RESUMEN
Surface modification of porous glass beads by ethanol-based 3-mercaptopropyltrimethoxysilane (MPTMS) grafting solutions is directly evidenced by nitrogen adsorption, elemental analysis, thermogravimetry, infrared and 29Si CP MAS NMR spectroscopy. Furthermore, the energetic characterization of the surface is essential to understand comprehensively the physico-chemical interactions between the pristine and MPTMS-modified surface and its gas/liquid-phase environment. In this study, inverse gas chromatography (IGC) is used to characterize the surface properties of porous glass (PG). By means of IGC at infinite dilution (IGC-ID), the dispersive component of the surface energy (γsd), the enthalpy and entropy of adsorption of C6-C10 hydrocarbon probes were determined at temperatures between 30 and 120⯰C. The specific component of the surface energy (γssp) at the temperature of 120⯰C has been obtained via the Van Oss theory and a least-squares procedure evaluating the IGC data of 8 polar probe molecules collectively. After surface silylation, the total surface energy (γst) decreased from 402 to 255â¯mJ/m² indicating both a reduced wettability and an increased hydrophobicity of the MPTMS-modified PG. Moreover, the acidity/basicity parameters according to the Van Oss and the Gutmann approach indicated that the acidity of the PG surface decreases by MPTMS grafting. Using n-octane and isopropanol probes, IGC at finite concentration (IGC-FC) was applied to obtain their adsorption isotherms and subsequently the BET specific surface areas. In addition, the surface heterogeneity of the studied PGs was also computed. The energy distribution functions of adsorption sites were monomodal (peak maximum at about 22â¯kJ/mol) for the n-octane probe, while isopropanol revealed a bimodal distribution function (maxima at about 18 and 25â¯kJ/mol) on both pristine and MPTMS-modified PG. Furthermore, the proportion of high energy sites (apparently assigned to SiOH groups) has been reduced by surface modification from 65% to only 35% despite a high surface coverage of Ë10 MPTMS species/nm2. These findings are in agreement with the results of 29Si CP MAS NMR measurements and are supported by DFT calculations on the adsorption of isopropanol and n-octane on the surface of a silica cluster model.
Asunto(s)
Cromatografía de Gases/métodos , Dióxido de Silicio/química , 2-Propanol/química , Ácidos/química , Adsorción , Alcanos/química , Teoría Funcional de la Densidad , Entropía , Espectroscopía de Resonancia Magnética , Conformación Molecular , Nitrógeno/química , Porosidad , Silanos/química , Espectroscopía Infrarroja por Transformada de Fourier , Propiedades de Superficie , Temperatura , TermogravimetríaRESUMEN
The amorphous to crystalline phase transformation of Ge2Sb2Te5 (GST) films by UV nanosecond (ns) and femtosecond (fs) single laser pulse irradiation at the same wavelength is compared. Detailed structural information about the phase transformation is collected by x-ray diffraction and high resolution transmission electron microscopy (TEM). The threshold fluences to induce crystallization are determined for both pulse lengths. A large difference between ns and fs pulse irradiation was found regarding the grain size distribution and morphology of the crystallized films. For fs single pulse irradiated GST thin films, columnar grains with a diameter of 20 to 60 nm were obtained as evidenced by cross-sectional TEM analysis. The local atomic arrangement was investigated by high-resolution Cs-corrected scanning TEM. Neither tetrahedral nor off-octahedral positions of Ge-atoms could be observed in the largely defect-free grains. A high optical reflectivity contrast (~25%) between amorphous and completely crystallized GST films was achieved by fs laser irradiation induced at fluences between 13 and 16 mJ/cm(2) and by ns laser irradiation induced at fluences between 67 and 130 mJ/cm(2). Finally, the fluence dependent increase of the reflectivity is discussed in terms of each photon involved into the crystallization process for ns and fs pulses, respectively.
RESUMEN
This study focuses on the development of novel biocompatible macroporous cryogels by electron-beam assisted free-radical crosslinking reaction of polymerizable dextran and hyaluronan derivatives. As a main advantage this straightforward approach provides highly pure materials of high porosity without using additional crosslinkers or initiators. The cryogels were characterized with regard to their morphology and their basic properties including thermal and mechanical characteristics, and swellability. It was found that the applied irradiation dose and the chemical composition strongly influence the material properties of the resulting cryogels. Preliminary cytotoxicity tests illustrate the excellent in vitro-cytocompatibility of the fabricated cryogels making them especially attractive as matrices in tissue regeneration procedures.
