Amorphous Elastomeric Ultra-High Molar Mass Polypropylene in High Yield by Half-Titanocene Catalysts.

Propylene polymerizations with different ketimide-modified half-titanocene catalysts, Cp'TiCl2(N=CtBu2) [Cp' = C5H5 (1), C5Me5 (2), Me3SiC5H4 (3)], with MAO as a cocatalyst, were investigated. The obtained polymers were studied in detail by determining their microstructure, molar masses, thermal, and mechanical properties. The Cp*-ketimide, (C5Me5)TiCl2(N=CtBu2) (2), exhibited higher catalytic activities than Cp'TiCl2(N=CtBu2) (1,3), yielding higher molar mass polymers, Mw up to 1400 Kg/mol. All the synthesized polypropylenes (PP) are atactic and highly regioregular, with predominant rrrr pentads, especially PP prepared with catalyst 1. Differential scanning calorimetry (DSC) established that the polymers are fully amorphous aPP, and no melting endotherm events are detected. Glass transition temperatures were detected between -2 and 2 °C. These polypropylenes have been established to be high-performance thermoplastic elastomers endowed with remarkably high ductility, and a tensile strain at break higher than 2000%.

Flexible Polyurethane Foams from Bio-Based Polyols: Prepolymer Synthesis and Characterization.

Bio-polyols (BPOs), characterized by a hydroxyl number up to around 90 mg KOH/g, narrow polydispersity index and relatively low molecular mass up to 2000 g/mol, were synthetized from partially and completely epoxidized soybean and linseed oils and caprylic acid or 3-phenyl butyric acid. These BPOs were used in the presence of toluene diisocyanate to produce polyurethane (PU) foams by using a quasi-prepolymer method involving a two-step reaction. A detailed structural investigation of the prepolymers from toluene diisocyanate and both BPOs and polypropylene glycol was conducted by SEC and solution NMR. The apparent density of the foams was in the range of 40-90 kg/m3, with higher values for foams from the aromatic acid. All the foams showed an open-cell structure with uniform and regular shape and uniform size. The specific Young's moduli and compression deflection values suggest superior mechanical properties than the reference foams. The novel synthesized polyurethanes are excellent candidates to partially replace petroleum-based materials.

High-Glass-Transition Polyesters Produced with Phthalic Anhydride and Epoxides by Ring-Opening Copolymerization (ROCOP).

Polyesters with a high glass transition temperature above 130 °C were obtained from limonene oxide (LO) or vinylcyclohexene oxide (VCHO) and phthalic anhydride (PA) in the presence of commercial salen-type complexes with different metals-Cr, Al, and Mn-as catalysts in combination with 4-(dimethylamino) pyridine (DMAP), bis-(triphenylphosphorydine) ammonium chloride (PPNCl), and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) as cocatalysts via alternating ring-opening copolymerization (ROCOP). The effects of the time of precontact between the catalyst and cocatalyst and the polymerization time on the productivity, molar mass (Mw), and glass transition temperature (Tg) were evaluated. The polyesters were characterized by a molar mass (Mw) of up to 14.0 kg/mol, a narrow dispersity Tg of up to 136 °C, and low (<3 mol%) polyether units. For poly(LO-alt-PA) copolymers, biodegradation tests were performed according to ISO 14851 using the respirometric biochemical oxygen demand method. Moreover, the vinyl double bond present in the poly(LO-alt-PA) copolymer chain was functionalized using three different thiols, methyl-3-mercaptopropionate, isooctyl-3-mercaptopropionate, and butyl-3-mercaptopropionate, via a click chemistry reaction. The thermal properties of poly(LO-alt-PA), poly(VCHO-alt-PA) and thiol-modified poly(LO-alt-PA) copolymers were extensively studied by DSC and TGA. Some preliminary compression molding tests were also conducted.

Biocomposite Foams with Multimodal Cellular Structures Based on Cork Granulates and Microwave Processed Egg White Proteins.

In an effort to reduce greenhouse gas emission, reduce the consumption of natural resources, and increase the sustainability of biocomposite foams, the present study focuses on the recycling of cork processing waste for the production of lightweight, non-structural, fireproof thermal and acoustic insulating panels. Egg white proteins (EWP) were used as a matrix model to introduce an open cell structure via a simple and energy-efficient microwave foaming process. Samples with different compositions (ratio of EWP and cork) and additives (eggshells and inorganic intumescent fillers) were prepared with the aim of correlating composition, cellular structures, flame resistance, and mechanical properties.

