Organocatalytic Ring-Opening Polymerization of ε-Caprolactone Using bis(N-(N′-butylimidazolium)alkane Dicationic Ionic Liquids as the Metal-Free Catalysts: Polymer Synthesis, Kinetics and DFT Mechanistic Study

In this work, we successfully synthesized high thermal sTable 1,n-bis(N-(N′-butylimidazolium)alkane bishexafluorophosphates (1,n-bis[Bim][PF6], n = 4, 6, 8, and 10) catalysts in 55–70% yields from imidazole which were applied as non-toxic DILs catalysts with 1-butanol as initiator for the bulk ROP of ε-caprolactone (CL) in the varied ratio of CL/nBuOH/1,4-bis[Bim][PF6] from 200/1.0/0.25–4.0 to 700/1.0/0.25–4.0 by mol%. The result found that the optimal ratio of CL/nBuOH/1,4-bis[Bim][PF6] 400/1.0/0.5 mol% at 120 °C for 72 h led to the polymerization conversions higher than 95%, with the molecular weight (Mw) of PCL 20,130 g mol−1 (Đ~1.80). The polymerization rate of CL increased with the decreasing linker chain length of ionic liquids. Moreover, the mechanistic study was investigated by DFT using B3LYP (6–31G(d,p)) as basis set. The most plausible mechanism included the stepwise and coordination insertion in which the alkoxide insertion step is the rate-determining step.

The Effect of Inorganic Salt on the Morphology and Nucleation of Polyaniline

Polyaniline nanofibers were fabricated through the addition of inorganic salt such as NaCl, MgSO4 and AlCl3 into the micelle-like composed of aniline and camphor sulfonic acid (CSA). The influence of types and concentration of inorganic salts, doped acids and temperature on polyaniline was studied by TEM, Uv-vis and FTIR spectroscopy. In addition, in situ Uv-vis and 1H NMR were applied to observe the process of aniline polymerization, and it was indicated the polymerization rate of aniline changed after the addition of inorganic salt NaCl into the initial solution.

Raman Spectroscopic Characterization of Polymerization Kinetics of Cyanoacrylate Embolic Glues for Vascular Embolization

Endovascular glue embolization is a minimally invasive technique used to selectively reduce or block the blood supply to specific targeted vessels. Cyanoacrylate glues, mixed with radiopaque iodized oil, have been widely used for vascular embolization owing to their rapid polymerization rate, good penetration ability and low tissue toxicity. Nevertheless, in clinical practice, the selection of the glue–oil proportion and the manual injection process of mixtures are mostly based on empirical knowledge of operators, as the crucial physicochemical effect of polymerization kinetics has rarely been quantitatively investigated. In this study, the Raman spectroscopy is used for studying the polymerization kinetics of n-butyl-cyanoacrylate-based glues mixed with an iodized oil. To simulate the polymerization process during embolization, glue–oil mixtures upon contact with a protein ionic solution mimicking blood plasma are manually constructed and their polymerization kinetics are systematically characterized by Raman spectroscopy. The results demonstrate the feasibility of Raman spectroscopy in the characterization of polymerization kinetics of cyanoacrylate-based embolic glues. The polymerization process of cyanoacrylate-based mixtures consists of a fast polymerization phase followed by a slow phase. The propagation velocity and polymerization time primarily depend on the glue concentrations. The commonly used 50% mixture polymerizes 1 mm over ∼21.8 s, while it takes ∼51 min to extend to 5 mm. The results provide essential information for interventional radiologists to help them understand the polymerization kinetics of embolic glues and thus regulate the polymerization rate for effective embolization.

Endovascular Use of Cyanoacrylate-Lipiodol Mixture for Peripheral Embolization: Properties, Techniques, Pitfalls, and Applications

Endovascular embolization agents are particles and fluids that can be released into the bloodstream through a catheter to mechanically and/or biologically occlude a target vessel, either temporarily or permanently. Vascular embolization agents are available as solids, liquids, and suspensions. Although liquid adhesives (glues) have been used as embolic agents for decades, experience with them for peripheral applications is generally limited. Cyanoacrylates are the main liquid adhesives used for endovascular interventions and have a major role in managing vascular abnormalities, bleeding, and many vascular diseases. They can only be injected as a mixture with ethiodized oil, which provides radiopacity and modulates the polymerization rate. This review describes the characteristics, properties, mechanisms of action, modalities of use, and indications of the cyanoacrylate-Lipiodol® combination for peripheral embolization.

