The quality of surface coating of magnetic nanoparticles destined as nanoprobes in clinical applications is of utmost significance for their colloidal stability and biocompatibility. A novel approach for the fabrication of such a coating involves the synthesis of well-defined diblock copolymers based on 2-(acetoacetoxy)ethyl methacrylate (chelating) and poly(ethylene glycol)methyl ether methacrylate (water-soluble, thermoresponsive), prepared by reversible addition-fragmentation chain transfer polymerization. Fabrication of magneto-responsive micelles was accomplished via chemical coprecipitation of Fe(III)/Fe(II) in the presence of diblock copolymers. Further to the characterization of micellar morphologies, optical and thermal properties, assessment of magnetic characteristics disclosed superparamagnetic behavior. The hybrid micelles did not compromise cell viability in cultures, while in vitro uptake by macrophage cells was significantly lower in comparison to that of the clinically applicable contrast agent Resovist, suggesting that these systems can evade rapid uptake by the reticuloendothelial system and be useful agents for in vivo applications.

This study deals with the preparation of novel multiresponsive (magnetoresponsive, thermoresponsive and pH-responsive) nanocomposite conetworks consisting of oleic acid-coated magnetite nanoparticles (OA·Fe(3)O(4)), hydrophilic/thermoresponsive hexa(ethylene glycol) methyl ether methacrylate (HEGMA), hydrophobic/metal binding 2-(acetoacetoxy)ethyl methacrylate (AEMA), and pH-responsive/thermoresponsive N-diethylaminoethyl methacrylate (DEAEMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) moieties. Conventional free radical copolymerization was employed for the synthesis of random conetworks in the absence and presence of preformed OA·Fe(3)O(4). Further, in characterization of these materials in regards to their swelling behavior in organic and aqueous solvents, thermal/thermoresponsive properties, and composition, assessment of their magnetic characteristics disclosed tunable superparamagnetic behavior. These systems were also evaluated toward their ability to adsorb and release a solute (benzoic acid) in a controlled manner upon varying the pH.

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h i g h l i g h t s" OME was treated by coagulation-flocculation, solvent extraction and solar-Fenton. " The solid particles were successfully removed (97%) by coagulation-flocculation. " Solvent extraction was applied to recover a fraction (36%) of the remaining TPs. " Solar-Fenton was able to reduce the residual COD and TP, at 73% and 87%, respectively.

Nano-immunotherapy improves breast cancer outcomes but not all patients respond and none are cured. To improve efficacy, research focuses on drugs that reprogram cancer-associated fibroblasts (CAFs) to improve therapeutic delivery and immunostimulation. These drugs, however, have a narrow therapeutic window and cause adverse effects. Developing strategies that increase CAF-reprogramming while limiting adverse effects is urgent. Here, taking advantage of the CAF-reprogramming capabilities of tranilast, we developed tranilast-loaded micelles. Strikingly, a 100-fold reduced dose of tranilast-micelles induces superior reprogramming compared to free drug owing to enhanced intratumoral accumulation and cancer-associated fibroblast uptake. Combination of tranilast-micelles and epirubicin-micelles or Doxil with immunotherapy increases T-cell infiltration, resulting in cures and immunological memory in mice bearing immunotherapy-resistant breast cancer. Furthermore, shear wave elastography (SWE) is able to monitor reduced tumor stiffness caused by tranilast-micelles and predict response to nano-immunotherapy. Micellar encapsulation is a promising strategy for TME-reprogramming and SWE is a potential biomarker of response.

