Exploring Functional Polymers in the Synthesis of Luminescent ZnO Quantum Dots for the Detection of Cr6+, Fe2+, and Cu2.

The main aim of this work is to demonstrate that well-defined methacrylate-based copolymers with oligoethylene glycol side chains and functional groups such as thiol and glycidyl, obtained by photo-initiated reversible addition-fragmentation chain transfer (RAFT) in ethanol, are highly suitable as templates in the synthesis and protection of ZnO quantum dots (ZnO QDs) with remarkable photoluminescent properties. While the affinity of thiol groups to metallic surfaces is well established, their interaction with metal oxides has received less scrutiny. Furthermore, under basic conditions, glycidyl groups could react with hydroxyl groups on the surface of ZnO, representing another strategy for hybrid synthesis. The size and crystalline morphology of the resulting hybrids were assessed using DLS, TEM, and XRD, indicating that both polymers, even with a low proportion of functional groups (5% mol) are appropriate as templates and ligands for ZnO QDs synthesis. Notably, thiol-containing polymers yield hybrids with ZnO featuring excellent quantum yield (up to 52%), while polymers with glycidyl groups require combination with the organosilane aminopropyl triethoxysilane (APTES) to achieve optimal results. In both cases, these hybrids exhibited robust stability in both ethanol and aqueous environments. Beyond fundamental research, due to the remarkable photoluminescent properties and affordability, these hybrid ZnO QDs are expected to have potential applications in biotechnology and green science; in particular, in this study, we examined their use in the detection of environmental contaminants like Fe2+, Cr6+, and Cu2+. Specifically, the limit of detection achieved at 1.13 µM for the highly toxic Cr6+ underscores the significant sensing capabilities of the hybrids.

RAFT Hydroxylated Polymers as Templates and Ligands for the Synthesis of Fluorescent ZnO Quantum Dots.

The remarkable photoluminescent properties, biocompatibility, biodegradability, and antibacterial properties of zinc oxide quantum dots (ZnO QDs) coupled with their low cost and nanoscale size guarantee bio-related and technological applications. However, the effect of the polymeric ligand during synthesis has hardly been investigated compared to other less environmentally friendly QDs. Thus, the objective of this work was to focus on the synthesis of fluorescent hybrid ZnO QDs by the sol-gel method using different polymers with hydroxyl groups as templates and ligands to obtain stable particles in different media. For this purpose, well-defined hydroxylated statistical polymers and block copolymers were synthesized using reversible-addition fragmentation chain transfer (RAFT) polymerization to establish the influence of molecular weight, hydrophobic/hydrophilic balance, and polymer architecture on the colloidal and photophysical properties of the synthesized hybrid ZnO QDs. Dynamic light scattering (DLS), TEM, and X-ray diffraction measurements indicated the formation of stable nanoparticles of a few nanometers. A remarkable enhancement in terms of fluorescence was observed when ZnO QDs were synthesized in the presence of the hydroxylated homopolymers and even more so with block copolymers architecture. Organosilanes combined with the hydroxylated polymers were used to improve the colloidal stability of ZnO QDs in aqueous media. These samples exhibited uniform and stable enhanced photoluminescence for nearly five months of being investigated. Among other applications, the hybrid ZnO QDs synthesized in this work exhibit high selectivity to detect Cr6+, Fe2+, or Cu2+ in water.

Concentration Effect over Thermoresponse Derived from Organometallic Compounds of Functionalized Poly(N-isopropylacrylamide-co-dopamine Methacrylamide).