Antibacterial Properties of Polyurethane Foams Additivated with Terpenes from a Bio-Based Polyol.

Water-blown polyurethane (PU) foams were prepared by bio-polyols from epoxidized linseed oils and caprylic acid in combination with toluene diisocianate (TDI). A series of terpenes (menthol, geraniol, terpineol, and borneol), natural compounds with recognized antibacterial properties, were included in the starting formulations to confer bactericidal properties to the final material. Foams additivated with Irgasan®, a broad-spectrum antimicrobial molecule, were prepared as reference. The bactericidal activity of foams against planktonic and sessile E. coli (ATCC 11229) and S. aureus (ATCC 6538) was evaluated following a modified AATCC 100-2012 static method. Menthol-additivated foams showed broad-spectrum antibacterial activity, reducing Gram+ and Gram- viability by more than 60%. Foams prepared with borneol and terpineol showed selective antibacterial activity against E. coli and S. aureus, respectively. NMR analysis of foams leaking in water supported a bactericidal mechanism mediated by contact killing rather than molecule release. The results represent the proof of concept of the possibility to develop bio-based PU foams with intrinsic bactericidal properties through a simple and innovative synthetic approach.

Maxillary Anterior Teeth Dimensions and Relative Width Proportions: A Narrative Literature Review.

Predictable results in the aesthetic treatment of anterior teeth can be obtained by resorting to the concept of dental aesthetics and, in particular, defining the ideal tooth dimensions and proportions to obtain a harmonious smile. Considering the great variety of articles dealing with the topic, and the lack of updated reviews, this narrative literature review aims to evaluate current knowledge on anterior teeth dimensions and to verify the existence and the potential applications of the anterior teeth proportioning theories (Golden Proportion, Golden Percentage, RED Proportion, and Golden Rectangle). PubMed, Embase, Cochrane Library, and Google Scholar databases were comprehensively searched using different keywords and term combinations. The research includes articles published up to June 2023, no time limits were set, and only articles in English were included. Inclusion criteria comprehended reviews, clinical studies, and in-vitro studies. A total of 66 articles were selected. Two main topics were identified: "Anterior teeth dimensions", "Golden Proportions, Golden Percentage, RED Proportions, and Golden Rectangle". As far as tooth dimensions are concerned, different width ranges are recognized for men and women and for different ethnic groups. Perfectly symmetric contralateral elements are found in low percentages of subjects. The correlation between dental dimensions and facial parameters is not always present, and it strongly depends on the sample's ethnicity and gender. Ideal tooth proportions were only partially identified.

Styrene-Free Bio-Based Thermosetting Resins with Tunable Properties Starting from Vegetable Oils and Terpenes.

The substitution of fossil-based monomers in the thermosetting formulations is a fundamental issue to face the environmental concerns related to the use of traditional resins. In this paper, styrene-free thermosetting resins were prepared to start from vegetable oils with different compositions and unsaturation degrees, namely soybean, hempseed, and linseed oils. Using terpenic comonomers such as limonene and ß-myrcene allows one to prepare thermosets avoiding the traditional fossil-based diluents such as styrene, thus obtaining an outstanding gain in terms of both environmental and safety concerns. Furthermore, the materials obtained reveal tunable physical properties upon the proper choice of the monomers, with glass transition temperature ranging from 40 to 80 °C and Young's modulus ranging from 200 to 1800 MPa. The possibility of preparing composite materials starting from the resins prepared in this way and natural fibres has also been explored due to the potential applications of bio-based composites in several industrial sectors.

Crystallization Behavior of Poly(ε-Caprolactone)-Hollow Glass Microspheres Composites for Rotational Molding Technology.

Composites suitable for rotational molding technology based on poly(ε-caprolactone) (PCL) and filled with hollow glass microspheres (HGM) or functionalized hollow glass microspheres (HGMf) were prepared via melt-compounding. The functionalization of glass microspheres was carried out by a silanization treatment in order to improve the compatibility between the inorganic particles and the polymer matrix and achieve a good dispersion of glass microspheres in the matrix and an enhanced filler-polymer adhesion. The crystallization behavior of materials was studied by DSC under isothermal and non-isothermal conditions and the nucleating effect of the glass microspheres was proven. In particular, the presence of silanized glass microspheres promoted faster crystallization rates and higher nucleation activity, which are enhanced by 75% and 50%, respectively, comparing neat PCL and the composite filled with 20 wt% HGMf. The crystalline and supermolecular structure of PCL and composites crystallized from the melt was evaluated by WAXD and SAXS, highlighting differences in terms of crystallinity index and structural parameters as a function of the adopted crystallization conditions.

