Silicon analogues of the retinoid agonists TTNPB and 3-methyl-TTNPB, disila-TTNPB and disila-3-methyl-TTNPB: chemistry and biology

Twofold sila-substitution (C/Si exchange) in the saturated ring of the tetrahydronaphthalene skeleton of the retinoid agonists TTNPB (1 a) and 3-methyl-TTNPB (2 a) leads to disila-TTNPB (1 b) and disila-3-methyl-TTNPB (2 b), respectively. The silicon compounds 1 b and 2 b were synthesized in multiple steps, and their identities were established by elemental analyses, multinuclear NMR experiments, and single-crystal X-ray diffraction studies. Like TTNPB (1 a) and 3-methyl-TTNPB (2 a), the analogous silicon-based arotinoids 1 b and 2 b are strong pan-RAR agonists and display the same strong differentiation and apoptosis-inducing activity in NB4 promyelocytic leukemia cells as the parent carbon compounds. These results are in keeping with the nearly isomorphous structures of 1 a and 1 b bound to the complex of the RARbeta ligand-binding domain with the nuclear receptor (NR) box 2 peptide of the SRC-1 coactivator. The contacts within the ligand-binding pocket are identical except for helix H11, for which two turns are shifted in the disila-TTNPB (1 b) complex. This study represents the first comprehensive structure-function analysis of a carbon/silicon switch in a signaling molecule and demonstrates that silicon analogues can have the same biological functionalities and conserved structures as their parent carbon compounds, and it illustrates at the same time that silicon analogues of biologically active compounds have the potential to induce alternative allosteric effects, as in the case of helix H11, which might allow for novel options in drug design.     

Variation of clearance considering viscosity of the solution used in the reservoir and following scleral lens wear over time

Purpose

This study aims to evaluate the settling of a scleral lens and if this process is influenced by the nature of the fluid layer.

Effect of Nitrogen on Properties of Na2O–CaO–SrO–ZnO–SiO2 Glasses

Glasses in the Na₂O–CaO–SrO–ZnO–SiO₂ system have previously been investigated for suitability as a reagent in Al‐free glass polyalkenoate cements (GPCs). These materials have many properties that offer potential in orthopedics. However, their applicability has been limited, to date, because of their poor strength. This study was undertaken with the aim of increasing the mechanical properties of a series of these Zn‐based GPC glasses by doping with nitrogen to give overall compositions of: 10Na₂O–10CaO–20SrO–20ZnO–(40?3x)SiO₂–xSi₃N₄ (x is the no. of moles of Si₃N₄). The density, glass‐transition temperature, hardness, and elastic modulus of each glass were found to increase fairly linearly with nitrogen content. Indentation fracture resistance also increases with nitrogen content according to a power law relationship. These increases are consistent with the incorporation of N into the glass structure in threefold coordination with silicon resulting in extra cross‐linking of the glass network. This was confirmed using ²⁹Si MAS‐NMR which showed that an increasing number of Q² units and some Q³ units with extra bridging anions are formed as nitrogen content increases at the expense of Q¹ units. A small proportion of Zn ions are found to be in tetrahedral coordination in the base oxide glass and the proportion of these increases with the presence of nitrogen.     

Reactive compatibilization of polypropylene/polyethylene terephthalate blends

The reactive compatibilization of polypropylene/polyethylene terephthalate (PP/PET) blends by addition of glycidyl methacrylate grafted PP (PP-g-GMA) was studied. Two PP-g-GMA copolymers, containing either 0.2 or 1.2 wt% of GMA, were used as interface modifiers. These were incorporated into PP blends (with either 70 or 90 wt% PET), replacing 1/5 of PP in the system. The use of these modifiers changed the blends' tensile mechanical behavior from fragile to ductile. Blend tensile strength was improved by 10% and elongation at break showed 10 to 20-fold increases while stiffness remained constant. Scanning electron micrographs showed the PP average domain size in injection molded specimens to decrease to the micron/sub-micron size upon addition of the GMA modified resins, while the unmodified blends exhibited heterogeneous morphology comprising large lamellae 10–20 μm wide. The low-GMA graft content PP seemed slightly more efficient than the high GMA content PP in emulsifiying PP/PET blends. The GMA grafting level on PP had very limited effects on the blends' mechanical behavior in the range of GMA graft density provided by the two modified resins investigated.     

Parameters regulating interfacial and mechanical properties of short glass fiber reinforced polypropylene

The performance of thermoplastic composites is known to depend on the intrinsic properties of the two composite components, the quality of the fiber–matrix interface, and the crystalline properties of their matrix. The objective of this work is to characterize the effect of the addition of modified polypropylene (PP) and silane coupling agent on the mechanical and interfacial properties of short fiber reinforced PP composites. Differential scanning calorimetry (DSC), single fiber composite fragmentation tests (SFC), and mechanical testing are used to understand the different parameters regulating the interfacial properties of composites. No influence of the modified PP on the level of crystallinity is observed. Some differences in the size of the spherulites are observed for acrylic acid grafted PP (PP‐g‐AA). Those samples also show lower mechanical properties in spite of good interfacial interactions. Maleic anhydride grafted PP (PP‐g‐MAh) leads to better mechanical performances than PP‐g‐AA. A high MAh content PP‐g‐MAh grade with low viscosity is the best polymeric additive used in the present work. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2047–2060, 2000