Non-Isocyanate Synthesis of Aliphatic Polyurethane by BiCl3-Catalyzed Transurethanization Polycondensation.

Non-isocyanate polyurethane synthesis by non-Sn catalysis is an essential challenge toward green polyurethane synthesis. Bismuth compounds are attractive candidates due to their low cost, low toxicity, and availability to urethane chemistry. This work applied various Bi catalysts to the self-polycondensation of a bishydroxyurethane monomer and found BiCl3 to be an excellent catalyst through optimization. The catalytic activity and price of BiCl3 are comparable to those of Bu2SnO, while its toxicity is significantly low. BiCl3 is, therefore, a promising alternative to Sn-based catalysts in non-isocyanate polyurethane synthesis.

Biodegradable epoxy thermosetting system with high adhesiveness based on glycidate-acid anhydride curing.

Biodegradable epoxy thermosets were developed by curing through copolymerization of a diglycidate monomer, a bifunctional epoxide bearing ester linkages, with cyclic acid anhydrides as a biosafe thermosetting system. The cured products of the glycidate exhibit high adhesiveness, identical to analogous cured products of conventional glycidyl ethers. Even an inert cycloolefin polymer and polyimide can be adhered. The cured products of the glycidate can be hydrolytically and biologically degraded. The biodegradation of the glycidate thermoset in compost completely proceeded within 2 weeks.

Comprehensive Study on Lemon Juice-Based Green Synthesis and Catalytic Activity of Bismuth Nanoparticles.

Bismuth nanoparticles have gained considerable interest in catalysis because of their small size, large surface-to-volume ratio, and low toxicity. In spite of these advantages, the toxic reagents and solvents used in the synthetic process are significant limitations to their development and utilization. In this study, a green approach employing easily accessible lemon juice was applied for the synthesis of bismuth nanoparticles (BiNPs) as a green alternative to conventional chemical ones. This study clarified the formation and growing process of green-synthesized BiNPs using lemon juice as a reducing and capping agent. The reaction time and amounts of lemon juice significantly affect the growth, morphology, and stability of BiNPs, as confirmed from XRD, DLS, SEM, and TEM analyses. The synthesized BiNPs effectively catalyzed the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4, and the reduction was significantly accelerated by sunlight and the removal of the fibrous coating layer around BiNPs. Moreover, the synthesized BiNPs also show excellent catalytic efficacy toward the reduction of organic dyes, namely, methyl orange, methylene blue, and rhodamine B. All catalytic reductions followed the pseudo-first-order kinetics, and the rate constants are in the order of k MB > k RhB > k MO > k 4-NP. The stated biogenic synthetic route paves the way for the green industrial fabrication of BiNPs and their uses in catalysis for wastewater treatment.

Synthesis of Bismuth-Containing Polymer Films with High Refractive Index and X-ray Shielding Property by Radical Polymerization of Styrylbismuthine Derivatives.

Highly refractive and X-ray shielding polymer films were prepared by bulk radical copolymerization of diphenylstyrylbismuthine (MStBi) with tristyrylbismuthine (TStBi). For example, a yellow transparent film was obtained by copolymerization of MStBi and TStBi in a ratio of 70:30 (w/w). The refractive index (nD) and radiopacity of the film of these polymers are 1.72 and 1.60 µm-Al/µm-polymer, respectively. These properties are higher than those of the reported bismuth-containing polymers. The thermal stability and flexural module of the polymer films were controllable by the feed ratio of TStBi. The polymer films also exhibited high surface hardness and solvent resistance due to the rigid and cross-linked structure. The chemical and thermal stability and higher refractive index and radiopacity of the polymers suggest the potential applications for X-ray shielding of optical materials with high refractive indices.

Synthesis of a Highly Selective Scavenger of Precious Metals from a Printed Circuit Board Based on Cellulose Filter Paper Functionalized with a Grafted Polymer Chain Bearing N-Methyl-2-hydroxyethylcarbamothioate Moieties.

We report the synthesis and practical application of a novel scavenger for precious metals. The scavenger was prepared from cellulose filter paper with grafted chains of poly(glycidyl methacrylate) modified with a novel ligand group of N-methyl-2-hydroxyethylcarbamothioate moieties, introduced by the reaction with O-1-mercapto-3-phenoxypropan-2-yl N-methyl-2-hydroxyethylcarbamothioate. Batch experiments were performed to evaluate the capability of the scavenger in ranges of pH and acid concentration as well as to determine the kinetics and isotherm models. The scavenger was found to adsorb only Ag(I), Pd(II), and Au(III) from an aqueous media in the presence of coexisting ions of different bases and precious metals at wide ranges of pH and acid concentration. The adsorption rates fit a pseudo-second-order kinetic equation, and the adsorption reached equilibrium within 60 min. The isotherm studies indicated that the obtained data were a good fit with the Langmuir model. The maximum adsorption capacities of Ag(I), Pd(II), and Au(III) were 126.95, 124.67, and 230.67 mg g-1, respectively. Regeneration experiments indicated that the adsorbent maintained 97% of its initial efficiency even after five adsorption/desorption cycles. The scavenger was effectively utilized to recover Ag(I), Pd(II), and Au(III) from an aqua regia solution of waste printed circuit boards.