Asunto(s)
Materiales Biocompatibles/síntesis química , Criogeles/síntesis química , Criogeles/toxicidad , Dextranos/química , Dextranos/toxicidad , Ácido Hialurónico/química , Ácido Hialurónico/toxicidad , Células 3T3 , Animales , Materiales Biocompatibles/toxicidad , Supervivencia Celular/efectos de los fármacos , Dextranos/efectos de la radiación , Módulo de Elasticidad , Electrones , Dureza , Ácido Hialurónico/efectos de la radiación , Ensayo de Materiales , Ratones , Conductividad TérmicaRESUMEN
Natural hydrogels such as gelatin are highly desirable biomaterials for application in drug delivery, biosensors, bioactuators and extracellular matrix components due to strong biocompatibility and biodegradability. Typically, chemical crosslinkers are used to optimize material properties, often introducing toxic byproducts into the material. In this present work, electron irradiation is employed as a reagent-free crosslinking technique to precisely tailor the viscoelasticity, swelling behavior, thermal stability and structure of gelatin. With increasing electron dose, changes in swelling behavior and rheology indicate increasing amounts of random coils and dangling ends as opposed to helical content, a result confirmed through Fourier transform infrared spectroscopy. Gel fraction, rheology and swelling measurements at 37 °C were used to verify thermal stability in biological conditions. Scanning electron microscopy images of dried gelatin samples support these conclusions by revealing a loss of free volume and apparent order in the fracture patterns. The degree of crosslinking and mesh size are quantified by rubber elasticity theory and the Flory-Rehner equation. Overall, precise control of material properties is demonstrated through the interplay of concentration and irradiation dose, while providing an extensive parameter-property database suitable for optimized synthesis.
RESUMEN
Two novel Zr(IV)- and Hf(IV)-based bisamido complexes bearing the 6-[2-(diethylboryl)phenyl]pyrid-2-yl motif, that is, [ZrCl(2){Me(2)Si(DbppN)(2)}(thf)] (9) and [HfCl(2){Me(2)Si(DbppN)(2)}(thf)(2)] (10) (DbppN=6-[2-(diethylboryl)phenyl]pyridine-2-amido) have been prepared. Their reactivities have been compared with that of a model precatalyst that does not bear the aminoborane motif. Upon activation with methylalumoxane, precatalysts 9 and 10 are active in the homopolymerization of ethylene (E) yielding high-density polyethylene (HDPE). In the copolymerization of E with cyclopentene (CPE), for example by the action of 9, the presence of CPE resulted in a dramatic increase in the polymerization activity of E, while CPE incorporation remained close to or at zero. In the vinyl-insertion copolymerization of norborn-2-ene (NBE) with E by the action of 9, statistical cyclic olefin copolymers of these two monomers were obtained. At higher NBE concentrations, however, 9 gave rise to reversible ring-opening metathesis (ROMP)/vinyl-insertion polymerization (VIP) of NBE with E, resulting in the formation of multi-block copolymers of the general formula poly(NBE)(ROMP)-co-poly(NBE)(VIP)-co-poly(E). This particular feature of precatalyst 9, that is, the ability to induce a reversible α-H elimination/α-H addition reaction, is attributed to the unique role of the 6-[2-(diethylboryl)phenyl]pyrid-2-yl ligand. Accordingly, a model precatalyst lacking this ligand does not have the ability to induce α-H elimination/α-H addition reactions. The different (11)B NMR shifts of various diethylborylphenylpyrid-2-ylamines and -amides permit a ranking of the strengths of the B-N bonds in these compounds. This strength of the B-N bond is correlated with the propensity of 9/MAO to produce poly(NBE)(ROMP)-co-poly(NBE)(VIP)-co-poly(E) at different temperatures.
RESUMEN
The propensity of a half-sandwich (η5-tetramethylcyclopentadienyl) dimethylsilylamido Ti(IV)-based catalyst bearing an auxiliary diethylboryl-protected pyridyl moiety (Ti-8), activated by methylaluminoxane (MAO) to homopolymerize α-olefins such as ethylene, 1-hexene and styrene as well as to copolymerize styrene with 1,3-cyclo-hexadiene is described. The reactivity of Ti-8 was investigated in comparison to a 6-(2-(diethylboryl)phenyl)pyrid-2-yl-free analogue (Ti-3).