The functionalization of smart polymers is opening a new perspective in catalysis, drug carriers and biosensors, due to the fact that they can modulate the response regarding conventional devices. This smart response could be affected by the presence of organometallic complexes in terms of interactions which could affect the physical chemical properties. In this sense, the thermoresponsive behavior of copolymers based on N-isopropylacrylamide (NIPAM) could be affected due to the presence of hydrophobic groups and concentration effect. In this work, the functionalization of a copolymer based on NIPAM and dopamine methacrylamide with different amounts of bis(cyclopentadienyl)titanium (IV) dichloride was carried out. The resulting materials were characterized, showing a clear idea about the mechanism of functionalization through FTIR spectroscopy. The thermoresponsive behavior was also studied for various polymeric solutions in water by UV-vis spectroscopy and calorimetry. The hydrophobic interactions promoted by the organometallic complex could affect the transition associated with the lower critical solution temperature (LCST), specifically, the segments composed by pure NIPAM. That fact would explain the reduction of the width of the LCST-transition, contrary to what could be expected. In addition, the hydrophobicity was tested by the contact angle and also DNA interactions.

The synthesis of switch-off fluorescent water-stable copper nanocluster Hg2+ sensors via a simple one-pot approach by an in situ metal reduction strategy in the presence of a thiolated polymer ligand template.

The fabrication of stable fluorescent copper nanoclusters (CuNCs) in aqueous media is still challenging, despite the low price and potential biomedical applications. Herein, we report a facile and efficient strategy for assembling CuNCs using multifunctional thiolated copolymers with pH and thermoresponsive features. The new nanohybrids are formed via a simple one-pot approach through the reduction of a copper salt with hydrazine in the presence of a multithiolated polymer, which provides a template during nanocluster assembly and further efficient protection against oxidation and aggregation. Furthermore, the thermo- and pH-responsive properties of the pristine copolymers endow the nanohybrids with these stimuli-responsive features. The thiol content and the macromolecular size of the polymer ligands exert strong influences on the final photophysical properties of these new hybrid luminescent nanoclusters. The existence of stable bright greenish-yellow emission in water over long periods of time, the high photostability under UV irradiation and the strong oxidation resistance toward hydrogen peroxide of the hybrid CuNCs suggest that they have great promise for nanomedicine, bioassay and nanosensor use. Furthermore, the polymeric CuNCs obtained have been successfully tested as optical switch-off sensors for the sensitive and highly selective detection of Hg2+ in the presence of other metal ions in liquid and solid states. Finally, we demonstrate the practical application of the new hybrid to Hg2+ detection in human urine.

Curcumin to Promote the Synthesis of Silver NPs and their Self-Assembly with a Thermoresponsive Polymer in Core-Shell Nanohybrids.

This work presents a simple one-pot protocol to achieve core-doped shell nanohybrids comprising silver nanoparticles, curcumin and thermoresponsive polymeric shell taking advantage of the reducing properties of phenolic curcumin substance and its ability to decorate metallic surfaces. Silver nanoparticles were synthesized, via sodium citrate and silver nitrate addition into a boiling aqueous solution of curcumin, monomers and surfactant. Curcumin and sodium citrate promoted silver nucleation, acting as reducing and stabilizing agents. These curcumin-capped AgNPs enabled, after adding the radical polymerization initiator, the assembling of the growing polymer chains around the hydrophobic AgNP surface. The resultant core-doped shell nanohybrids exhibit plasmonic, luminescent and volume thermoresponsive properties, with improved possibilities to be used as successful therapeutic platforms. In fact, the possibility to nanoconfine the synergistic antioxidant, antiviral, antibacterial features of silver and curcumin in one bioavailable hybrid paves the way to promising applications in the biomedical field.

Synthesis of Au@polymer nanohybrids with transited core-shell morphology from concentric to eccentric Emoji-N or Janus nanoparticles.

The combination of multifunctionality and synergestic effect displayed by hybrid nanoparticles (NPs) has been revealed as an effective stratagem in the development of advanced nanostructures with unique biotechnology and optoelectronic applications. Although important work has been devoted, the demand of facile, versatile and efficient synthetic approach remains still challenging. Herein, we report a feasible and innovative way for polymer-shell assembling onto gold nanoparticles in competitive conditions of hydrophobic/hydrophilic feature and interfacial energy of components to generate core-shell nanohybrids with singular morphologies. The fine control of reaction parameters allows a modulated transformation from concentric to eccentric nanostructure-geometries. In this regard, a rational selection of the components and solvent ratio guarantee the reproducibility and efficiency on hybrid-nanoassembly. Furthermore, the simplicity of the synthetic approach offers the possibility to obtain asymmetric Janus NPs and new morphologies (quizzical-aspheric polymer-shell, named Emoji-N-hybrids) with adjustable surface-coating, leading to new properties and applications that are unavailable to their symmetrical or single components.

