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Cancer is the second leading cause of death worldwide. To combat this disease, novel and specialized therapeutic systems are urgently needed. This is the first study to explore a system that combines shark variable domain (Fv) of new antigen receptor (VNAR) antibodies (hereinafter VNARs), PEGylated nanogels (pH-sensitive poly( N , N -diethylaminoethyl methacrylate, PDEAEM), and the anticancer drug 5-fluorouracil (5-FU) to explore its potential applications in colon cancer therapies. Nanogels were functionalized in a scalable reaction with an N -hydroxysuccinimide (NHS)-terminated polyethylene glycol derivative and bioconjugated with shark antibodies. Dynamic light scattering measurements indicated the presence of monodispersed nanogels (74 to 236 nm). All systems maintained the pH-sensitive capacity to increase in size as pH decreased. This has direct implications for the release kinetics of 5-FU, which was released faster at pH 5 than at pH 7.4. After bioconjugation, the ELISA results indicated VNAR presence and carcinoembryonic antigen (CEA) recognition. In vitro evaluations of HCT-116 colon cancer cells indicated that functionalized empty nanogels are not cytotoxic and when loaded with 5-FU, the cytotoxic effect of the drug is preserved. A 15% reduction in cell viability was observed after two hours of contact with bioconjugated nanogels when compared to what was observed with non-bioconjugated nanogels. The prepared nanogel system shows potential as an effective and site-specific nanocarrier with promising applications in in vivo studies of colon cancer therapies.

In the presence of naphthylbutadiyne (DNB) and dinitronaphthylbutadiyne (DNNB), ESR signals of propagating PMMA radicals with concentration of the order of 10 14 –10 15 radicals per ml were observed from early stage of polymerization, and their concentration increased with conversion. The concentration of the DNNB system was about double of that of the DNB system, indicating that electron accepting groups increase the stabilization of PMMA radicals. No fragment of the butadiynes are found in the PMMA obtained, indicating that the aromatic diacetylenes stabilize free radicals without suffering the addition reaction.

Currently, there is a demand for effective flocculant systems that can be used without adverse impact on the environment and health. However, the challenge is to find the minimum dose to achieve the same efficacy as conventional flocculants. One technique involves using a mixture of natural and synthetic flocculants, the synergistic effects of which can enhance treatment efficiency. Thus, this work provides an approach using a low-cost chitosan (CH56)–polyaluminum chloride (PAC) mixture as a flocculant system for river water. Therefore, water quality was monitored in the Tamazula and Humaya rivers, which are sources of water for potabilization plants. According to the results of flocculation tests, the use of the mixture required a lower dosage (0.75 mg L−1 of CH56 with 1 mg L−1 of PAC; 0.75 mg L−1 of CH56 with 2 mg L−1 of PAC) than that used with individual flocculants (3 mg L−1 of CH56; 5 mg L−1 of PAC). Conveniently, the mixture produced larger and more compact flocs, favoring sedimentation kinetics and thus flocculation. Fractal dimension (FD) and lacunarity (Λ) from microscopy images were used as indicators of the quality of the flocs formed. In general, CH56 and the mixture performed better than PAC, and the mixture allowed the best removal of the model microplastic (polystyrene). Flocculant mixtures reduced the concentration of copper ions by 58%, of tetracycline by 22%, of microplastics by 80%, and of bacteria by >90%. Hence, the authors believe that this work offers valuable information that could be used for potabilization plants aiming to reduce the dose of PAC and introduce chitosan into their coagulation–flocculation process.

Chemically crosslinked hydrogels based on poly(N-vinylcaprolactam) (PNVCL) were synthetized by a photoinitiated chemical method. A galactose-based monomer, 2-lactobionamidoethyl methacrylate (LAMA), and N-vinylpyrrolidone (NVP) were added with the aim to improve the physical and chemical properties of hydrogels. The effects of both comonomers on the swelling ratio (Q), volume phase transition temperature (VPTT), glass transition temperature (Tg), and Young’s moduli by mechanical compression below and above the VPTT were studied. Gold nanorods (GNRDs) and 5-fluorouracil (5FU) were embedded into the hydrogels, to study the drug release profiles with and without the excitation of GNRDs by irradiation in the near-infrared region (NIR). Results showed that the addition of LAMA and NVP increased the hydrogels’ hydrophilicity, elasticity, and VPTT. The loading of GNRDs in the hydrogels changed the release rate of 5FU when irradiated intermittently with an NIR laser. The present study reports on the preparation of a hydrogel-based platform of PNVCL-GNRDs−5FU as a potential hybrid anticancer hydrogel for chemo/photothermal therapy that could be applied against skin cancer for topical 5FU delivery.