A facile aqueous production of bisphosphonated-polyelectrolyte functionalized magnetite nanoparticles for pH-specific targeting of acidic-bone cells.

Bone malignancy treatment is being hindered due to the insufficient selectivity of therapeutic nanoparticles towards malignant bone sites. Polyelectrolyte functionalized magnetic nanoparticles having dually specific pH-sensing ability and bisphosphonate moieties, can be an effective solution for selective targeting of bone malignancies. First, polyelectrolyte was prepared via N-carboxycitraconyzation of chitosan (NCCS) followed by successive functionalization with alendronic acid (AL) and fluorescein isothiocyanate (FITC). Then, Fe3O4-NCCS-FITC-AL nanoparticles were synthesized by a facile one-step microwave-assisted aqueous method via in situ surface functionalization. The formation, crystal structure, and surface conjugation of Fe3O4 nanoparticles with polyelectrolytic stabilizer were confirmed by Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analyses. Synthesized Fe3O4-NCCS-FITC-AL nanoparticles were superparamagnetic, colloidally stable and highly hemocompatible under physiological conditions. Moreover, at pH 5.0, Fe3O4-NCCS-FITC-AL nanoparticles formed a precipitate due to inversion of their surface charge. This pH-dependent charge-inversion drastically changed the interactions with erythrocytes and bones. Selective membranolysis of erythrocytes occurred at pH 5.0. The designed nanoparticles showed enough potential for selective targeting of pathological bone sites in early-stage magnetofluorescent imaging and as a therapeutics carrier to treat malignant bone diseases.

Glycidate as a High-Strength Epoxy Adhesive Curable with Amine under Ambient Conditions.

This paper reports that glycidates bearing epoxy moieties with adjacent ester can be cured with diethylenetriamine (DETA) under mild conditions and exhibit high adhesiveness. Curing of bifunctional glycidates with DETA gave cross-linked products. The curing started at a lower temperature (7 °C) than the analogous glycidyl ether (27 °C), while the rate of the curing was slower due to the lower activation energy (Ea = 57 kJ/g) and exothermicity (ΔH = 58 J/g) as confirmed by DSC analysis. The curing system of neopentyl glycol diglycidate and DETA effectively adhered aluminum plates by curing at 25 °C, and the strength was more than five times higher than the curing with analogous glycidyl ether. The higher adhesive strength under curing of ambient conditions and facile preparation of monomers are the significant advantages of this curing.

Synthesis and Selective Au(III) Adsorption of Ureido Polymers Containing Large Repeating Rings.

Two polymers (polyBAUEE and polyBAUP) containing 25- and 20-membered rings are synthesized by the cyclopolymerization of bifunctional monomers 1,2-bis(acryloyloxyethyl-ureidoethoxyl)-ethane (BAUEE) and 1,3-bis(acryloyloxyethylureido)propane (BAUP) and studied for the adsorption of precious metal ions. PolyBAUEE and polyBAUP selectively adsorb Au(III) with the adsorption efficiencies above 99.0% after adsorption equilibrium. PolyBAUEE adsorbed faster than polyBAUP, and the Au(III) adsorption is selective in the presence of nine interfering metal ions with similar concentrations (ca. 1 mg/L) in an aqueous solution including Pd(II) and Pt(II). The maximum Au(III) adsorption capacities of polyBAUEE and polyBAUP are 37.6 and 31.8 mg/g, respectively. Au(III) is reduced to Au(0) nanoparticles during the adsorption process. The selective adsorption behavior depends on the controlling regioselective recognition of the ring structure and the ureido groups.

Biogenic Synthesis and Catalytic Efficacy of Silver Nanoparticles Based on Peel Extracts of Citrus macroptera Fruit.

Biogenically synthesized silver nanoparticles (AgNP) increase the fascination over chemical ones due to their facile and green synthetic process. This study reports the development of an eco-friendly and cost-effective synthesis of AgNPs using an aqueous extract of Citrus macroptera fruit peel, an agricultural waste, as a sole agent with both reducing and capping abilities. The formation of AgNPs was verified by the surface plasmon resonance peak at 426 nm in the UV-vis spectrum, X-ray diffraction pattern, and transmission electron micrography images. The AgNPs obtained under the optimized conditions consist of face-centered cubic crystals and spherical morphology with an average size of 11 nm. The AgNPs are coated with phytochemicals in the C. macroptera fruit peel extract and are stably dispersible due to their negatively charged nature. The AgNPs effectively catalyzed the reduction of 4-nitrophenol to 4-aminophenol and the degradation of methyl orange and methylene blue in the presence of sodium borohydride. This method employing a fruit peel extract is facile, efficient, eco-friendly, and cost-effective and has potential for industrial green fabrication of AgNPs.

