RAFT-derived polymer-drug conjugates: poly(hydroxypropyl methacrylamide) (HPMA)-7-ethyl-10-hydroxycamptothecin (SN-38) conjugates

A series of well‐defined polymer–drug conjugates were prepared in order to modify the physical properties of a known cytotoxic drug, 7‐ethyl‐10‐hydroxycamptothecin (SN‐38), the active metabolite of irinotecan (CPT‐11). Reversible addition–fragmentation chain transfer (RAFT) polymerisation was used to covalently and site‐specifically append a defined N‐(2‐hydroxypropyl)methacrylamide (HPMA) polymer to SN‐38 using a graft‐from process. These poly‐HPMA–SN‐38 conjugates displayed excellent aqueous solubility and stability, whilst retaining the cytotoxic activity of the parent SN‐38. In vitro co‐culture assays containing both cancer and noncancer cell lines demonstrated the specificity of RAFT‐derived poly‐HPMA–SN‐38 conjugates for cancerous cells. The concept of post‐optimisation modification of small‐molecule drugs through a graft‐from polymer conjugation method is introduced.     

Effect of montmorillonite clay addition on the morphological and physical properties of Jatropha curcas L. and Glycine max L. protein concentrate films

Protein concentrates from jatropha (JPC) and soy seeds (SPC) were obtained by solubilization and acid precipitation of proteins. JPC and SPC films were prepared by the casting method, using two different montmorillonite (MMT) clay concentrations and plasticized with glycerol. Film properties were evaluated by scanning electron microscopy, transmission electron microscopy, X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis, tensile properties, water retention, and water vapor transmission rate (WVRT). Typical tactoid microcomposite structures were found to be heterogeneously dispersed in the films containing MMT. A small XRD peak was found in films with MMT. Slight improvements in thermal stability and tensile strength were observed in the films with MMT. Reductions in water retention and WVRT were obtained when MMT was added into the films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44459.     

The Synthesis of Ba‐ and Fe‐ Substituted CsAlSi2O6 Pollucites

Barium‐substituted CsAlSi₂O₆ pollucites, Cs_xBa_(1?x)/2AlSi₂O₆, and barium‐ and iron‐substituted pollucites, Cs_xBa_(1?x)/2Al_xFe_1?xSi₂O₆ and Cs_xBa_1?xAl_xFe_1?xSi₂O₆ were synthesized with 1 ≥ x≥ 0.7 using a hydrothermal synthesis procedure. Rietveld analysis of X‐ray diffraction data confirmed the substitution of Ba for Cs and Fe for Al, respectively. The crystallographic analysis also describes the effects of three different types of pollucite substitutions on the pollucite unit cell: Ba²⁺ for Cs¹⁺ cation results in little effect on cell dimensions, intermediate concentrations of Ba²⁺ and Fe³⁺ substitution result in net minor expansion due to Fe³⁺ addition, and large Ba and Fe substitutions result in overall framework contraction. Elemental analysis combined with microscopy further supports the phase purity of these new phases. These materials can be used to study the stability of CsAlSi₂O₆ as a durable ceramic waste form, which could accommodate with time Cs and its decay product, Ba. Furthermore, success in iron substitution for aluminum into the pollucite lattice predicts that redox charge compensation for Cs cation decay is possible.     

Reactive and stimuli-responsive maleic anhydride containing macromers – multi-functional cross-linkers and building blocks for hydrogel fabrication

