Self‐welding 1‐butene/ethylene copolymers from metallocene catalysts: Structure,morphology, and mechanical properties

Samples of random copolymers consisting of 1‐butene modified with a low ethylene content (4, 5, 8% by weight) produced with metallocene catalysts were studied to elucidate the polymorphic behavior of this new class of materials and to characterize them from a structural, morphological, and mechanical point of view. The samples cooled down from the melt are in amorphous phase and crystallize in a mixture of form I and I′ or in pure form I′ with aging time, according to the C2 content. Infrared and nuclear magnetic resonance spectroscopy, X‐ray diffraction and microscopic techniques were used to follow the changes of the material with aging time and to correlate the structural and morphological behavior with the peculiar mechanical properties that differentiate the samples with increasing C2 content. The presence, in the aged samples with higher C2 content, of the pure form I′ induces the peculiar ability to self‐welding and these copolymers combine high flexibility with good elasticity and ductility and can be processed directly or used as modifying agents in polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40119.     

Diatomite silica nanoparticles for drug delivery

Diatomite is a natural fossil material of sedimentary origin, constituted by fragments of diatom siliceous skeletons. In this preliminary work, the properties of diatomite nanoparticles as potential system for the delivery of drugs in cancer cells were exploited. A purification procedure, based on thermal treatments in strong acid solutions, was used to remove inorganic and organic impurities from diatomite and to make them a safe material for medical applications. The micrometric diatomite powder was reduced in nanoparticles by mechanical crushing, sonication, and filtering. Morphological analysis performed by dynamic light scattering and transmission electron microscopy reveals a particles size included between 100 and 300 nm. Diatomite nanoparticles were functionalized by 3-aminopropyltriethoxysilane and labeled by tetramethylrhodamine isothiocyanate. Different concentrations of chemically modified nanoparticles were incubated with cancer cells and confocal microscopy was performed. Imaging analysis showed an efficient cellular uptake and homogeneous distribution of nanoparticles in cytoplasm and nucleus, thus suggesting their potentiality as nanocarriers for drug delivery.

PACS

87.85.J81.05.Rm; 61.46. + w     

Potential Effect of CD271 on Human Mesenchymal Stromal Cell Proliferation and Differentiation

The Low-Affinity Nerve Growth Factor Receptor (LNGFR), also known as CD271, is a member of the tumor necrosis factor receptor superfamily. The CD271 cell surface marker defines a subset of multipotential mesenchymal stromal cells and may be used to isolate and enrich cells derived from bone marrow aspirate. In this study, we compare the proliferative and differentiation potentials of CD271⁺ and CD271⁻ mesenchymal stromal cells. Mesenchymal stromal cells were isolated from bone marrow aspirate and adipose tissue by plastic adherence and positive selection. The proliferation and differentiation potentials of CD271⁺ and CD271⁻ mesenchymal stromal cells were assessed by inducing osteogenic, adipogenic and chondrogenic in vitro differentiation. Compared to CD271⁺, CD271⁻ mesenchymal stromal cells showed a lower proliferation rate and a decreased ability to give rise to osteocytes, adipocytes and chondrocytes. Furthermore, we observed that CD271⁺ mesenchymal stromal cells isolated from adipose tissue displayed a higher efficiency of proliferation and trilineage differentiation compared to CD271⁺ mesenchymal stromal cells isolated from bone marrow samples, although the CD271 expression levels were comparable. In conclusion, these data show that both the presence of CD271 antigen and the source of mesenchymal stromal cells represent important factors in determining the ability of the cells to proliferate and differentiate.     

Defined Conjugation of Glycans to the Lysines of CRM197 Guided by their Reactivity Mapping

Systematic characterisation of the reactivity of the lysine moieties in CRM₁₉₇ towards N‐hydroxysuccinimide linkers bearing alkynes or azides is described. This involves two‐step conjugation of various glycans to CRM₁₉₇ by click chemistry in a well‐defined manner. By semiquantitative LC‐MS/MS analysis of proteolytic digests of the conjugates formed, the reactivity of lysine residues in the protein was mapped and ranked. Computational analysis of the solvent accessibility of each lysine residue (based on the CRM₁₉₇ crystal structure) established a correlation between reactivity and surface exposure. By this approach, conjugation involving lysine residues (normally a random process) can be controlled. It enables the preparation of lysine‐mediated glycoconjugates with improved batch‐to‐batch reproducibility, thereby producing neo‐glycoconjugates with more‐consistent biological activity.     

Soft X‐ray Ptychographic Imaging and Morphological Quantification of Calcium Silicate Hydrates (C–S–H)

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC‐based systems but are still only partially known. Here we introduce the first soft X‐ray ptychographic imaging of tricalcium silicate (C₃S) hydration products. The results are compared using both scanning transmission X‐ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C₃S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high‐resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q^?3 regime, whereas the inner product C–S–H transitions to a q^?2 regime. Various hypotheses are discussed to explain these regimes.     

