Thioxanthone-Based Siloxane Photosensitizer for Cationic/Radical Photopolymerization and Photoinduced Sol-Gel Reactions.

In this investigation, a multifunctional visible-light TX-based photosensitizer containing a siloxane moiety (TXS) was designed with a good overall yield of 54%. The addition of a siloxane moiety enabled the incorporation of a TX photosensitizer into a siloxane network by photoinduced sol-gel chemistry, thus avoiding its release. Both liquid 1H and solid-state 29Si NMR measurements undeniably confirmed the formation of photoacids resulting from the photolysis of the TXS/electron acceptor molecule (Iodonium salt), which promoted the photoinduced hydrolysis/condensation of the trimethoxysilane groups of TXS, with a high degree of condensation of its inorganic network. Notably, the laser flash photolysis, fluorescence, and electron paramagnetic resonance spin-trapping (EPR ST) experiments demonstrated that TXS could react with Iod through an electron transfer reaction through its excited states, leading to the formation of radical initiating species. Interestingly, the TXS/Iod was demonstrated to be an efficient photoinitiating system for free-radical (FRP) and cationic (CP) polymerization under LEDs@385, 405, and 455 nm. In particular, whatever the epoxy monomer mixtures used, remarkable final epoxy conversions were achieved up to 100% under air. In this latter case, we demonstrated that both the photoinduced sol-gel process (hydrolysis of trimethoxysilane groups) and the cationic photopolymerization occurred simultaneously.

Design of Collagen and Gelatin-based Electrospun Fibers for Biomedical Purposes: An Overview.

Collagen and gelatin are essential natural biopolymers commonly utilized in biomaterials and tissue engineering because of their excellent physicochemical and biocompatibility properties. They can be used either in combination with other biomacromolecules or particles or even exclusively for the enhancement of bone regeneration or for the development of biomimetic scaffolds. Collagen or gelatin derivatives can be transformed into nanofibrous materials with porous micro- or nanostructures and superior mechanical properties and biocompatibility using electrospinning technology. Specific attention was recently paid to electrospun mats of such biopolymers, due to their high ratio of surface area to volume, as well as their biocompatibility, biodegradability, and low immunogenicity. The fiber mats with submicro- and nanometer scale can replicate the extracellular matrix structure of human tissues and organs, making them highly suitable for use in tissue engineering due to their exceptional bioaffinity. The drawbacks may include rapid degradation and complete dissolution in aqueous media. The use of gelatin/collagen electrospun nanofibers in this form is thus greatly restricted for biomedicine. Therefore, the cross-linking of these fibers is necessary for controlling their aqueous solubility. This led to enhanced biological characteristics of the fibers, rendering them excellent options for various biomedical uses. The objective of this review is to highlight the key research related to the electrospinning of collagen and gelatin, as well as their applications in the biomedical field. The review features a detailed examination of the electrospinning fiber mats, showcasing their varying structures and performances resulting from diverse solvents, electrospinning processes, and cross-linking methods. Judiciously selected examples from literature will be presented to demonstrate major advantages of such biofibers. The current developments and difficulties in this area of research are also being addressed.

Influence of Placement of Lumbar Interbody Cage on Subsidence Risk: Biomechanical Study.

OBJECTIVE: Lumbar spinal fusion is a common surgical procedure that can be done with a variety of different instrumentation and techniques. Despite numerous research studies investigating subsidence risk factors, the impact of cage placement on subsidence is not fully elucidated. This study aims to determine whether placement of an expandable transforaminal lumbar interbody fusion cage at the center end plate or at the anterior apophyseal ring affects cage subsidence. METHODS: A transforaminal lumbar interbody fusion cage was placed centrally or peripherally between 2 synthetic vertebral models of L3 and L4. A compression plate attached to a 10 KN load cell was used to uniaxially compress the assembly. The ultimate force required for the assembly to fail and subsidence stiffness were analyzed. Computed tomography scans of each L3 and L4 were obtained, and maximum end plate subsidence was measured in the frontal plane. RESULTS: Anterior apophyseal cage placement resulted in higher stiffness of the vertebrae-cage assembly (Ks, 962.89 N/mm) and a higher subsidence stiffness (Kb,987.21 N/mm) compared with central placement (P < 0.05). Ultimate compressive load of the vertebrae-cage assembly did not increase. Moreover, the maximum subsidence depth did not significantly vary between placements. CONCLUSIONS: The subsidence stiffness increased with anterior apophyseal cage placement. Periphery end plate cortical bone architecture may play a role in resisting the impact of cage subsidence. To fully understand the effect of cage placement on cage subsidence, future studies should investigate its implications on native and diseased spine.

Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites.

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12-15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, Tg (DSC data), and the temperature of α relaxation, Tα (DMTA data), by 45-55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher Tα values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E', at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99-3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO2, He), and diffusion coefficients (CO2) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5-4 times (CO2), respectively, and the diffusion coefficient of CO2 increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH2 group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of -NH2 and -NH- groups with -O-C≡N groups from CER.