This paper describes the synthesis, crystal structure, and physicomechanical properties of a biobased polyester prepared from 2,5-furandicarboxylic acid (FDCA) and 1,4-butanediol. Melt-polycondensation experiments were conducted by a two-stage polymerization using titanium tetraisopropoxide (Ti[OiPr] 4 ) as a catalyst. Polymerization conditions (catalyst concentration, reaction time and second stage reaction temperature) were varied to optimize poly(butylene-FDCA), PBF, and molecular weight. A series of PBFs with different M w were characterized by DSC, TGA, DMTA, X-ray diffraction and tensile testing. Influence of molecular weight and melting/ crystallization enthalpy on PBF material tensile properties was explored. Cold-drawing tensile tests at room temperature for PBF with M w 16K to 27K showed a brittle-to-ductile transition. When M w reaches 38K, the Young modulus of PBF remains above 900 MPa, and the elongation at break increases to above 1000%. The mechanical properties, thermal properties and crystal structures of PBF were similar to petroleum derived poly(butylenes-terephthalate), PBT. Fiber diagrams of uniaxially stretched PBF films were collected, indexed, and the unit cell was determined as triclinic (a = 4.78(3) Å, b = 6.03(5) Å, c = 12.3(1) Å, α = 110.1(2)°, β = 121.1(3)°, γ = 100.6(2)°). A crystal structure was derived from this data and final atomic coordinates are reported. We concluded that there is a close similarity of the PBF structure to PBT αand β-forms.

Image-guided combined chemo-thermal therapy assists in optimizing treatment time, enhancing therapeutic efficiency, and circumventing side effects. In the present study, we developed a chemo-photothermal theranostic platform based on polydopamine (PDA)-coated gold nanorods (GNRs). The PDA coating was thin; however, it significantly suppressed the cytotoxicity of the cetyltrimethylammonium bromide template and allowed high cisplatin loading efficiency, arginine-glycine-aspartic acid (RGD) peptide (c(RGDyC)) conjugation, and chelator-free iodine-125 labeling (RGD-IPt-PDA@GNRs). While loaded cisplatin was released in a pH-sensitive manner, labeled I was outstandingly stable under biological conditions. RGD-IPt-PDA@GNRs had a high specificity for αvβ integrin, and consequently, they could selectively accumulate in tumors, as revealed by single photon emission computed tomography/CT imaging, and in target tumor angiogenic vessels, as shown by high-resolution photoacoustic imaging. As RGD-IPt-PDA@GNRs targets tumor angiogenesis, it is a highly potent tumor therapy. Combined chemo-photothermal therapy with probes could thoroughly ablate tumors and inhibit tumor relapse via a synergistic antitumor effect. Our studies demonstrated that RGD-IPt-PDA@GNRs is a robust platform for image-guided, chemo-thermal tumor therapy with outstanding synergistic tumor killing and relapse inhibition effects.

This Article describes the synthesis and physicomechanical properties of bioplastics prepared from methyl ω-hydroxytetradecanoic acid (Me-ω-OHC14), a new monomer available by a fermentation process using an engineered Candida tropicalis strain. Melt-condensation experiments were conducted using titanium tetraisopropoxide (Ti[OiPr](4)) as a catalyst in a two-stage polymerization (2 h at 200 °C under N(2), 4 h at 220 °C under 0.1 mmHg). Poly(ω-hydroxytetradecanoate), P(ω-OHC14), M(w), determined by SEC-MALLS, increased from 53K to 110K as the Ti(OiPr)(4) concentration increased from 50 to 300 ppm. By varying the polymerization conditions (catalyst concentration, reaction time, second-stage reaction temperature) a series of P(ω-OHC14) samples were prepared with M(w) values from 53K to 140K. The synthesized polyesters with M(w) ranging from 53K to 140K were subjected to characterization by DSC, TGA, DMTA, and tensile testing. Influences of P(ω-OHC14) molecular weight, melting point, and enthalpies of melting/crystallization on material tensile properties were explored. Cold-drawing tensile tests at room temperature for P(ω-OHC14) with M(w) 53K-78K showed a brittle-to-ductile transition. In contrast, P(ω-OHC14) with M(w) 53K undergoes brittle fracture. Increasing P(ω-OHC14) M(w) above 78K resulted in a strain-hardening phenomena and tough properties with elongation at break ~700% and true tensile strength of ~50 MPa. Comparisons between high density polyethylene and P(ω-OHC14) mechanical and thermal properties as a function of their respective molecular weights are discussed.

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α-Chymotrypsin catalyzed oligomerization of the "dipeptide lego" KL-ethyl ester (OEt) in aqueous media triggers a rapid sol-gel transition due to formation of alternating (KL)x. Resulting mixed chain oligomers, at alkaline pH, self-assemble into β-sheets. Thereafter, intermolecular backbone hydrogen bonding between peptides causes formation of physically entangled nanofibrillar networks.

A green manufacturing technique, reactive extrusion (REx), was employed to improve the mechanical properties of polylactide (PLA). To achieve this goal, a fully biosourced PLA based polymer blend was conceived by incorporating small quantities of poly(ω-hydroxytetradecanoic acid) (PC14). PLA/PC14 blends were compatibilized by transesterification reactions promoted by 200 ppm titanium tetrabutoxide (Ti(OBu)4) during REx. REx for 15 min at 150 rpm and 200 °C resulted in enhanced blend mechanical properties while minimizing losses in PLA molecular weight. SEM analysis of the resulting compatibilized phase-separated blends showed good adhesion between dispersed PC14 phases within the continuous PLA phase. Direct evidence for in situ synthesis of PLA-b-PC14 copolymers was obtained by HMBC and HSQC NMR experiments. The size of the dispersed phase was tuned by the screw speed to "tailor" the blend morphology. In the presence of 200 ppm Ti(OBu)4, inclusion of only 5% PC14 increased the elongation at break of PLA from 3 to 140% with only a slight decrease in the tensile modulus (3200 to 2900 MPa). Furthermore, PLA's impact strength was increased by 2.4× that of neat PLA for 20% PC14 blends prepared by REx. Blends of PLA and PC14 are expected to expand the potential uses of PLA-based materials.

Gold nanoparticles (AuNPs) have recently garnered great interest as potential radiosensitizers in tumor therapy. However, major challenges facing their application in this regard are further enhancement of tumor accumulation of the particles in addition to enhanced permeability retention (EPR) effect and an understanding of the optimal particle size and time for applying radiotherapy after the particle administration. In this study, we fabricated novel cyclic c(RGDyC)-peptide-conjugated, Gd- and 99 mTc-labeled AuNPs (RGD@AuNPs-Gd99 mTc) probes with different sizes (29, 51, and 80 nm) and evaluated their potential as radiosensitization therapy both in vitro and in vivo. We found that these probes have a high specificity for αvβ3 integrin positive cells, which resulted in their high cellular uptake and thereby enhanced radiosensitization. Imaging in vivo with MRI and SPECT/CT directly showed that the RGD@AuNPs-Gd99 mTc probes specifically target tumors and exhibit greater accumulation within tumors than the RAD@AuNPs-Gd99 mTc probes. Interestingly, we found that the 80 nm RGD@AuNPs-Gd99 mTc probes exhibit the greatest effects in vitro; however, the 29 nm RGD@AuNPs-Gd99 mTc probes were clearly most efficient in vivo. As a result, radiotherapy of tumors with the 29 nm probe was the most potent. Our study demonstrates that RGD@AuNPs-Gd99 mTc probes are highly useful radiosensitizers capable of guiding and enhancing radiation therapy of tumors.