Morphology and surface properties of some siloxane–organic copolymers

BACKGROUND: It is well known that, due to their extremely low polarity, polysiloxanes are incompatible with almost any organic system. This incompatibility leads to phase separation in mixed siloxane–organic systems. RESULTS: Three siloxane–organic copolymers, poly[(5,5′‐methylene‐bis‐salicylaldehyde)‐imine‐(1,3‐bis(propylene)tetramethyldisiloxane)] (Paz1), poly[(2,5‐dihydroxy‐1,4‐benzoquinone)‐imine‐(1,3‐bis(propylene)tetramethyldisiloxane)] (Paz2) and poly[1,3‐bis(propylene)tetramethyldisiloxane diamide] (Pam), were prepared by the reaction of 1,3‐bis(3‐aminopropyl)tetramethyldisiloxane with appropriate organic partners (5,5′‐methylene‐bis‐salicylaldehyde, 2,5‐dihydroxy‐1,4‐benzoquinone and oxalyl chloride, respectively). The morphologies dictated by the incompatibility between siloxane and polar organic moieties were investigated using differential scanning calorimetry and scanning electron microscopy. The surface activity of the copolymers and water vapour sorption capacity were also measured. CONCLUSION: Even though the polar sequences are very short ones, the highly flexible siloxane‐containing sequence permits the self‐assembly of these into more or less polar domains. Such an organization influences the properties of the resulting materials, an important place being occupied by the surface properties. Copyright © 2009 Society of Chemical Industry     

Metallopolymers based on a polyazomethine ligand containing rigid oxadiazole and flexible tetramethyldisiloxane units

Soluble, easily processable polymer–metal complexes with improved optical and dielectric properties for optoelectronic functional materials were obtained. For this, a new polyazomethine (PAZ2) was prepared by the reaction of a siloxane dialdehyde and bis(formyl‐p‐phenoxymethyl) tetramethyldisiloxane with 2,5‐bis(p‐aminophenyl)‐1,3,4‐oxadiazole, and it was used as a ligand for Cu(II), Co(II), and Zn(II) ions on the basis of the presence of the electron‐donor nitrogen atoms from the azomethine group and oxadiazole ring. The structure of the PAZ2 was determined by spectral [Fourier transform infrared (FTIR) and ¹H‐NMR spectroscopy] techniques. The metal complexation was proven by FTIR spectroscopy, and the silicon‐to‐metal ratios in the complexes were established by energy‐dispersive X‐ray fluorescence. The new materials were characterized by gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. The optical properties of PAZ2 and the derived metal complexes were studied by ultraviolet–visible and fluorescence spectroscopies. PAZ2 shows fluorescence emission, and it was significantly enhanced by metal complexation. The emission was enhanced by protonation; this behavior is useful, especially for sensors. The electrical properties were investigated by dielectric spectroscopy at various frequencies and temperatures, and this emphasized the existence of dipolar relaxations. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41631.     

Structure–property relationship of sodium deoxycholate based poly(ester ether)urethane ionomers for biomedical applications

New sodium deoxycholate based poly(ester ether)urethane ionomers were prepared for the development of biomedical materials. A structure–property relationship in the tested biomaterials was established by cross‐examination of the dynamic mechanical and dielectric properties, attenuated total reflection–Fourier transform infrared investigation, thermogravimetric analysis, and surface morphology characterization. A stronger ionic interaction and solvation capacity of the ions and a higher ionic conductivity were manifested in the case of poly(ethylene oxide)‐rich segments than for poly(propylene oxide)‐rich segments in these polyurethane ionomers. The molecular and ionic interactions of the bile‐salt moiety with different polyether cosoft segments influenced chain packing and conformation, supramolecular organization, and the resulting surface morphological microstructures of the polyurethane biomembranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42921.     

Pullulan: A versatile coating agent for superparamagnetic iron oxide nanoparticles

Ultrasmall superparamagnetic iron oxide (Fe₃O₄) nanoparticles coated by biocompatible pullulan (Pu‐USPIO) with sizes below 10 nm and having a magnetite core and a hydrophilic outer shell of pullulan were prepared. The formed Pu‐USPIOs were thoroughly characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, atomic force microscopy, and small‐angle X‐ray scattering experiments. The content of magnetic nanoparticles embedded into the pullulan matrix was determined by thermogravimetric analysis. Vibrating sample magnetometry analysis was used to evaluate the magnetic properties of the Pu‐USPIO samples. Because of the presence of pullulan, these nanoparticles could be conditioned in many versatile forms, from a clear solution to magnetic films, for potential applications, including magnetic hyperthermia mediators. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42926.     

On the preparation of porous crosslinked poly(ethylene dimethacrylate esters): Polymers and copolymers

Macroreticular polymers and copolymers based on poly(ethylene glycol dimethacrylate esters) possessing a permanent porosity (white opaque beads, 40–60% porosity, 354 m²/g, the apparent density less than 1.060 g/mL, etc.) were prepared. The influence of the porogen thermodynamic quality and its weight fraction used in the polymerization mixture on the bead structure was also studied. The porous structure of the matrices was investigated and proved by SEM analyses, the N₂ adsorption (BET) method, etc. The thermal degradation mechanism of the macroreticular beads based on dimethacrylate esters shows that the thermal stability of samples depends on the monomer structure, i.e., the chain length between the two vinyl groups. © 1996 John Wiley & Sons, Inc.     