Flexible Polyurethane Foams from Epoxidized Vegetable Oils and a Bio-Based Diisocyanate.

Bio-polyols from epoxidized soybean and linseed oils and caprylic acid or 3-phenyl butyric acid were prepared using an environmentally friendly, solvent-free method evaluating the presence of triethylamine as catalyst. Side reactions, leading to a cross-linking structure with high density, were reduced, introducing the catalyst and properly tuning the reaction conditions. A medium functionality value of around 3 along with a hydroxyl number up to around 90 mg KOH/g, narrow polydispersity index, and relatively low molecular mass up to 2400 g/mol were the experimental targets. From selected bio-polyols and an aliphatic partially bio-based isocyanate, a series of water blown polyurethane (PU) foams was produced, estimating the effect of the chemical nature of substituents in the polyol backbone on the PU properties. The apparent density of the foams was in the range of 79-113 kg/m3, with higher values for foams from the aromatic acid. Flexible polyurethane foams with open cell structure from bio-based polyols were obtained, with higher cavity size and lower pore sizes for foams from caprylic acid. The bio-based flexible PU foams showed comparable Young's moduli (14-18 kPa) and compression deflection values (4.6-5.5 kPa) and exhibited an almost complete recovery of their initial size.

Polyurethane-Based Coatings with Promising Antibacterial Properties.

In coatings technology, the possibility of introducing specific characteristics at the surface level allows for the manufacture of medical devices with efficient and prolonged antibacterial properties. This efficiency is often achieved by the use of a small amount of antibacterial molecules, which can fulfil their duty while limiting eventual releasing problems. The object of this work was the preparation and characterization of silver, titanium dioxide and chitosan polyurethane-based coatings. Coatings with the three antibacterials were prepared using different deposition techniques, using a brush or a bar coater automatic film applicator, and compared to solvent casted films prepared with the same components. For silver containing materials, an innovative strategy contemplating the use and preparation of silver nanoparticles in a single step-method was employed. This preparation was obtained starting from a silver precursor and using a single compound as the reducing agent and stabilizer. Ultraviolet-visible spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, contact angle measurements and adhesion test experiments were used to characterize the prepared coatings. Promising antibacterial properties, measured via direct and indirect methods, were registered for all the silver-based materials.

Polyurethane-Based Composites: Effects of Antibacterial Fillers on the Physical-Mechanical Behavior of Thermoplastic Polyurethanes.

The challenge to manufacture medical devices with specific antibacterial functions, and the growing demand for systems able to limit bacterial resistance growth, necessitates the development of new technologies which can be easily produced at an industrial level. The object of this work was the study and the development of silver, titanium dioxide, and chitosan composites for the realization and/or implementation of biomedical devices. Thermoplastic elastomeric polyurethane was selected and used as matrix for the various antibacterial functions introduced during the processing phase (melt compounding). This strategy was employed to directly incorporate antimicrobial agents into the main constituent material of the devices themselves. With the exception of the composite filled with titanium dioxide, all of the other tested composites were shown to possess satisfactory mechanical properties. The best antibacterial effects were obtained with all the composites against Staphylococcus aureus: viability was efficiently inhibited by the prepared materials in four different bacterial culture concentrations.

Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes.

Herein, we report the homo- and co-polymerization of ethylene (E) with norbornene (NB) catalyzed by vanadium(III) phosphine complexes of the type VCl3(PMenPh3-n)2 [n = 2 (1a), 1 (1b)] and VCl3(PR3)2 [R = phenyl (Ph, 1c), cyclohexyl (Cy, 1d), tert-butyl (tBu, 1e)]. In the presence of Et2AlCl and Cl3CCOOEt (ETA), 1a-1e exhibit good activities for the polymerization of ethylene, affording linear, semicrystalline PEs with a melting temperature of approximately 130 °C. Mainly alternating copolymers with high comonomer incorporation were obtained in the E/NB copolymerization. A relationship was found between the electronic and steric properties of the phosphine ligands and the catalytic performance. Overall, the presence of electron-withdrawing ligand substituents increases the productivity, complexes with aryl phosphine (weaker σ-donor character) exhibiting a higher (co)polymerization initiation rate than those with alkyl phosphines (stronger σ-donor character). Steric effects also seem to play a key role since 1d and 1e, having large size phosphines (PCy3 θ = 170° and PtBu3 θ = 182°, respectively) are more active than 1a (PMe2Ph θ = 122°). In this case, the larger size of PtBu3 and PCy3 likely compensates for their higher donor strength compared to PMe2Ph.