Green synthesis of crystalline bismuth nanoparticles using lemon juice.

Lemon juice effectively served as a reducing and capping agent for an easy, cost-effective, and green synthesis of crystalline bismuth nanoparticles (BiNPs) in basic aqueous media. Spherical BiNPs with a rhombohedral crystalline structure are capped by phytochemicals and stably dispersible in aqueous media. The BiNPs effectively catalyze the reduction of 4-nitrophenol to 4-aminophenol by NaBH4.

Green Synthesis and Catalytic Activity of Silver Nanoparticles Based on Piper chaba Stem Extracts.

A green synthesis of silver nanoparticles (AgNPs) was conducted using the stem extract of Piper chaba, which is a plant abundantly growing in South and Southeast Asia. The synthesis was carried out at different reaction conditions, i.e., reaction temperature, concentrations of the extract and silver nitrate, reaction time, and pH. The synthesized AgNPs were characterized by visual observation, ultraviolet-visible (UV-vis) spectroscopy, dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), energy dispersive x-ray (EDX), and Fourier transform infrared (FTIR) spectroscopy. The characterization results revealed that AgNPs were uniformly dispersed and exhibited a moderate size distribution. They were mostly spherical crystals with face-centered cubic structures and an average size of 19 nm. The FTIR spectroscopy and DLS analysis indicated that the phytochemicals capping the surface of AgNPs stabilize the dispersion through anionic repulsion. The synthesized AgNPs effectively catalyzed the reduction of 4-nitrophenol (4-NP) and degradation of methylene blue (MB) in the presence of sodium borohydride.

Milling in Seconds Accelerates Acetylation of Cellulose in Hours.

A new sustainable synthetic method for cellulose acetate was developed by a combination of I2-catalyzed solid-liquid acetylation of cellulose and a milling process reducing the crystallinity of cellulose within a few seconds. Milled low-crystalline cellulose was acetylated faster than the original cellulose with higher crystallinity. The plausible factors of acceleration were the conversion of the hydroxy group in hydrogen bonds into reactive ones and the efficient formation of the catalytic species I+ by the enhanced formation of I3 - assisted by the amorphous domain of the milled cellulose, while the morphological and structural changes were ignorable.

pH-Responsive Charge-Conversional and Hemolytic Activities of Magnetic Nanocomposite Particles for Cell-Targeted Hyperthermia.

Magnetic nanocomposite particle (MNP)-induced hyperthermia therapy has been restricted by inefficient cellular targeting. pH-responsive charge-conversional MNPs can enhance selective cellular uptake in acidic cells like tumors by sensing extracellular acidity based on their charge alteration. We have synthesized new, pH-induced charge-conversional, superparamagnetic, and single-cored Fe3O4 nanocomposite particles coated by N-itaconylated chitosan (NICS) cross-linked with ethylene glycol diglycidyl ether (EGDE) (Fe3O4-NICS-EGDE) using a simple, one-step chemical coprecipitation-coating process. The surface of the Fe3O4-NICS-EGDE nanocomposite particles was modified with ethanolamine (EA) via aza-Michael addition to enhance their buffering capacity, aqueous stability, and pH sensitivity. The designed Fe3O4-NICS-EGDE-EA nanocomposite particles showed pH-dependent charge-conversional properties, colloidal stability, and excellent hemocompatibility in physiological media. By contrast, the charge-conversional properties enabled microwave-induced hemolysis only under weakly acidic conditions. Therefore, the composite particles are highly feasible for magnetically induced and targeted cellular thermotherapeutic applications.

Development of Hierarchical Polymer@Pd Nanowire-Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink.

A facile one-pot approach for preparing hierarchical nanowire-networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal-complexation-induced phase separation with functionalized graft copolymers and subsequent self-assembly of PdNPs. The nanospheres hierarchically assembled into the nanowire-network upon drying. The Pd nanowire-network served as an active catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling reactions. As low as 500 µmol % Pd was sufficient for quantitative reactions, and the origin of the high activity is ascribed to the highly active sites originating from high-index facets, kinks, and coalesced structures. The catalyst can be recycled via simple filtration and washing, maintaining its high activity owing to the micrometer-sized hierarchical structure of the nanomaterial. The polymer@Pd nanosphere also served as a printable conductive ink for a translucent grid pattern with excellent horizontal conductivity (7.5×10(5) S m(-1)).