Reaction of KVO 3 with 2-[N,N'-(carboxymethyl)aminomethyl]-5-methylhydroquinone (H 4 mecah) in aqueous solution at pH 8.2 results in the isolation of mononuclear K 2 [V V (O) 2 {Hmecah(-3)}]ؒ2H 2 O complex. On the other hand, reaction with the 2-[N,N'-(carboxymethyl)aminomethyl]-5-tert-butylhydroquinone (H 4 tbutcah) under the same condi tions gives the tetranuclear mixed-valent complex K 6 [{V V O(μ-O)V IV O}{μ-tbutbicah(-6)}] 2 ؒ10.5H 2 O (H 6 tbutbicah, 2,2'-({2-[bis(carboxymethyl)amino]-3,6-dihydroxy-4-methylbenzyl}azanediyl)diacetic acid). The structures of both complexes were determined by single-crystal X-ray crystallography. The coordination environment of vanadium ions in both complexes is octahedral, with four out of the six positions to be occupied by the two cis carboxylate oxygens, one hydroquinonate oxygen, and one amine nitrogen atoms of the ligands' tripod binding sites. The importance of the chelate ring strains in the stabilization of the p-semiquinone radical is also discussed. A protonation of the ligated to vanadium(IV) ion hydroquinonate oxygen at low pH was revealed by continuous wave (cw) X-band electron paramagnetic resonance (EPR) and UV-vis spectroscopies. Scheme 1 Drawings of the ligands used in this work.The mononuclear complex 1 was prepared by treatment of KVO 3 aqueous solution with an equivalent amount of the H 4 mecah at pH 8.2. The same conditions were used for the synthesis of the tetranuclear compound 2 from KVO 3 and H 4 tbutcah. However, the yield of the reaction was increased by reacting 2 equiv of KVO 3 with 1 equiv of H 4 tbutcah. During the reaction the ligand is further substituted by an additional iminodiacetate group forming the ligand tbutbicah 6- (Schemes 1 and 2). A possible mechanism of this condensation reaction is shown in Scheme 3. According to this, the first step should be the formation of a vanadium(V) mononuclear complex similar to 1 followed by reduction of the metal ion to vanadium(IV) and simultaneous oxidation of ligand to semiquinone radical. Then, an iminodiacetic group from another Htbutcah 3nucleophilically attacks the semiquinone. The new bifunctional hydroquinonate derivative ligates one additional vanadium(V) and two of these units connect through V IV -O-V V bridges to form the mixed-valent tetranuclear complex 2. The difference of the

Electrospun microfibrous membranes comprised of poly(methyl methacrylate)-poly((2diethylaminoethyl) methacrylate) random copolymers (PMMA-co-PDEAEMA) of various chemical compositions blended together with a commercially available PMMA have been fabricated with diameters between 4.0-6.4 µm and further evaluated as adsorbents for bacteria removal from aqueous media. The morphology and thermal stability of the membranes were determined by scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA), respectively. Tensile tests were also performed in order to investigate their mechanical properties. Membrane evaluation as adsorbents against two gram-negative bacteria namely Pseudomonas aeruginosa and Advenella species revealed that the membranes containing the highest percentage of the cationic moieties (DEAEMA) exhibited the highest adsorption efficiency. The bacteria removal by the microfibrous membranes was studied by UV-vis spectrophotometry upon measuring the optical density (OD) of the microorganisms. The highest recorded bacteria removal percentages after 8 hr were approximately 70% and 45%, for the Pseudomonas aeruginosa and Advenella species respectively, whereas in both cases complete (100%) bacteria removal was observed after 24 hr of membrane immersion in bacteria-containing aqueous solutions. The experimental adsorption isotherms for P. aeruginosa and Advenella sp. were well-fitted with the Langmuir isotherm model indicating a monolayer adsorption process. SEM was also used to confirm the adhesion of the bacteria onto the electrospun microfibers. Most importantly, these materials exhibited great performance on the removal of microorganisms from urban wastewater as determined via the standard plating technique prepared by agar. Methyl methacrylate (MMA, Fluka, ≥ 99%), poly(methyl methacrylate) (PMMA) (Mw ∼ 350 000, Sigma-Aldrich), n-hexane (Scharlau, 96%), tetrahydrofuran (THF, Scharlau, extra pure) and ethyl acetate (EA, Scharlau, GC grade, 99.8%) were used without further purification. 2-(diethylaminoethyl) methacrylate (DEAEMA, Sigma-Aldrich, 99%) was passed through a basic alumina column prior to the polymerizations and used without further purification. The radical initiator 2,2'-azobis(2-methylpropionitrile) (AIBN, Sigma-Aldrich, 95%) was recrystallized twice from ethanol. Deuterated chloroform (CDCl 3 , Merck), glutaraldehyde (Sigma-aldrich, 25% in water), calcium chloride dihydrate (CaCl 2 .2H 2 O, Scharlau, Reagent grade), ammonium sulfate ((NH 4 ) 2 SO 4 , Scharlau, reagent grade), sucrose (Himedia), potassium phosphate dibasic (K 2 HPO 4 , Sigma-aldrich, ≥98%), magnesium chloride (MgCl 2 , Sigma, ≥98%) and sodium chloride (NaCl, Himedia) were used as received by the manufacturer. The selected gram-negative microorganisms Pseudomonas aeruginosa LVD-10 and Advenella species LVX-4 were provided by the Applied Microbiology Laboratory culture collection of the Cyprus University of Technology. They were previously isolated and deposited in GenBank with accession number KF728673.1 for P. ...