Asunto(s)
Alquenos/química , Ciclohexenos/química , Polímeros/química , Estireno/química , Titanio/química , Catálisis , Espectroscopía de Resonancia MagnéticaRESUMEN
A series of Ru(IV)-alkylidenes based on unsymmetrical imidazolin-2-ylidenes, that is, [RuCl(2){1-(2,4,6-trimethylphenyl)-3-R-4,5-dihydro-(3H)-imidazol-1-ylidene}(CHPh)(pyridin)] (R = CH(2)Ph (5), Ph (6), ethyl (7), methyl (8)), have been synthesized. These and the parent initiators [RuCl(2)(PCy(3)){1-(2,4,6-trimethylphenyl)-3-R-4,5-dihydro-(3H)-imidazol-1-ylidene}(CHC(6)H(5))] (R = CH(2)C(6)H(5) (1), C(6)H(5) (2), ethyl (3)) were used for the alternating copolymerization of norborn-2-ene (NBE) with cis-cyclooctene (COE) and cyclopentene (CPE), respectively. Alternating copolymers, that is, poly(NBE-alt-COE)(n) and poly(NBE-alt-CPE)(n) containing up to 97 and 91% alternating diads, respectively, were obtained. The copolymerization parameters of the alternating copolymerization of NBE with CPE under the action of initiators 1-3 and 5-8 were determined by using both a zero- and first-order Markov model. Finally, kinetic investigations using initiators 1-3, 6, and 7 were carried out. These revealed that in contrast to the 2nd-generation Grubbs-type initiators 1-3 the corresponding pyridine derivatives 6 and 7 represent fast and quantitative initiating systems. Hydrogenation of poly(NBE-alt-COE)(n) yielded a fully saturated, hydrocarbon-based polymer. Its backbone can formally be derived by 1-olefin polymerization of CPE (1,3-insertion) followed by five ethylene units and thus serves as an excellent model compound for 1-olefin polymerization-derived copolymers.
RESUMEN
Catalytic rivals: Both CO(2)-protected tetrahydropyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and Sn(II)-1,3-dimesitylimidazol-2-ylidene, as well as Sn(II)-1,3-dimesitylimidazolin-2-ylidene complexes (example displayed), have been identified as truly latent catalysts for polyurethane (PUR) synthesis rivaling all existing systems both in activity and latency.A series of CO(2)-protected pyrimidin-2-ylidenes as well as 1,3-dimesitylimidazol-2-ylidene and dimesitylimidazolin-2-ylidene complexes of Sn(II) have been prepared. Selected single-crystal X-ray structures are reported. The new compounds were investigated for their catalytic behavior in polyurethane (PUR) synthesis. All compounds investigated showed excellent catalytic activity, rivaling the industrially most relevant catalyst dibutyltin dilaurate. Even more important, all compounds displayed pronounced latent behavior, in selected cases rivaling and exceeding the industrially relevant latent catalyst phenylmercury neodecanoate both in terms of latency and catalytic activity. This allows for creating one-component PUR systems with improved pot lifetimes. Pseudo-second-order kinetics were found for both CO(2)-protected tetrahyropyrimidin-2-ylidenes and for [SnCl(2)(1,3-dimesityldihydroimidazol-2-ylidene)], indicating a fast pre-catalyst decomposition prior to polyurethane formation. 1,3-Di(2-propyl)tetrahydropyrimidin-2-ylidene was additionally found to be active in the cyclotrimerization of various isocyanates, offering access to a broad variability in polymer structure, that is, creating both urethane and isocyanurate moieties within the same polymer.
RESUMEN
Electron beam (EB) curing-derived monolith materials were prepared from ethyl methacrylate (EMA), trimethylolpropane triacrylate (TMPTA), 2-propanol, 1-dodecanol, and toluene within the confines of 3 mmx100 mm id glass columns, applying a total dose of 22 kGy for curing. Monolithic columns were checked for their separation behavior for selected dansylated (DNS)-amino acids as well as for cyclophilin 18. Their separation performance was compared to that of a C18-modified silica-based rigid rod (Chromoliths). In the separation of dansylated amino acids, retention times were reduced on EB-derived columns, where the peak resolution was significantly better than on a Chromolith. This finding was attributed to a larger fraction of small pores (<2.15 nm) in the EB curing-derived monoliths. Finally, EB curing-derived monoliths have been used to separate cyclophilin 18 from crude cell lysis mixtures.