Cellular and Molecular Targets for Non-Invasive,Non-Pharmacological Therapeutic/Rehabilitative Interventions in Acute Ischemic Stroke

BACKGROUND: Cerebral circulation delivers the blood flow to the brain through a dedicated network of sanguine vessels. A healthy human brain can regulate cerebral blood flow (CBF) according to any physiological or pathological challenges. The brain is protected by its self-regulatory mechanisms, which are dependent on neuronal and support cellular populations, including endothelial ones, as well as metabolic, and even myogenic factors. OBJECTIVES: Accumulating data suggest that “non-pharmacological” approaches might provide new opportunities for stroke therapy, such as electro-/acupuncture, hyperbaric oxygen therapy, hypothermia/cooling, photobiomodulation, therapeutic gases, transcranial direct current stimulations, or transcranial magnetic stimulations. We reviewed the recent data on the mechanisms and clinical implications of these non-pharmaceutical treatments. METHODS: To present the state-of-the-art for currently available non-invasive, non-pharmacological-related interventions in acute ischemic stroke, we accomplished this synthetic and systematic literature review based on the Preferred Reporting Items for Systematic Principles Reviews and Meta-Analyses (PRISMA). RESULTS: The initial number of obtained articles was 313. After fulfilling the five steps in the filtering/selection methodology, 54 fully eligible papers were selected for synthetic review. We enhanced our documentation with other bibliographic resources connected to our subject, identified in the literature within a non-standardized search, to fill the knowledge gaps. Fifteen clinical trials were also identified. DISCUSSION: Non-invasive, non-pharmacological therapeutic/rehabilitative interventions for acute ischemic stroke are mainly holistic therapies. Therefore, most of them are not yet routinely used in clinical practice, despite some possible beneficial effects, which have yet to be supplementarily proven in more related studies. Moreover, few of the identified clinical trials are already completed and most do not have final results. CONCLUSIONS: This review synthesizes the current findings on acute ischemic stroke therapeutic/rehabilitative interventions, described as non-invasive and non-pharmacological.     

Structural investigation of xFe2O3 · (100 − x)[P2O5 · TeO2] glass system by FT-IR study and EPR spectroscopy

Glasses from xFe₂O₃ · (100 − x)[P₂O₅ · TeO₂] system, with 0 ≤ x ≤ 50 mol%, were investigated by X-ray diffraction, FT-IR and EPR spectroscopies. The XRD patterns show a vitreous state of studied samples for x ≤ 35 mol% Fe₂O₃. The FT-IR spectrum of the P₂O₅ · TeO₂ glass matrix reveals a structure formed from PO₄, TeO₄ and TeO₃ units. The addition and the increasing of Fe₂O₃ content modify progressively the structure of the glass matrix. The local structure in the investigated glasses was revealed by means of EPR using Fe³⁺ (3d⁵; ⁶S_5/2) ions as paramagnetic probes. The EPR spectra present two resonance absorption lines characteristic to Fe³⁺ ions centred at g_eff ≈ 2.0, for 0.5 ≤ x ≤ 35 mol% and g_eff ≈ 4.3, for 0.5 ≤ x ≤ 5 mol%. The variation of the EPR parameters, the intensity and line-width of these absorption lines, with iron ions composition has been followed.     

Phosphorus‐containing poly(ester‐imide)–polydimethylsiloxane copolymers

New phosphorus‐containing poly(ester‐imide)‐polydimethylsiloxane copolymers were prepared by solution polycondensation of 1,4‐[2‐(6‐oxido‐6H‐dibenz < c,e > < 1, 2 > oxaphosphorin‐6‐yl)]naphthalene‐bis(trimellitate) dianhydride with a mixture of an aromatic diamine (1,3‐bis(4‐aminophenoxy)benzene) and α,ω‐bis(3‐aminopropyl)oligodimethylsiloxane of controlled molecular weight, in various ratios. Poly(amic acid) intermediates were converted quantitatively to the corresponding polyimide structures using a solution imidization procedure. The polymers are easily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylformamide, as well as in less polar solvents such as tetrahydrofuran. They show good thermal stability, the decomposition temperature being above 370 °C. The glass transition temperatures are in the range 165–216 °C. Solutions of the polymers in N‐methyl‐2‐pyrrolidone exhibit photoluminescence in the blue region. Copyright © 2010 Society of Chemical Industry     

Towards understanding of the photosensitive properties in lead-vanadate-tellurate unconventional glasses

This paper describes photosensitive properties and spectroscopic studies on the xPbO(100 − x)[6TeO₂·4V₂O₅] (where x = 0-100 mol%) glass system. Our FTIR, UV-vis spectroscopic data and density measurements exhibit compositional dependent trends and the existence of characteristic vanadate (orthovanadate, pyrovanadate) structural units in these glasses. By laser exposures of the samples, variations observed in the FTIR and UV-vis spectra show that the existence a redox couple between lead ions and vanadate network.     

Organosoluble asymmetric aromatic polyamides bearing pendent phenoxy groups

This study focuses on the synthesis and characterization of new polyamides based on an aromatic asymmetric diamine‐containing phenoxy‐substituted benzophenone segment. Low‐temperature solution polycondensation reactions of this diamine with various aromatic diacid chlorides containing ether, hexafluoroisopropylidene or diphenylsilane groups resulted in polyamides with molecular weights in the range 102 900–113 200 g mol^?1. The structures of these monomers and the corresponding polymers were fully confirmed using elemental analysis and infrared and NMR spectroscopy. All polyamides were easily soluble at room temperature in polar aprotic solvents and even in less polar solvents such as tetrahydrofuran. The polymers showed excellent thermal stability, up to 385 °C, and displayed glass transition temperatures in the range 225–256 °C. All the polymers presented blue florescence upon irradiation with UV light and thus show promise for applications in electroluminescent devices. Copyright © 2011 Society of Chemical Industry