Effects of environmental parameters and composition of poly(2-hydroxyethyl methacrylate)-graft-polyamine copolymers on the retention of rat lymphocyte subpopulations (B- and T-cells)

Retention behavior of rat lymphocyte subpopulations (B- and T-cells) was investigated on poly(2-hydroxyethyl methacrylate)-graft-polyamine (HA) copolymers with various copolymer compositions. Separation mechanism of B- and T-cells was then evaluated by focusing on several parameters, such as pH, temperature, and ionic strength. The interaction of lymphocytes with HA surfaces was mainly through the electrostatic force from their retention profile at varying ionic strengths of the medium. Temperature also has a crucial effect on the response of lymphocytes toward pH-induced phase transition of polyamine grafts at the polymer interface with aqueous milieu. At 4°C, both B- and T-cells showed minimal retention on HA surfaces at pH 8. At this pH, polyamine grafts existed in a compact conformation with a low degree of protonation. However, at pHs below 8, at which polyamine grafts existed in extended conformation, the resolution of B- and T-cells was achieved. In contrast, at 23°C, the phase transition of polyamine grafts significantly influenced T-cell retention, resulting in a decrease in the retention of T-cells on HA with polyamine in a compact conformation. Consequently, preferential retention of B-cells was achieved under this condition. The polyamine content was found to be another important factor affecting the retention behavior of lymphocyte subpopulations. On HA copolymers with low polyamine content (HA7, HA10), conformational transition of polyamine grafts showed a significant influence for B-cell retention, although the influence decreased with increasing polyamine content. From the study estimating the effect of neuraminidase treatment of lymphocytes on their retention to HA surfaces, sialic acid residues on the plasma membrane surface of lymphocytes are suggested as feasible anionic sites showing electrostatic interaction with polyamine grafts.     

The role of protonation and conformational transition of polyamine grafts in platelet retention to polyamine-graft-PHEMA copolymer surfaces

Blood platelet retention on polyamine-graft-poly(2-hydroxyethyl methacrylate) (PHEMA) copolymer (HA) surface was investigated, focusing on pH and ionic strength of the surrounding medium to elucidate the nature of ionic interaction between platelets and HA copolymer surfaces. The conformational transition of polyamine graft chain in response to the protonation degree of amino groups was demonstrated to be an important factor influencing platelet retention on HA surfaces. When the polyamine graft chain exists in an extended conformation, protonated amino groups distribute from the matrix interface into the aqueous interior, resulting in the effective ionic interaction with platelets to increase their retention on HA copolymer surfaces. The number of protonated amino groups in polyamine portions crucially affected platelet retention. Worth noticing is that an introduction of a small but definite amount of cationic sites on the polymer surface led to significantly minimized platelet retention. It is considered that the surface property of PHEMA was drastically changed to a non-adhesive surface by introducing a small amount of protonated amino groups.     

Cell-attachment activities of surface immobilized oligopeptides RGD,RGDS, RGDV,RGDT, and YIGSR toward five cell lines

Tetrapeptides, Arg-Gly-Asp-Ser (RGDS), Arg-Gly-Asp-Val (RGDV), and Arg-Gly-Asp-Thr (RGDT), respectively, appearing in the cell-attachment domains of fibronectin, vitronectin, and collagen, and pentapeptide Tyr-Ile-Gly-Ser-Arg (YIGSR) appearing in B1 chain of laminin, were synthesized by liquid-phase procedure. Bioactivities of RGD, RGDX (X=S, V and T), YIGSR, and YIGSR-NH₂ as cell recognition determinants were investigated by cell-attachment test using these oligopeptides immobilized to ethylene-acrylic acid copolymer (PEA) film. The cell lines used were A431, NRK, CHO-K1, HeLa.S3, and RLC-16 cells. It was found that the residue X in RGDX plays an important role for cell-attachment activity of RGDX, and, regarding YIGSR, introduction of NH₂ residue at the C-terminal of the pentapeptide enhances the cell-attachment activity.     

Polystyrene‐block‐Polyisoprene Diblock‐Copolymer Micelles: Coupled Pressure and Temperature Effects

The structural changes of diblock‐copolymer micelles under pressures from 200 to 16 000 psi are investigated using small‐angle neutron scattering (SANS). Asymmetric polystyrene‐block‐polyisoprene (PS–PI) diblock copolymers are dissolved in decane, a selective solvent for PI, to form spherical micelles with a core of PS and a corona of PI. The micellar solutions are put under pressure at temperatures of 25 to 60 °C. At room temperature, elevating the pressure from 200 to 16 000 psi has no effect on the size of the micelles. While the micellar solutions remain stable, instantaneous association of micelles is detected. In contrast to micelles at atmospheric pressure, increasing the temperature at elevated pressures does not lead to dissociation of micelles; instead, the micelles aggregate and evolve into sheet‐like structures, reminiscent of a macroscopic phase separation. Furthermore, higher pressures lead to a smaller temperature range in which shape transitions take place.