Acenaphthoquinoxaline Derivatives as Dental Photoinitiators of Acrylates Polymerization

A series of dyes based on the acenaphthoquinoxaline skeleton was synthesized. Their structure was modified by introducing electron-withdrawing and electron-donating groups, increasing the number of conjugated double bonds and the number and position of nitrogen atoms, as well as the arrangement of aromatic rings (linear or angular). The dyes were investigated as a component in the photoinitiating systems of radical polymerization for a potential application in dentistry. They acted as the primary absorber of visible light and the acceptor of an electron, which was generated from a second component being an electron donor. Thus, the radicals were generated by the photoinduced intermolecular electron transfer (PET) process. Electron donors used differed in the type of heteroatom, i.e., O, S and N and the number and position of methoxy substituents. To test the ability to initiate the polymerization reaction by photoinduced hydrogen atom transfer, we used 2-mercaptobenzoxazole as a co-initiator. The effectiveness of the photoinitiating systems clearly depends on both the modified acenaphthoquinocaline structure and the type of co-initiator. The lower amount of heat released during the chain reaction and the polymerization rate comparable to this achieved for the photoinitiator traditionally used in dentistry (camphorquinone) indicates that the studied dyes may be valuable in this field.

Self-Initiated Butyl Acrylate Polymerizations in Bulk and in Solution Monitored By In-Line Techniques

High-temperature acrylate polymerizations are technically relevant, but yet not fully understood. In particular the mechanism and the kinetics of the thermal self-initiation is a topic of current research. To obtain more detailed information the conversion dependence of the polymerization rate, rbr, is determined via in-line DSC and FT-NIR spectroscopy for reactions in bulk and in solution at temperatures ranging from 80 to 160 °C. Solution polymerizations revealed that dioxane is associated with the highest rbr, while aromatic solvents result in the lowest values of rbr. Interestingly, rbr for polymerizations in solution with dioxane depends on the actual monomer concentration at a given time in the system, but is not depending on the initial monomer concentration. The overall rate of polymerization in bulk and in solution is well represented by an equation with three or four parameters, respectively, being estimated by multiple linear regression and the temperature as additional parameter.

Adhesive Resins with High Shelf-Life Stability Based on Tetra Unsaturated Monomers with Tertiary Amines Moieties

This work reports the use of two monomers with two tertiary amines and four methacrylic (TTME) or acrylic (TTAC) terminal groups as co-initiators in the formulation of experimental resin adhesive systems. Both monomers were characterized by FT-IR and 1H NMR spectroscopies. The control adhesive was formulated with BisGMA, TEGDMA, HEMA, and the binary system CQ-EDAB as a photo-initiator system. For the experimental adhesives, the EDAB was completely replaced for the TTME or the TTAC monomers. The adhesives formulated with TTME or TTAC monomers achieved double bond conversion values close to 75%. Regarding the polymerization rate, materials formulated with TTME or TTAC achieved lower values than the material formulated with EDAB, giving them high shelf-life stability. The degree of conversion after shelf simulation was only reduced for the EDAB material. Ultimate tensile strength, translucency parameter, and micro-tensile bond strength to dentin were similar for control and experimental adhesive resins. Due to their characteristics, TTME and TTAC monomers are potentially useful in the formulation of photopolymerizable resins for dental use with high shelf-life stability.

Acrylic plant oil-based monomers with high content of oleic acid esters

New acrylic monomers were obtained via transesterification of olive, canola, and high-oleic soybean oils by N-hydroxyethylacrylamide. The kinetic features of homopolymerization of these monomers were studied and the influence of linoleic (C18: 2) and linolenic (C18: 3) acid esters on the polymerization rate and the molecular weight of homopolymers were compared. It was found that the chain transfer and propagation rate constants increase in monomer’s range: olive (CM = 0.016) <high-oleic soybean (CM = 0.018) <canola (CM = 0.025). Features of homopolymerization are associated with varying degrees of unsaturation of fatty acid fragments.

Spontaneous polarization and cell guidance on asymmetric nanotopography

Asymmetric nanotopography with sub-cellular dimensions has recently been demonstrated to be able to provide a unidirectional bias in the migration of cells. The details of this guidance depend both on the type of cell studied and the design of the nanotopography. This behavior is not yet well understood, so there is a pressing need for a predictive description of cell migration on such nanotopography that captures both the initiation of migration and the manner in which cell migration evolves. Here, we employ a three-dimensional, physics-based model to study cell guidance on asymmetric nanosawteeth. In agreement with experimental data, our model predicts that asymmetric sawteeth lead both to spontaneous motion and changes in motion phenotypes. Our model demonstrates that asymmetric nanosawteeth induce a unidirectional bias in guidance direction that is dependent upon the actin polymerization rate and the sawtooth dimensions. Motivated by this model, an analysis of previously reported experimental data indicates that the degree of guidance by asymmetric nanosawteeth increases with the cell velocity.