Isoselective Polymerization of 1-Vinylcyclohexene (VCH) and a Terpene Derived Monomer S-4-Isopropenyl-1-vinyl-1-cyclohexene (IVC), and Its Binary Copolymerization with Linear Terpenes.

The advancement of stereoregular polymerization techniques for linear 1,3-dienes has enabled the production of polymers with precise stereocontrol, influencing their physical and chemical properties significantly. While 1,3-butadiene and isoprene yield diverse stereoregular polymers, cyclic dienes have received less attention due to catalyst challenges and limited application in the rubber industry. However, the growing interest in bio-based monomers, particularly those derived from terpenes and terpenoids, has revitalized interest in cyclic monomers with conjugated double bonds.

Synthesis and Characterization of β-Myrcene-Styrene and β-Ocimene-Styrene Copolymers.

The structure-properties relationships of sustainable materials derived from biomass-based monomers are investigated, focusing on hybrid styrene/terpene-based copolymers with blocky microstructures, such as β-myrcene- and β-ocimene-styrene copolymers. The samples show complex glass transition dynamics, as evidenced by the physical aging experienced by the amorphous phase in styrene-rich copolymers. The tendency of styrene- and terpene-rich sequences to give heterogeneous morphologies with correlation strength extending over 10-40 nm is outlined, through small-angle X-ray scattering analysis.

Solid-State Reaction of Alkylamines with CO in Ambient Air.

This paper explores possible procedures to accelerate CO capture from ambient air by a crystalline alkylamine surfactant (octadecylamine), leading to the corresponding crystalline ammonium-carbamate. Conversion of the amine to the carbamate, in different conditions, is studied by four different techniques: WAXD, FTIR, TGA, and DSC. The WAXD study also gives relevant information on the crystal structures of both amine and derived carbamate.

Pluronic F68 Micelles as Carriers for an Anti-Inflammatory Drug: A Rheological and Scattering Investigation.

Age-long ambition of medical scientists has always been advancement in healthcare and therapeutic medicine. Biomedical research indeed claims paramount importance in nanomedicine and drug delivery, and the development of biocompatible storage structures for delivering drugs stands at the heart of emerging scientific works. The delivery of drugs into the human body is nevertheless a nontrivial and challenging task, and it is often addressed by using amphiphilic compounds as nanosized delivery vehicles.

The Rainbow Arching over the Fluorescent Thienoviologen Mesophases.

Thermofluorochromic materials exhibit tunable fluorescence emission on heating or cooling. They are highly desirable for applications ranging from temperature sensing to high-security anti-counterfeiting. Luminescent matrices based on liquid crystals are very promising, particularly those based on liquid crystals with intrinsic fluorescence.

Molecular Features Behind Formation of α or β Co-Crystalline and Nanoporous-Crystalline Phases of PPO.

Guest molecular features determining the formation of α and β phases of poly(2-6-dimethyl-1,4-phenylene) oxide (PPO) are explored by collecting literature data and adding many new film preparations, both by solution casting and by guest sorption in amorphous films. Independently of the considered preparation method, the α-form is favored by the hydrophobic and bulky guest molecules, while the hydrophilic and small guest molecules favor the β-form. Furthermore, molecular modeling studies indicate that the β-form inducer guests establish stronger dispersive interactions with the PPO units than the α-form inducer guests.

Ethylene--norbornene Copolymerization Using a Dual Catalyst System in the Presence of a Chain Transfer Agent.

Ethylene--norbornene copolymers were synthesized by a dual catalyst system at three concentrations of norbornene in the feed and variable amounts of ZnEt₂, as a possible chain transfer agent. The dual catalyst system consists of two -metallocenes, isopropyliden(ηcyclopentadienyl)(η⁵-indenyl)zirconium dichloride () and isopropyliden(η⁵-3-methylcyclopentadienyl)(η⁵-fluorenyl)zirconium dichloride (), activated with dimethylanilinium tetrakis(pentafluorophenyl)borate, in presence of TIBA. Values of norbornene content, molecular mass, glass transition temperature, and reactivity ratios and of copolymers prepared in the presence of + are intermediate between those of reference copolymers.

Time-Resolving Study of Stress-Induced Transformations of Isotactic Polypropylene through Wide Angle X-ray Scattering Measurements.