Lightweight Poly(ε-Caprolactone) Composites with Surface Modified Hollow Glass Microspheres for Use in Rotational Molding: Thermal, Rheological and Mechanical Properties.

In this work, novel composites based on poly(ε-caprolactone) (PCL) were prepared and characterized in terms of morphological, thermal, rheological and mechanical properties. Hollow glass microspheres (HGM), alone or surface modified by treatment with (3-aminopropyl)triethoxysilane (APTES) in order to enhance the compatibility between the inorganic particles and the polymer matrix, were used to obtain lightweight composites with improved properties. The silanization treatment implies a good dispersion of filler particles in the matrix and an enhanced filler⁻polymer adhesion. The addition of HGM to PCL has relevant implications on the rheological and mechanical properties enhancing the stiffness of the material. Furthermore, the presence of HGM strongly interferes with the crystallization behavior and thermo-oxidative degradation of PCL. The increase of PCL crystallization rate was observed as a function of the HGM amount in the composites. Finally, rotational molding tests demonstrated the possibility of successfully producing manufactured goods in PCL and PCL-based composites on both a laboratory and industrial scale.

Terpolymerization of Substituted Cycloolefin with Ethylene and Norbornene by Transition Metal Catalyst.

Ethylene-norbornene terpolymerization experiments using 5-alkyl-substituted norbornenes (5-pentyl-2-norbornene (C5N) and 5-octyl-2-norbornene (C8N)) or dicyclopentadiene (DCPD) were conducted with two ansa-metallocenes, [Zr{(η5-C9H6)2C2H4}Cl2] (1) and [Zr{(η5-2,5-Me2C5H2)2CHEt}Cl2] (2), activated by methylaluminoxane (MAO). The terpolymers obtained were investigated in detail by determining the microstructure and termonomer contents by 13C NMR, molar masses and thermal properties. Results were compared to those of ethylene (E)-norbornene (N) terpolymerizations with 1-octene. 2, with lower steric hindrance and a shorter bridge, gave the best activities, termonomer incorporation and molar masses. The size of the substituent in 5-alkyl substituted norbornene also plays a role. C8N gives the highest activities and molar masses, while DCPD terpolymers have the highest cycloolefin content. Terpolymers are random; their molar masses, much higher than those in 1-octene terpolymers, are in a range useful for industrial applications. Finally, Tg values up to 152 °C were obtained. For similar N content, poly(E-ter-N-ter-C8N)s and poly(E-ter-N-ter-DCPD)s have the lowest and the highest Tg values, respectively. Thus, the presence of an eight-carbon atom pendant chain in C8N increases the flexibility of the polymer chain more than a five-carbon atom pendant chain in C5N. The higher rigidity of C5N may lead to lower activities and to increasing probability of σ-bond metathesis and chain termination, as evidenced by chain-end group analysis.

A controlled approach to iron oxide nanoparticles functionalization for magnetic polymer brushes.

In this article, we report a detailed study of surface modification of magnetite nanoparticles by means of three different grafting agents, functional for the preparation of magnetic polymer brushes. 3-Aminopropyltriethoxysilane (APTES), 3-chloropropyltriethoxysilane (CPTES), and 2-(4-chlorosulfonylphenyl)ethyltrichlorosilane (CTCS) were chosen as grafting models through which a wide range of polymer brushes can be obtained. By means of accurate thermogravimetric analysis a good control over the amount of immobilized molecules is achieved, and optimal operating conditions for each grafting agent are consequently determined. Graft densities ranging from approximately 4 to 7 molecules per nm(2) are obtained, depending on the conditions used. In addition, the surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) carried out with CTCS-coated nanoparticles is presented as an example of polymer brushes, leading to a well-defined and dense polymeric coating of around 0.6 PMMA chains per nm(2).

A randomized clinical trial comparing at-home and in-office tooth whitening techniques: A nine-month follow-up.