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation.

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO3 to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag-PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation.

The surface modification of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymers to improve the attachment of urothelial cells.

Biocompatible and biodegradable poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB-co-HHx)] substrates were modified to improve the attachment of porcine urothelial cell culture. The pristine copolymer exhibits excellent mechanical properties to replace the bladder tissue, but its surface lacks chemical functionalities to interact with cells. Thus, wet chemical treatments based on NaOH and ethylenediamine in aqueous [ED(aq)] and isopropanol [ED(isoOH)] media to functionalize the P(HB-co-HHx) films surfaces were compared. Among these treatments, short ED(aq) treatment was able to decrease the hydrophobicity, rendering a surface with amino groups and without a significant alteration of the mechanical properties. Furthermore, to enhance the interaction with urothelial cells, laminin derived YIGSR sequence was covalently bound to these amino functionalized substrates. The focal attachment was clearly improved with this last treatment, comparing with those results found with the unmodified and first-step functionalized P(HB-co-HHx).

Surface modification of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer films for promoting interaction with bladder urothelial cells.

Often bladder dysfunction and diseases lead to therapeutic interventions that require partial or complete replacement of damaged tissue. For this reason, the development of biomaterials to repair the bladder by promoting the adhesion and growth of urothelial cells is of interest. With this aim, a modified copolyester of biocompatible and biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB-co-HV)] was used as scaffold for porcine urothelial cell culture. In addition to good biocompatibility, the surface of P(HB-co-HV) substrates was modified to provide both, higher hydrophilicity and a better interaction with urothelial cells. Chemical treatments with ethylenediamine (ED) and sodium hydroxide (NaOH) led to substrate surfaces with decreasing hydrophobicity and provided functional groups that enable the grafting of bioactive molecules, such as a laminin derived YIGSR sequence. Physico-chemical properties of modified substrates were studied and compared with those of the pristine P(HB-co-HV). Urothelial cell morphology on treated substrates was studied. The results showed that focal attachment and cell-related properties were improved for peptide grafted polymer compared with both, the unmodified and functionalized copolyester.

Diffusion of small molecules in a chitosan/water gel determined by proton localized NMR spectroscopy.

Proton localized NMR spectroscopy (MRS) has been applied to study the diffusion of three small molecules, caffeine, theophylline and caprolactam, in chitosan gels with different concentration of water. This technique allows the non-destructive monitorization of diffusant concentration as a function of time and location. Concentration profiles were compared with theoretical curves based on solutions of Fick's diffusion equation for the best fitting, with the appropriate boundary conditions. The measured concentration profiles show a good agreement with the Fickian law. Values of the diffusion coefficients D ranging from 6.1×10(-6) to 3.4×10(-6)cm(2)s(-1) depending on chitosan concentration and type of diffusant molecule were determined. In addition, measurements of diffusion coefficients at equilibrium conditions with proton pulsed field gradient NMR methods supported the observed Fickian behavior and showed values of D in excellent agreement with those determined by proton MRS. All these facts demonstrate that proton MRS is an appropriate method for investigating diffusion process in complex systems, such as polymer gels.

Dependence of copolymer composition, swelling history, and drug concentration on the loading of diltiazem hydrochloride (DIL.HCl) into poly[(N-isopropylacrylamide)-co-(methacrylic acid)] hydrogels and its release behaviour from hydrogel slabs.