     

Tandem Action of SNS–Cr and CGC–Ti in Preparation of Ethylene–1‐Hexene Copolymers from Ethylene Feedstock

Ethylene–1‐hexene copolymer materials, ranging from semicrystalline linear low‐density poly­ethylene (LLDPE) to completely amorphous polyethylenes (PEs), are prepared from ethylene alone in a single reactor by the tandem polymerization of bis(2‐dodecylsulfanyl‐ethyl)amine–CrCl₃ (SNS–Cr) and (N‐tert‐butylamido) (tetramethylcyclopentadienyl)–titanium dichloride (CGC–Ti) at 75 °C and under atmospheric pressure. The polymerization activities are on the order of 10⁵–10⁶ g (mol Ti)^?1 h^?1. 1‐Hexene incorporation in the resulting copolymers can be adjusted by varying the Cr–Ti molar ratio and/or applying a short period of pre‐trimerization. Copolymers with high 1‐hexene incorporation up to 15 mol% are obtained. Few vinyl and vinylene chain ends are detected by ¹³C NMR, suggesting that 1‐hexene does not act as a chain‐transfer agent. Narrow molecular‐weight distributions with polydispersities from 1.9 to 2.6 are obtained, characteristic of a single‐active‐site nature of the catalyst system.

     

Long-term effects of various cleaning methods on polypropylene/ethylene copolymer retainer material

Objectives:To evaluate long-term light transmittance, surface roughness, and flexural modulus of polypropylene/ethylene copolymer retainer material after exposure to different cleaning methods.Materials and Methods:Standardized polypropylene/ethylene copolymer retainer specimens (n = 70, 50.8 mm × 12.7 mm × 1.0 mm) were subjected to seven chemical cleaning solutions: Invisalign cleaning crystals, Retainer Brite, Polident, Listerine mouthwash, 2.5% acetic acid, 0.6% NaClO, and 3% H₂O₂ for 6 months. The specimens were exposed to the different solutions twice a week for 15 minutes or according to manufacturer''s instructions, then stored in artificial saliva at 37°C. Another group of specimens (n = 10) were brushed with a standardized toothbrushing machine for 2 minutes twice a week. At baseline and 6 months, light transmittance, surface roughness, and flexural modulus of the specimens were quantified using spectrophotometry, profilometry and three-point bend testing, respectively. Qualitative analysis was performed using a scanning electron microscope (SEM). Statistical analyses were performed at a significance level of .05.Results:The results showed that light transmittance decreased significantly from baseline for all cleaning methods at 6 months. For an individual method, no significant differences were observed between specimens at baseline and 6 months in surface roughness and flexural modulus. No discernible differences in surface features were observed on SEM images.Conclusions:The results indicate that different cleaning methods affect the long-term light transmittance of the studied polypropylene/ethylene copolymer retainer material. However, for an individual cleaning method, no significant differences were shown for surface roughness or flexural modulus values at 6-months compared to baseline.     

Unidirectionally aligned line patterns driven by entropic effects on faceted surfaces

A simple, versatile approach to the directed self-assembly of block copolymers into a macroscopic array of unidirectionally aligned cylindrical microdomains on reconstructed faceted single crystal surfaces or on flexible, inexpensive polymeric replicas was discovered. High fidelity transfer of the line pattern generated from the microdomains to a master mold is also shown. A single-grained line patterns over arbitrarily large surface areas without the use of top-down techniques is demonstrated, which has an order parameter typically in excess of 0.97 and a slope error of 1.1 deg. This degree of perfection, produced in a short time period, has yet to be achieved by any other methods. The exceptional alignment arises from entropic penalties of chain packing in the facets coupled with the bending modulus of the cylindrical microdomains. This is shown, theoretically, to be the lowest energy state. The atomic crystalline ordering of the substrate is transferred, over multiple length scales, to the block copolymer microdomains, opening avenues to large-scale roll-to-roll type and nanoimprint processing of perfectly patterned surfaces and as templates and scaffolds for magnetic storage media, polarizing devices, and nanowire arrays.     

