order or intraparticle diffusion. The presence of Na2SO4 and cationic surfactant in the aqueous solutions inhibited dye retention by the DPVO-EGDMA-TMVS. Adsorbent regeneration efficiency does not exceed 60% using 1 M NaCl and 1 M HCl solutions in the presence of 50% v/v methanol.

Synthesis and Anti-influenza Activity of Vinylphosphonic Acid (Co)polymers.

New copolymers of vinylphosphonic acid (VPA) with 2-deoxy-2-methacrylamido-D-glucose, 4-acryloylmorpholine (4-AM), and acrylamide have been synthesized, and their antiviral activity against influenza virus has been studied in in vitro and in vivo experiments. Optimal antiviral characteristics and low cytotoxicity were exhibited by the copolymer of VPA with 4-AM, composition 56 : 44 mol %, molecular weight 33 000. The polymer exhibited virus-inhibiting properties with an IC50 = 1 µg/mL and a selectivity index of 302. Prophylactic intranasal administration of the polymer in a murine model of influenza pneumonia completely prevented the virus-induced death of animals, whereas the level of mortality in the placebo group was 90%. The results of this study indicate a high antiviral potential of polymeric compounds based on VPA.

Polymer-Supported Phosphoric, Phosphonic and Phosphinic Acids-From Synthesis to Properties and Applications in Separation Processes.

Efficient separation technologies are crucial to the environment and world economy. The challenge posed to scientists is how to engineer selectivity towards a targeted substrate, especially from multicomponent solutions. Polymer-supported reagents have gained a lot of attention in this context, as they eliminate a lot of inconveniences concerning widely used solvent extraction techniques. Nevertheless, the choice of an appropriate ligand for immobilization may be derived from the behavior of soluble compounds under solvent extraction conditions. Organophosphorus compounds play a significant role in separation science and technology. The features they possess, such as variable oxidation states, multivalence, asymmetry and metal-binding properties, highlight their status as a unique and versatile class of compounds, capable of selective separations proceeding through different mechanisms. This review provides a detailed survey of polymers containing phosphoric, phosphonic and phosphinic acid functionalities in the side chain and covers main advances in the preparation and application of these materials in separation science, including the most relevant synthesis routes (Arbuzov, Perkow, Mannich, Kabachnik-Fields reactions, etc.), as well as the main stages in the development of organophosphorus resins and the most important achievements in the field.

Synthesis, Characterization and Application of a New Functionalized Polymeric Sorbent Based on Alkenylphoshine Oxide.

A novel phosphorus-containing sorbent (CyP(Ph)4-DVB) was prepared by copolymerizing divinylbenzene (DVB) with bis α,ß-unsaturated phosphorylated cyclohexene (CyP(Ph)4). ATR-FT-IR indicated that the phosphinoyl group was introduced into the sorbent structure. The thermal properties of the sorbent were investigated using a differential scanning calorimeter (DSC), which revealed that (CyP(Ph)4-DVB) is more stable than poly(DVB). The CyP(Ph)4-DVB was applied for cationic dye removal, such as C.I. Basic Yellow 2 (BY2) and C.I. Basic Blue 3 (BB3). Batch adsorption tests suggested that the Freundlich isotherm model seemed to be the better one for the description of equilibrium sorption data at equilibrium, rather than the Langmuir or Temkin models. The Freundlich constants concerning the adsorption capacity of CyP(Ph)4-DVB, kF, were calculated as 14.2 mg1-1/nL1/n/g for BY2 and 53.7 mg1-1/nL1/n/g for BB3.

Phosphorus-Containing Telomers as UV-Curable Binders of Solvent-Free Varnish Coatings.

The synthesis of novel phosphorus-containing telomers (P-telomers) was conducted via a solution-free UV-initiated telomerization process of butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and styrene, different phosphorus telogens (dimethyl phosphite (DMPh), dibutyl phosphite (DBPh), diphenyl phosphite (DPPh) or dibutyl phosphate (DBP)), and a radical photoinitiator-acylphosphine oxide (APO). The course of the UV-phototelomerization process was monitored by photo-DSC and the chemical structures of telomers were assessed by FTIR. Final UV-photocurable varnish compositions consisted of prepared P-telomer syrups, crosslinking monomer (pentaerythritol triacrylate; PETIA), and a radical UV-photoinitiator (α-hydroxyalkylphenone, HAP). The influence of P- telomers on the optical and mechanical features of coatings was investigated. Relatively the highest hardness and satisfactory scratch values, as well as water and solvent resistance, were observed for varnish based on DMPh-telomers. While the strongest adhesive bond to a glass substrate was reported for DPPh-telomers. It is worth pointing out that the P-telomers did not affect the gloss values of varnishes in comparison to the telomer-free reference sample.