The development of a highly oriented fiber morphology by effect of tensile deformation of stereodefective isotactic polypropylene (iPP) samples, starting from the unoriented γ form, is studied by following the transformation in real time during stretching through wide angle X-ray scattering (WAXS) measurements. In the stretching process, after yielding, the initial γ form transforms into the mesomorphic form of iPP through mechanical melting and re-crystallization. The analysis of the scattering invariant measured in the WAXS region highlights that the size of the mesomorphic domains included in the well oriented fiber morphology obtained at high deformations increases through a process which involves the coalescence of the small fragments formed by effect of tensile stress during lamellar destruction with the domain of higher dimensions.

Nano-in-Nano Approach for Enzyme Immobilization Based on Block Copolymers.

We set up a facile approach for fabrication of supports with tailored nanoporosity for immobilization of enzymes. To this aim block copolymers (BCPs) self-assembly has been used to prepare nanostructured thin films with well-defined architecture containing pores of tailorable size delimited by walls with tailorable degree of hydrophilicity. In particular, we employed a mixture of polystyrene-block-poly(l-lactide) (PS-PLLA) and polystyrene-block-poly(ethylene oxide) (PS-PEO) diblock copolymers to generate thin films with a lamellar morphology consisting of PS lamellar domains alternating with mixed PEO/PLLA blocks lamellar domains.

Isotactic and Syndiotactic Alternating Ethylene/Propylene Copolymers Obtained Through Non-Catalytic Hydrogenation of Highly Stereoregular cis-1,4 Poly(1,3-diene)s.

The homogeneous non-catalytic hydrogenation of -1,4 poly(isoprene), isotactic -1,4 poly(1,3-pentadiene) and syndiotactic -1,4 poly(1,3-pentadiene) with diimide, formed by thermal decomposition of -toluenesulfonylhydrazide, is examined. Perfectly alternating ethylene/propylene copolymers having different tacticity (i.e.

Controlling Size and Orientation of Lamellar Microdomains in Crystalline Block Copolymers.

Highly ordered lamellar nanostructures with high orientation of lamellar microdomains have been obtained by epitaxial crystallization of crystalline diblock copolymers constituted by crystalline polyethylene (PE) linked to an amorphous block of a propene-ethene random copolymer (EP). The epitaxial crystallization onto crystals of p-chlorobenzoic acid induces formation of crystalline PE lamellae highly aligned along one direction, resulting in ordered lamellar nanostructures with perfectly aligned layers of crystalline PE alternating to amorphous layers of EP block. The periodicity of the lamellar structure can be modulated by modifying the molecular mass of the amorphous EP block.

Tuning Ordered Pattern of Pd Species through Controlled Block Copolymer Self-Assembly.

We report a method for the preparation of ordered patterns of Pd species on a substrate based on the use of polystyrene-block-poly(ethylene oxide) copolymer (PS-b-PEO) templates and selective inclusion of palladium (Pd) species in the PEO domains. PS-b-PEO samples of different total molecular masses self-assemble in a cylindrical microphase-separated morphology, in which vertically aligned PEO cylinders, with different diameters depending on the molecular mass, are organized in a hexagonal array of different lateral spacings. The cylindrical nanostructure is maintained after the selective inclusion of Pd species (Pd acetate and Pd nanoparticles (NPs) after reduction of Pd ions of the salt) in the PEO cylinders so that the characteristic sizes (diameters and lateral spacings) of the included Pd species are tuned by the characteristic sizes of the block copolymer (BCP) template, which are regulated by molecular mass.

Stereocomplexed poly(limonene carbonate): a unique example of the cocrystallization of amorphous enantiomeric polymers.

We report the cocrystallization of the regio- and stereoregular chiral copolymer poly(limonene carbonate). To the best of our knowledge, this marks the first example of an amorphous, enantiomerically pure polymer that becomes crystalline upon stereocomplexation with its complementary enantiomer. By analyzing X-ray powder diffraction data, we propose a packing model in which sheets of enantiopure chains interdigitate with layers of the opposite enantiomer, forming a "steric zipper".

Small angle X-ray scattering investigation of norbornene-terminated syndiotactic polypropylene and corresponding comb-like poly(macromonomer).