One-Pot Synthesis of Organic-Sulfur-Zinc Hybrid Materials via Polycondensation of a Zinc Salt and Thiols Generated in Situ from Cyclic Dithiocarbonates.

Soluble organic-sulfur-zinc hybrid polymers were prepared via a one-pot reaction consisting of ring-opening addition and subsequent polycondensation. The first reaction is the nucleophilic ring-opening addition of 2-ethylhexylamine to multifunctional cyclic dithiocarbonates giving multiple thiols in situ. The sequential polycondensation of the in situ generated thiols with Zn(OAc)2 gave the target hybrid polymers. This one-pot method enabled the use of a shorter amine than the previous polycondensation of Zn(OAc)2 and purified thiols, which required octadecylamine to obtain a soluble product. The obtained hybrid polymers may be cast as composite films with polystyrene and poly(methyl methacrylate). Owing to the shorter alkyl chain, the calculated nD values of the products (1.60 or 1.61) are higher than that of the previous product bearing octadecyl chains (1.53).

Organic-sulfur-zinc hybrid nanoparticle for optical applications synthesized via polycondensation of trithiol and Zn(OAc)2.

Organic-sulfur-zinc hybrid materials were prepared via polycondensation of Zn(OAc)2 and trithiols bearing various alkyl groups. A soluble nanoparticle could be obtained by the polycondensation using a trithiol bearing octadecyl moieties. The good dispersing ability as nano-scaled particles was confirmed by dynamic light scattering and atomic force microscopy analyses. This hybrid nanoparticle was miscible with poly(methyl methacrylate) and served as a refractive additive to increase refractive indexes. The calculated refractive index value for the nanoparticle was 1.58.

Formation of flat, homogeneous surfaces of organized molecular films of three-armed polymerizable amphiphiles with metal-scavenging properties.

Surface complexing (i.e., metal-bridged polymerization in this study) of a three-armed amphiphilic compound with metal-scavenging properties has been investigated using the surface pressure-area (π-A) isotherms of a Langmuir monolayer from the subphase. Inductively coupled plasma mass spectrometry (ICP-MS) was also carried out on eluted solutions from corresponding multilayers of the solid. Furthermore, the molecular arrangement and surface morphology of organized molecular films of the resultant comb polymer were estimated by in-plane and out-of-plane X-ray diffraction (XRD) and by atomic force microscopy. From an analysis of the wide-angle X-ray diffraction of the corresponding monomer in the bulk, the long hydrocarbon chains are observed to pack hexagonally in the solid state. Compared to their monolayer on distilled water as the subphase, a polymerized monolayer on a buffer solution containing Cd(2+) ions is remarkably expanded at 15 °C. From ICP-MS and IR measurements, it is found that this monolayer stoichiometrically contains Cd(2+) ions on the -SH group. It is found by XRD that highly ordered layer structures and regular 2D lattices are constructed in the organized molecular films of the Cd-bridged comb polymer. Furthermore, the surface morphology of Langmuir-Blodgett films fabricated from the monolayers on a buffer solution containing Cd(2+) and Pd(2+) shows flat and smooth domains upon metal scavenging and polymerization.

Synthesis of rare-metal absorbing polymer by three-component polyaddition through combination of chemo-selective nucleophilic and radical additions.

Sequential three-component polyaddition has been difficult, because the first addition typically consumes the two reactive monomers to produce a stable intermediate that cannot react smoothly with the remaining most stable monomer. The combination of nucleophilic and radical additions has overcome this thermodynamic problem. The first nucleophilic addition of diamines to cyclic dithiocarbonates produces bis(mercaptothiourethane)s that can attack diethynylbenzene radically, which consequently gives poly(thiourethane-phenylenevinylenesulfide)s in high atom efficiency up to 95%. The resulting polymer extracted palladium and gold cations from their aqueous solutions in excellent efficiencies.

Controlled cyclopolymerization through quantitative 19-membered ring formation.

Cyclopolymerization of a bis-methacrylate monomer derived from trans-cyclohexanediol and 2-methacryloyloxyethyl isocyanate proceeded through 19-membered ring formation. The unusual large ring formation originated from the designed steric regulation by the cyclohexane ring and the hydrogen bonds. The RAFT polymerization employing cumyl dithiobenzoate attained controlled polymerization, which supported the quantitative cyclization.

Chiroptical inversion induced by sandwiching units in chiral polythiourethane.

Chiroptical behavior of a hydrogen-bond-regulated chiral polythiourethane segment was inversed by sandwiching sterically demanding segments in copolymers prepared by cationic ring-opening copolymerization of chiral cyclic thiourethanes derived from L-serine.