The loading of an antihypertensive cationic drug, diltiazem hydrochloride (DIL.HCl), into poly(N-isopropylacrylamide) [P(N-iPAAm)], poly(methacrylic acid) [P(MAA)], and their poly[(N-isopropylacrylamide)-co-(methacrylic acid)] P[(N-iPAAm)-co-(MAA)] hydrogels as well as their release behaviour have been investigated. For this purpose, two series of hydrogels have been tested, one previously soaked under acidic pH (treated hydrogels) and the other from the synthesis and washed in deionized water (untreated hydrogels). For the drug loading, these two series of hydrogels have been soaked in drug solutions with different concentrations. DIL.HCl amounts loaded by the gels as well as swelling degrees as a function of both hydrogel composition and DL.HCl concentration in the loading solution have been analyzed. Due to the interactions among DIL.HCl and the MAA group, "untreated" enriched MAA copolymer hydrogels present the highest drug load and loading efficiency. A DIL.HCl concentration of 320 microm/mL has been employed to load copolymers for release experiments, because for this concentration, hydrogels reach relative high drug load with a still high efficiency of loading. Release has been tested in three media, namely, fresh water (Milli-Q grade, pH 7.0), 0.1 N hydrogen chloride (pH 1.2), and a phosphate buffer (pH 7.0). In general, release is lower in fresh water and acidic media than in phosphate buffer. To explain these results, the effect of temperature, medium, and composition on the pH and thermo sensitivity of the hydrogels as well as the diltiazem-polymer interactions have been taken into account.

The influence of the copolymer composition on the diltiazem hydrochloride release from a series of pH-sensitive poly[(N-isopropylacrylamide)-co-(methacrylic acid)] hydrogels.

A series of poly[(N-isopropylacrylamide)-co-(methacrylic acid)] (P[(N-iPAAm)-co-(MAA)]) hydrogels was investigated to determine the composition that exhibits a better pH-modulated release of diltiazem hydrochloride (DIL.HCl). For this purpose hydrogel slabs were loaded with DIL.HCl by the immersion method, and its release under acidic medium (0.1N HCl, pH 1.2) and in phosphate buffer pH 7.2, using United States Pharmacopeia (USP) 24 Apparatus 1, was investigated. According to the results from the slabs, copolymers with 85% mol N-iPAAm content were selected to prepare tablets with different particle size. The effect of pH and particle size changes on DIL.HCl release from these last hydrogel tablets was investigated by a stepwise pH variation of the dissolution medium. The amount of DIL.HCl released from high N-iPAAm content copolymer slabs under acidic pH medium was not only very low but it was also released at a slow rate. In the 85% N-iPAAm tablets, significant differences between and within release profiles were found as a function of particle size and pH, respectively. A relationship between particle size and release rate has been found. The lower DIL.HCl release at acidic pH from enriched N-iPAAm copolymers is interpreted by a cooperative thermal- and pH-collapse. Although for the whole range of copolymer composition a dependence of the equilibrium of swelling on the pH was found, DIL.HCl release experiments indicated that hydrogels with 85% mol N-iPAAm are the more adequate to be used for modulated drug delivery systems. Additionally, the particle size of the tablet can be used to tailor the release rate.

In situ deuteron NMR investigations of sheared liquid crystalline polymers.

The flow behavior of nematic liquid crystalline polysiloxanes of the side-chain type is studied by in situ 2H NMR spectroscopy on samples under shear in a cone-and-plate cell. The director orientation as a function of applied shear rate is determined from the quadrupole splitting of the spectra. The data analysis yields the two Leslie viscosity coefficients alpha2 and alpha3 and the flow-alignment parameter lambda = -(alpha3 + alpha2)/(alpha3 - alpha2). The values of lambda were determined for several homopolymers with only one type of side chain and random copolymers containing two different side chains. The results show that the flow behavior is related to the phase structure of the polymers, which varies with their composition. Only polymers with large amounts of smectic clusters in the nematic state show the tumbling instability (absolute value(lambda) < 1); other polymers are flow aligning (absolute value(lambda) > or = 1). For some polymers, a transition from tumbling at low temperature to flow aligning at high temperatures was observed.