Dual-function nanogels (particle size from 98 to 224 nm) synthesized via surfactant-free emulsion polymerization (SFEP) were tested as smart carriers toward synergistic chemo- and photothermal therapy. Cisplatin (CDDP) or doxorubicin (DOX) and gold nanorods (GNRDs) were loaded into galacto-functionalized PNVCL-based nanogels, where the encapsulation efficiency for CDDP and DOX was around 64 and 52%, respectively. PNVCL-based nanogels were proven to be an efficient delivery vehicle under conditions that mimic the tumor site in vitro. The release of CDDP or DOX was slower at pH 7.4 and 37 °C than at tumor conditions of pH 6 and 40 °C. On the other hand, in the systems with GNRDs at pH 7.4 and 37 °C, the sample was irradiated with a 785 nm laser for 10 min every hour, obtaining that the release profiles were even higher than in the conditions that simulated a cancer tissue (without irradiation). Thus, the present study demonstrates the synergistic effect of chemo- and photothermal therapy as a promising dual function in the potential future use of PNVCL nanogels loaded with GNRDs and CDDP/DOX to achieve an enhanced chemo/phototherapy in vivo.

The effect on the RAFT polymerization of di(ethylene glycol) methyl ether methacrylate (DEGMA) and oligo(ethylene glycol) methyl ether methacrylates M n  = 300 g mol −1 (OEGMA) was studied when the R leaving group of the chain transfer agent (CTA) 4-cyano-4-(propylsulfanylthiocarbonyl)sulfanyl pentanoic acid ( CPP ) changes due to its partial auto-hydrolysis of the nitrile group to form the corresponding amide, therefore a different CTA ( APP ). In the best of our knowledge, this partial hydrolysis of this compound had not been reported. Characterization of all compounds and polymers was carried out by FTIR-ATR, NMR, DSC and TGA. Monomer conversion was evaluated by 1 H NMR; M n , M w and Đ were obtained by GPC; finally, their thermo-responsive character was evaluated. By using CTA in polymer synthesis, average molecular weights were lower than by conventional free radical polymerization (FRP), when CPP and APP mediated polymerizations were compared, there were differences in rate polymerization of DEGMA resulting in different molecular weights and Đ ; however in the RAFT polymerization of OEGMA similar products were obtained. Finally, their thermo-responsive character was evaluated, in which cloud point temperatures for PDEGMA and POEGMA using APP were observed between 23 and 24 and 65–68 °C respectively.

This work shows an optimized enzymatic hydrolysis of high molecular weight potato galactan yielding pectic galactan-oligosaccharides (PGOs), where endo-β-1,4-galactanase (galactanase) from Cellvibrio japonicus and Clostridium thermocellum was used. For this, response surface methodology (RSM) by central composite design (CCD) was applied. The parameters varied were temperature (°C), pH, incubation time (min), and enzyme/substrate ratio (U/mg). The optimized conditions for the production of low degree of polymerization (DP) PGOs were obtained for each enzyme by spectrophotometric assay and confirmed by chromatography. The optimal conditions predicted for the use of C. japonicus galactanase to obtain PGOs of DP = 2 were T = 51.8 °C, pH 5, E/S = 0.508 U/mg, and t = 77.5 min. For DP = 3, they were T = 21 °C, pH 9, E/S = 0.484 U/mg, and t = 12.5 min; and for DP = 4, they were T = 21 °C, pH 5, E/S = 0.462 U/mg, and t = 12.5 min. The efficiency results were 51.3% for substrate hydrolysis. C. thermocellum galactanase had a lower yield (35.7%) and optimized conditions predicted for PGOs of DP = 2 were T = 60 °C, pH 5, E/S = 0.525 U/mg, and time = 148 min; DP = 3 were T = 59.7 °C, pH 5, E/S = 0.506 U/mg, and time = 12.5 min; and DP = 4, were T = 34.5 °C, pH 11, E/S = 0.525 U/mg, and time = 222.5 min. Fourier transformed infrared (FT-IR) and nuclear magnetic resonance (NMR) characterizations of PGOs are presented.