Macromers with functional groups that allow for chemical derivatization, polymerization reactions or impart specific physico-chemical properties are functional building blocks for polymeric systems used in different biomedical applications. With this motivation, a series of oligomeric macromers was synthesized by free radical polymerization of maleic anhydride (MA) with N-isopropylacrylamide (NiPAAm) and pentaerythritol diacrylate monostearate (PEDAS). This chemical design provides anhydride groups for effective reactivity of the macromers with amines and other nucleophiles, copolymerized NiPAAm for temperature responsiveness and lipophilic stearate domains for increased hydrogel stability. Macromers were synthesized with different MA co-monomer feeds and oligomeric molecules (Mn below 5000 Da) were obtained with MA contents between 7% and 27% as determined by titration. The fraction of chemically intact anhydrides was calculated to range from 75% to 80%. The ability of the macromers to cross-link di- or oligovalent amines as a function of MA content was investigated rheologically. It was also demonstrated that monovalent amines, e.g. aminofluorescein, could be grafted to the macromer chain utilizing only a fraction of the anhydride functionalities. The derivatized macromers could still participate in cross-linking reactions due to the remaining anhydrides. Temperature sensitivity was shown for aqueous solutions of macromers with fully dissociated anhydride groups. The solutions were additionally responsive to changes in calcium ion concentration and pH. Extracts from macromer cross-linked polyether hydrogels showed no toxicity on L929 fibroblasts.The macromers have perspective as biocompatible cross-linkers for hydrogel fabrication from various biomacromolecules with the opportunity to decorate the gels with monoamine molecules that alter the biological or physico-chemical properties.     

Effects of annealing on performances of 1.3-μm InAs-InGaAs-GaAs quantum dot electroabsorption modulators

In this work, we investigated the effects of quantum dot (QD) annealing (as-grown, 600°C-annealed, and 750°C-annealed) on the preliminary performances of 1.3-μm InAs-InGaAs-GaAs quantum dot electroabsorption modulators (QD-EAMs). Both extinction ratio and insertion loss were found to vary inversely with the annealing temperature. Most importantly, the 3-dB response of the 750°C-annealed lumped-element QD-EAM was found to be 1.6 GHz at zero reverse bias voltage - the lowest reverse bias voltage reported. We believe that this work will be beneficial to researchers working on on-chip integration of QD-EAMs with other devices since energy consumption will be an important consideration.     

Thermochemistry and Aqueous Durability of Ternary Glass Forming Ba-Titanosilicates: Fresnoite (Ba2TiSi2O8) and Ba-Titanite (BaTiSiO5)

Barium titanosilicates are possible oxide forms for the immobilization of short-lived fission products in radioactive waste. Ba₂TiSi₂O₈ (fresnoite) and BaTiSiO₅ (Ba-titanite) samples were prepared by a solid-state synthesis. The enthalpies of formation of Ba₂TiSi₂O₈ crystal and glass at 25°C and of BaTiSiO₅ glass were obtained from drop solution calorimetry in a molten lead borate (2PbO–B₂O₃) solvent at 701°C. The enthalpy of formation for fresnoite composition samples from constituent oxides was exothermic and became more exothermic with increasing crystallinity. Differential scanning calorimetry revealed that the crystallization rate of the fresnoite glasses increased with increasing devitrification. A modified Product Consistency Test-Procedure B (PCT-B) was used to collect solubility data on the fresnoite and titanate phases. The tests suggest that both glassy and crystalline fresnoite exhibit favorable aqueous stability and should be explored further as radioactive waste forms for long-term storage.     

Torrefied agro-industrial residue as filler in natural rubber compounds

This study explored the feasibility of using torrefied biomass as a reinforcing filler in natural rubber compounds. Carbon black was then replaced with the torrefied biomass in elastomer formulations for concentrations varying from 0% to 100% (60 parts per hundred rubber or phr total). Their influence on the curing process, dynamic properties, and mechanical properties was investigated. Results were compared with the properties of vulcanizates containing solely carbon black fillers. Time to cure (t₉₀) for compounds with torrefied biomass fillers increased, while filler-filler interactions (ΔG') decreased, compared to carbon black controls. At low strains, the tan δ values of the torrefied fillers vulcanizates were similar to the controls. Incorporation of torrefied biomass into natural rubber decreased compound tensile strength and modulus but increased elongation. Replacement with torrefied fillers resulted in a weaker filler network in the matrix. Still, results showed that moderate substitution concentrations (~20 phr) could be feasible for some natural rubber applications.