Thermal behavior and structural study of ZrO2/poly(ε-caprolactone) hybrids synthesized via sol-gel route

The thermal behavior of pure ZrO₂ and four ZrO₂-based organic-inorganic hybrids (OIHs) containing increasing amount (6, 12, 24 and 50?wt%) of poly(ε-caprolactone) (PCL) (named Z, ZP6, ZP12, ZP24 and ZP50 respectively) has been studied by simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC). The FTIR analysis of the gas mixture evolved at defined temperatures from the samples submitted to the TG experiments identified the mechanism of each thermally activated process. The obtained results suggest that the inorganic matrix of the OIHs prepared by this method exerts a stabilizing effect on the polymer, in particular for poor-PCL hybrid materials. In fact, the different thermal behavior of the ZP50 sample suggests that the polymer is not entirely bonded to the -OH groups of the zirconia matrix due to their saturation. For this reason a part of PCL is not affected by the stabilizing effect of the matrix and is subjected to thermal degradation. Finally, by observing their thermal behavior it was possible to select the most suitable temperatures for thermal pretreatment: 400, 600 and 1000?°C. The structural analysis by X-ray diffraction (XRD) revealed that at 400?°C the materials are amorphous, while at 600?°C they are mostly tetragonal, and the content of the tetragonal phase decreases with increasing the amount of PCL in the OIHs. All the materials treated at 1000?°C are monoclinic, but their crystallinity decreases with increasing the PCL content.     

Experimental study on performance and emissions of a high speed diesel engine fuelled with n-butanol diesel blends under premixed low temperature combustion

In the present paper, results of an experimental investigation carried out in a modern diesel engine running at different operative conditions and fuelled with blends of diesel and n-butanol, are reported. The exploration strategy was focused on the management of the timing and injection pressure to achieve a condition in which the whole amount of fuel was delivered before ignition. The aim of the paper was to evaluate the potential to employ fuel blends having low cetane number and high resistance to auto-ignition to reduce engine out emissions of NOx and smoke without significant penalty on engine performance. Fuel blends were mixed by the baseline diesel (BU00) with 20% and 40% of n-butanol by volume. The n-butanol was taken by commercial production that is largely produced through petrochemical pathways although the molecule is substantially unchanged for butanol produced through biological mechanisms.The experimental activity was performed on a turbocharged, water cooled, DI diesel engine, equipped with a common rail injection system. The engine equipment includes an exhaust gas recirculation system controlled by an external driver, a piezo-quartz pressure transducer to detect the in-cylinder pressure signal and a current probe to acquire the energizing current to the injectors. Engine tests were carried out at 2500 rpm and 0.8 MPa of BMEP exploring the effect of start of injection, O₂ concentration at intake and injection pressure on combustion behavior and engine out emissions. The in-cylinder pressure and rate of heat release were investigated for the neat diesel and the two blends to evaluate engine performance and exhaust emissions both for the conventional diesel and the advanced premixed combustion processes.The management of injection pressure, O₂ concentration at intake and injection timing allowed to realize a partial premixed combustion by extending the ignition delay, particularly for blends. The main results of the investigation made reach smoke and NOx emissions due to the longer ignition delay and a better mixing control before combustion. The joint effect of higher resistance to auto ignition and higher volatility of n-butanol blends improved emissions compared to the neat diesel fuel with a low penalty on fuel consumption.     

Core Cross-Linked Amphiphilic Star-Block Copolymers with (Meth)acrylic Acid Shells Prepared by Atom Transfer Radical Polymerization

Core cross-linked amphiphilic star-block copolymers were prepared by hydrolysis of the outer shell of star-block copolymers prepared using copper mediated atom transfer radical polymerization (ATRP). In an arm-first approach, linear poly(tert-butyl methacrylate) macroinitiators (PtBMA-Cl) were extended with styrene to yield PtBMA-b-PS-Cl and then cross-linked with divinylbenzene (DVB) in order to yield (PtBMA-b-PS)_arms-PDVB_core star-block copolymers. Then, PMAA-b-PS block and (PMAA-PS)_arms-PDVB_core star-block copolymers were obtained by hydrolysis of the PtBMA blocks in both linear and cross-linked copolymers, as confirmed by ¹H NMR analyses. The amphiphilic character of these copolymers was confirmed by solubilisation in water. Several factors affecting the polymer aggregation and solubility such as the length, the composition of the arms and the catalyst used were studied. An acrylate analogue, that is, (PAA-b-PS)_arms-PDVB_core, was also prepared for comparison purposes. Atomic force microscopy (AFM) and differential scanning calorimetry (DSC) were used to elucidate the morphology and the thermal behaviour of the star-block copolymers.     

Click-Chemistry (CuAAC) Trimerization of an αvβ6 Integrin Targeting Ga-68-Peptide: Enhanced Contrast for in-Vivo PET Imaging of Human Lung Adenocarcinoma Xenografts

α_vβ₆ Integrin is an epithelial transmembrane protein that recognizes latency-associated peptide (LAP) and primarily activates transforming growth factor beta (TGF-β). It is overexpressed in carcinomas (most notably, pancreatic) and other conditions associated with α_vβ₆ integrin-dependent TGF-β dysregulation, such as fibrosis. We have designed a trimeric Ga-68-labeled TRAP conjugate of the α_vβ₆-specific cyclic pentapeptide SDM17 (cyclo[RGD-Chg-E]-CONH₂) to enhance α_vβ₆ integrin affinity as well as target-specific in-vivo uptake. Ga-68-TRAP(SDM17)₃ showed a 28-fold higher α_vβ₆ affinity than the corresponding monomer Ga-68-NOTA-SDM17 (IC₅₀ of 0.26 vs. 7.4 nM, respectively), a 13-fold higher IC₅₀-based selectivity over the related integrin α_vβ₈ (factors of 662 vs. 49), and a threefold higher tumor uptake (2.1 vs. 0.66 %ID/g) in biodistribution experiments with H2009 tumor-bearing SCID mice. The remarkably high tumor/organ ratios (tumor-to-blood 11.2; -to-liver 8.7; -to-pancreas 29.7) enabled high-contrast tumor delineation in PET images. We conclude that Ga-68-TRAP(SDM17)₃ holds promise for improved clinical PET diagnostics of carcinomas and fibrosis.