BACKGROUND: The aim of this split-mouth, randomized controlled trial was to compare the whitening results of at-home and in-office tooth bleaching techniques and the longevity of their effects at nine months after teeth had been bleached. METHODS: The authors conducted a study involving a 14-day bleaching period, during which the first maxillary premolars of 17 participants, who were 20 to 25 years of age, were bleached by means of either an at-home technique involving 10 percent carbamide peroxide or an in-office technique involving 38 percent hydrogen peroxide. The authors recorded color variables as proposed by the Commission Internationale de l'Eclairage-lightness (L*), redness (a*) and yellowness (b*)-by using a spectrophotometer at baseline and at one week, one month and nine months after bleaching. They also calculated a whiteness (W) index that was based on the distance of the color value in the color space from a nominal white point. RESULTS: At the nine-month recall visit, comparison between the at-home and the in-office techniques did not show significantly different values for L* (P = .448), a* (P = .350), b* (P = .144) and W (P = .151) color variables. None of the participants experienced any adverse events related to the bleaching during the treatment period. CONCLUSIONS: The study results showed no clinically significant difference in bleaching efficacy. Both techniques produced satisfactory and long-lasting bleaching results. CLINICAL IMPLICATIONS: In young adults, either the at-home or the in-office technique can be used effectively.

Crown-root reattachment of a severe subgingival tooth fracture: a 15-month periodontal evaluation.

Traumatic tooth fractures represent an intriguing challenge for clinicians, particularly when they involve the anterior region of the maxilla. In such situations, esthetic, psychosocial, functional, and therapeutic problems may have a negative effect on the patient's quality of life. In addition, fractures that involve the biologic width of the periodontium are even more difficult to treat. An interdisciplinary approach based on crown lengthening with or without orthodontic extrusion and the definitive prosthetic rehabilitation represent the standard modality of treatment for these conditions to restore the appropriate biologic dimension and to reduce the damage esthetically. However, if the margins of the fragment and the tooth show perfect juxtaposition with no interfragmentary space, an adhesive technique may be indicated. The aim of this case report is to describe the treatment of a severe subgingival tooth fracture by means of adhesive reattachment of the fragment followed by a periodontal evaluation over a 15-month period.

Nanophase separation in polystyrene-polyfluorene block copolymers thin films prepared through the breath figure procedure.

The amphiphilic block copolymer formed by a hydrophobic body of polystyrene and a hydrophilic head of poly[9,9-di(2-(2-tetrahydropyranyl-oxy)hexyl)fluorene-alt-9,9-dioctylfluorene] was synthesized, and its solution was used to create thin films with ordered pattern of holes, by means of the breath figure technique. These porous films, after a thermal treatment, were found to show ordered aggregates of the pi-conjugated blocks in the place of the cavities. This is probably due to a preorganization of the two different blocks of the copolymer occurring during the breath figure formation, which is driven by the condensation of water microdroplets on the polymer solution, and to a following phase segregation occurring during the thermal annealing. This approach is a promising tool to be employed for the organization of organic materials at the micro and nanoscale.

An 8-year follow-up of a fractured endodontically treated incisor restored with a modified laminate veneer.

This clinical report describes the restoration of a left maxillary first incisor using an all-ceramic one-piece coronal post and a laminate veneer feature. This proposed restoration technique represents an alternative to traditional restoration procedures such as metal-ceramic restorations, all ceramic crowns and porcelain laminate veneers. This restoration preserves the remaining tooth structure, re-establishes function and offers good esthetic results.

Influence of operator skill on microleakege of total-etch and self-etch bonding systems.

OBJECTIVES: To evaluate the influence of operator skill on microleakage in class V restorations using simplified bonding systems. METHODS: Two cavities were carried out on the buccal and lingual surfaces of 50 human bicuspid teeth. The teeth were randomly assigned to two groups according to the operator's skill: student group and expert group. The two cavities of each tooth were randomly treated with Adper Scotchbond 1 XT (total-etch adhesive) and Adper Prompt L-Pop (self-etch adhesive). All cavities were restored with a 0.2mm thick layer of flowable composite (Filtek flow) followed by one bulk increment of resin composite (Filtek Supreme XT). Specimens were thermocycled, immersed in 2% methylene blue and sectioned in a bucco-lingual plane. They were then examined under a stereomicroscope and scored according to microleakage. The data was subjected to a multilevel statistical model. RESULTS: At the dentine margin the microleakage resulting from both the self-etch adhesive and the total-etch one was similar in the student and in the expert groups. The interaction term skill x adhesive was not statistically significant (p=0.4156). At the enamel margin the self-etch adhesive microleakage within the student group resulted lower than that within the expert group. On the other hand, the total-etch adhesive microleakage within the expert group resulted lower than that within the student group. The interaction term skill x adhesive was statistically significant (p=0.0037). CONCLUSIONS: Both the adhesives used were sensitive to operator skill in obtaining a reliable seal with the enamel. On the dentine, both adhesives demonstrated little sensitivity to operator skill.