Polyethyleneglycol- block -poly( N,N′ -diethylaminoethyl methacrylate) (PEG- b -PDEAEM) copolymers were used as nanoreactors for the preparation of gold nanoparticles (AuNPs) in aqueous and alcoholic medium. These copolymers were synthesized changing the size of the PDEAEM block by using reversible addition–fragmentation chain transfer (RAFT) polymerization as demonstrated by nuclear magnetic resonance and gel permeation chromatography measurements. The PEG- b -PDEAEM block copolymers were dispersed in water to form aggregates with sizes around 100 nm, depending on the lengths of the PDEAEM segment as well as the pH of the solution. The corresponding unimers were evident when these same copolymers were dissolved in alcohol or tetrahydrofuran medium showing hydrodynamic diameters ( D h ) between 4 and 10 nm. The aggregates and unimers were used as nanoreactors for the synthesis of AuNPs and were characterized using UV–Vis spectroscopy, dynamic light scattering and transmission electron microscopy. The AuNPs had a sphere-like shape with a diameter from 7 ± 1.7 to 34 ± 6 nm depending on the type of aggregate/unimer used in the synthesis. Nevertheless, when very large aggregates were used, AuNPs with different morphologies were observed.

In this study, six-arm star-shaped poly(N-vinylcaprolactam) (PNVCL) polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization were subjected to aminolysis reaction using hexylamine. Chemically crosslinked gels or highly end-functionalized star polymers can be obtained depending mainly on the type of solvent used during the transformation of the RAFT functional group. An increase in the viscosity of the solution was observed when the aminolysis was carried out in THF. In contrast, when the reaction was conducted in dichloromethane, chain-end thiol (PNVCL)6 star polymers could be obtained. Moreover, when purified (PNVCL-SH)6 star polymers are in contact with THF, the gelation occurs in just a few minutes, with an obvious increase in viscosity, to form physical gels that become chemically crosslinked gels after 12 h. Interestingly, when purified (PNVCL-SH)6 star polymers were stirred in distilled water, even at high aqueous solution concentration (40 mg/mL), there was no increase in the viscosity or gelation, and no evident gels were observed. The analysis of the hydrodynamic diameter (Dh) by dynamic light scattering (DLS) did not detect quantifiable change even after 4 days of stirring in water. On the other hand, the thiol groups in the (PNVCL-SH)6 star polymers were easily transformed into trithiocarbonate groups by addition of CS2 followed by benzyl bromide as demonstrated by UV-Vis spectroscopical analysis and GPC. After the modification, the (PNVCL)6 star polymers exhibit an intense yellow color typical of the absorption band of trithiocarbonate group at 308 nm. To further demonstrate the highly effective new trithiocarbonate end-functionality, the PNVCL polymers were successfully chain extended with N-isopropylacrylamide (NIPAM) to form six-arm star-shaped PNIPAM-b-PNVCL block copolymers. Moreover, the terminal thiol end-functionality in the (PNVCL-SH)6 star polymers was linked via disulfide bond formation to l-cysteine to further demonstrate its reactivity. Zeta potential analysis shows the pH-responsive behavior of these star polymers due to l-cysteine end-functionalization. By this using methodology and properly selecting the solvent, various environment-sensitive star polymers with different end-groups could be easily accessible.

Poly(N,N′-diethylaminoethyl methacrylate) (PDEAEM) with different molecular weights was used to stabilize gold nanoparticles (AuNPs) obtained by in situ reduction of tetrachloroauric acid using citrates under acidic conditions and in organic/alcoholic medium. The influence of the pH value on gold nanoparticle size in the presence of PDEAEM was investigated. Results show that the pH of the reacting mixture has a dramatic effect on the size, polydispersity, and morphology of the resulting AuNPs. Moreover, the size of the nanoparticles (NPs) may be modified by changing the solution’s pH or by changing the solvent type. Electron microscope images showed that the sizes of AuNPs coated with PDEAEM were not sensitive to the variation of the polymer molecular weight in the range between 9000 and 29300 g/mol; however their aggregation behavior depended strongly on the polymer molecular weight as revealed by dynamic light scattering studies. AuNPs stabilized with PDEAEM (AuNP@PDEAEM) are stable in water at acidic pH and in organic polar solvents.