Docetaxel-loaded nanoparticles based on star-shaped mannitol-core PLGA-TPGS diblock copolymer for breast cancer therapy

A star-shaped biodegradable polymer, mannitol-core poly(d,l-lactide-co-glycolide)-d-α-tocopheryl polyethylene glycol 1000 succinate (M-PLGA-TPGS), was synthesized in order to provide a novel nanoformulation for breast cancer chemotherapy. This novel copolymer was prepared by a core-first approach via three stages of chemical reaction, and was characterized by nuclear magnetic resonance, gel permeation chromatography and thermogravimetric analysis. The docetaxel-loaded M-PLGA-TPGS nanoparticles (NPs), prepared by a modified nanoprecipitation method, were observed to be near-spherical shape with narrow size distribution. Confocal laser scanning microscopy showed that the uptake level of M-PLGA-TPGS NPs was higher than that of PLGA NPs and PLGA-TPGS NPs in MCF-7 cells. A significantly higher level of cytotoxicity was achieved with docetaxel-loaded M-PLGA-TPGS NPs than with commercial Taxotere®, docetaxel-loaded PLGA-TPGS and PLGA NPs. Examination of the drug loading and encapsulation efficiency proved that star-shaped M-PLGA-TPGS could carry higher levels of drug than linear polymer. The in vivo experiment showed docetaxel-loaded M-PLGA-TPGS NPs to have the highest anti-tumor efficacy. In conclusion, the star-like M-PLGA-TPGS copolymer shows potential as a promising drug-loaded biomaterial that can be applied in developing novel nanoformulations for breast cancer therapy.     

Shear bond strength of an autopolymerizing repair resin to injection-molded thermoplastic denture base resins

Abstract

Objective. This study investigated the shear bond strength of an autopolymerizing repair resin to injection-molded thermoplastic denture base resins. Materials and methods. Four injection-molded thermoplastic resins (two polyamides, a polyethylene terephthalate copolymer and a polycarbonate) were used in this study. The specimens were divided into eight groups according to the type of surface treatment given: (1) no treatment, (2) air abrasion with alumina, (3) dichloromethane, (4) ethyl acetate, (5) 4-META/MMA-TBB resin, (6) alumina and 4-META/MMA-TBB resin, (7) tribochemical silica coating or (8) tribochemical silica coating and 4-META/MMA-TBB resin. Half of the specimens in groups 1, 5, 6 and 8 were thermocycled for 10,000 cycles in water between 5–55°C with a dwell time of 1 min at each temperature. The shear bond strengths were determined. Results. The shear bond strengths to the two polyamides treated with alumina, dichloromethane and ethyl acetate and no treatment were very low. The greatest post-thermocycling bond strengths to polyamides were recorded for the specimens treated with tribochemical silica coating and 4-META/MMA-TBB resin (PA12: 16.4 MPa, PACM12: 17.5 MPa). The greatest post-thermocycling bond strengths to polyethylene terephthalate copolymer and polycarbonate were recorded for the treatment with alumina and 4-META/MMA-TBB resin (22.7 MPa, 20.8 MPa). Conclusion. Polyamide was exceedingly difficult to bond to an autopolymerizing repair resin; the shear bond strength improved using tribochemical silica coating followed by the application of 4-META/MMA-TBB resin. Both polyethylene terephthalate copolymer and polycarbonate were originally easy to bond to an autopolymerizing repair resin. However, with 4-META/MMA-TBB resin, the bond was more secure.     

Subclassification and Treatment Results of Ethanol Embolotherapy of Type II Arteriovenous Malformations of the Extremity and Body

PurposeTo evaluate the safety and efficacy of ethanol and coil embolization of type II arteriovenous malformation (AVM) according to a new subtype classification.Materials and MethodsEighty-four type II AVMs in the body or extremity of 79 patients who underwent AVM treatment from 1996 to 2017 were retrospectively subclassified according to the angiographic morphology of the draining vein as type IIa (arterioles shunt to focal segment of single draining vein), type IIb (arterioles shunt to venous sac with multiple draining veins), and type IIc (arterioles shunt along long segment of draining vein). Coil and ethanol embolization of the focal or long segment of the draining vein or the venous sac was performed with direct puncture or transvenous approach according to subtype. Treatment outcomes, number of treatment sessions, and complications were analyzed.ResultsAVM cure (ie, complete embolization) rates were 95%, 76%, and 65% in types IIa, IIb, and IIc AVMs, respectively. The cure rate of type IIa AVMs was significantly better than that of type IIc AVMs (P = .015). Median numbers of treatment sessions were 1 in types IIa and IIb AVMs and 2.5 in type IIc AVMs, with a significant difference between type IIc and the other 2 types (P < .05). Minor complications occurred in 20% of patents and major complications occurred in 7%.ConclusionsThe cure rate of type IIa AVMs was significantly better than that of type IIc AVMs, which also required significantly more treatment sessions than the other 2 types.