The structure and crystallization properties of a norbornene end-functionalized syndiotactic polypropylene (sPP) macromonomer (MMsPP) with [rrrr] = 80 mol % and molecular mass Mn = 3600 g/mol and corresponding comb-like poly(macromonomer) (pMMsPP) with Mn = 100000 g/mol have been investigated using wide angle (WAXS) and small angle (SAXS) X-ray scattering, atomic force (AFM), transmission electron (TEM), and optical (OM) microscopy. The analysis reveals the tendency of the macromonomer and poly(macromonomer) to form structures characterized by layers of sPP chains alternated to layers occupied by the cyclic groups (norbornene or polynorbornene), and a small degree of interdigitation of sPP chains belonging to adjacent layers facing each other in an end-to-end arrangement. It is argued that this layering is dictated, upon crystallization, by nanophase separation of the flexible sPP chains in regions apart from those occupied by the cyclic groups coupled to formation of sPP crystals organized in the lamellar morphology.

Nanocomposites from block copolymer lamellar nanostructures and selective gold deposition.

Innovative hybrid nanocomposites based on a nanostructured block copolymer (BCP) matrix whose lamellar nanodomains are selectively loaded with metal nanoparticles, have been prepared. A symmetric poly(styrene-b-methylmethacrylate) (PS-b-PMMA) amorphous BCP showing a lamellar morphology has been employed. Thin films of PS-b-PMMA were deposited by spin-coating or drop casting on indium thin oxide (ITO) substrate in order to achieve orientation of lamellae with the lamellar surface perpendicular to the substrate.

Time-resolving analysis of cryotropic gelation of water/poly(vinyl alcohol) solutions via small-angle neutron scattering.

The structural transformations occurring in initially homogeneous aqueous solutions of poly(vinyl alcohol) (PVA) through application of freezing (-13 degrees C) and thawing (20 degrees C) cycles is investigated by time resolving small-angle neutron scattering (SANS). These measurements indicate that formation of gels of complex hierarchical structure arises from occurrence of different elementary processes, involving different length and time scales. The fastest process that could be detected by our measurements during the first cryotropic treatment consists of the crystallization of the solvent.

Mesoscopic and microscopic investigation on poly(vinyl alcohol) hydrogels in the presence of sodium decylsulfate.

The structure of poly(vinyl alcohol) (PVA) hydrogels formed as a result of freeze/thaw treatments of aqueous solutions of the polymer (11 wt % PVA) in the freshly prepared state is analyzed through the combined use of small (SANS) and ultrasmall (USANS) angle neutron scattering techniques. The structure of these hydrogels may be described in terms of polymer rich regions, with dimensions of the order of 1-2 microm, dispersed in a water rich phase, forming two bicontinuous phases. The PVA chains in the polymer rich phase form a network where the cross-linking points are mainly crystalline aggregates of PVA having average dimensions of approximately 45 A.

A study of the microstructural and diffusion properties of poly(vinyl alcohol) cryogels containing surfactant supramolecular aggregates.

Surfactant-containing poly(vinyl alcohol) (PVA) cryogels have been prepared by drying and reswelling hydrogel patches, previously obtained by the freeze/thaw procedure, in decyltrimethylammonium bromide (C10TAB) aqueous solutions. The microstructural and diffusive properties of the resulting material have been characterized by a combined experimental strategy. Gravimetric measurements show that the cryogel maximum swelling is not affected by the surfactant.

Structural-mechanical phase diagram of isotactic polypropylene.

The polymorphic transformations associated with the plastic deformation of isotactic polypropylene samples of different stereoregularity, prepared with different metallocene catalysts, have been studied. Crystals of alpha or gamma forms, present in the unstretched samples, transform into the mesomorphic form by stretching. The formation of the mesophase facilitates successive further deformation up to very high strains and produces development of outstanding unusual properties of high flexibility and elasticity.

A microscopic insight into the deformation behavior of semicrystalline polymers: the role of phase transitions.

The deformation behavior of semicrystalline polymers associated with polymorphic transformations under tensile deformation is discussed in the case of syndiotactic polypropylene. We report a phase diagram of this polymer where the regions of stability of the different polymorphic forms are defined as a function of the degree of stereoregularity and deformation. The values of critical strain corresponding to the structural transformations depend on the stereoregularity that affects the relative stability of the involved polymorphic forms and the state of the entangled amorphous phase.

Crystals and crystallinity in polymeric materials.

A new view of the concepts of crystallinity and crystals in synthetic macromolecules is discussed. In polymeric materials, crystallinity may be present with the concomitant occurrence of large amounts of structural disorder and in the absence of true three-dimensional long-range order. The structures of semicrystalline polymeric materials are discussed in terms of idealized limit models of crystals, where long-range order may be achieved for structural features that are not necessarily coincident with single atoms and are not necessarily point-centered.