Emerging Design Principle of Near-Infrared Upconversion Sensitizer Based on Mitochondria-Targeted Organic Dye for Enhanced Photodynamic Therapy

Upconversion luminescent (UCL) triggered photodynamic therapy (PDT) affords superior outcome for cancer treatment. However, conventional UCL materials which all work by a multiphoton absorption (MPA) process inevitably need extremely high power density far over the maximum permissible exposure (MPE) to laser. Here, a one-photon absorption molecular upconversion sensitizer Cy5.5-Br based on frequency upconversion luminescent (FUCL) is designed for PDT. The unusual super heavy atom effect (SHAE) in Cy5.5-Br strongly enhances its spin-orbit coupling (0.23 cm⁻¹), triplet quantum yield (11.1 %) and triplet state lifetime (18.8 μs) while the potential hot-band absorption of Cy5.5-Br is well maintained. Importantly, Cy5.5-Br can efficiently target the tumour site and kill cancer cells by destroying mitochondria under a biosafety MPE to 808 nm laser. The photostability and antitumor results are obviously superior to that of a Stokes process. This work provides a design criterion for FUCL dyes to realize effective PDT upon a biosafety optical density, possibly bringing more clinical benefits than conventional MPA materials.     

Thermal-oxidative degradation of high-amylose corn starch

Thermal oxidation degradation of high-amylose (80 %) cornstarch has been studied using thermogravimetry analyser coupled to Fourier transform infrared spectroscopy (TG-FTIR). The linear structure of amylose provides a modal material to understand how the starch microstructure affects on the decomposition mechanisms. Kinetics of the thermal oxidation has been studied using different methods. It is found that the thermal oxidation degradation is more complex than thermal degradation, thermal oxidation degradation kinetics of the starch can be interpreted in terms of multi-step degradation mechanism, the activation energies obtain from Flynn–Wall–Ozawa (F–W–O) method and modified Coats–Redfern method are in good agreement. TG-FTIR and FTIR results confirm that the thermal oxidation mechanism of starch is a process containing long chain scission and glowing combustion.     

Synthesis of Cationic Dumbbell-shaped Fullerene Nanostructures as Potential Photodynamic Sensitizers

A design of novel hydrophilic tetracationic dumbbell-shaped [60]fullerene nanostructures was made by balancing the hydrophilicity and hydrophobicity characteristics of the fullerene adduct for their potential application as photodynamic sensitizers in the PDT treatment. A sequential protection-deprotection reaction pathway was applied for the functional differentiation between primary and secondary amine moieties of pentaethylene hexamine. Synthesis of the target molecule involves two key steps of unsymmetrical esterification and amidation of malonic acid and subsequent fullerenation. The synthetic strategy was accomplished using mild reaction conditions in the intermediate molecule preparation and led a moderate overall product yield.     

Conversion of Penicillin G Into Cephalexin Employing a Second-Order Asymmetric Transformation

2′5- and 2′R- and S- cephalexin, (5b) and (5c) respectively, both available in six stages from penicillin G, have each been converted to the more useful 2′R-isomer (5a) by a base catalysed epimerization and selective crystallization process involving the N-nitrosoimidazolidinyl derivatives (7).     

Segmented block copolyesters using click chemistry

Copper(I) catalyzed azide‐alkyne 1,3‐Huisgen cycloaddition reaction afforded the synthesis of triazole‐containing polyesters and segmented block copolyesters at moderate temperatures. Triazole‐containing homopolyesters exhibited significantly increased (～40 °C) glass transition temperatures (T_g) relative to high temperature, melt synthesis of polyesters with analogous structures. Quantitative synthesis of azido‐terminated poly(propylene glycol) (PPG) allowed for the preparation of segmented polyesters, which exhibited increased solubility and mechanical ductility relative to triazole‐containing homopolyesters. Differential scanning calorimetry demonstrated a soft segment (SS) T_g near ?60 °C for the segmented polyesters, consistent with microphase separation. Tensile testing revealed Young's moduli ranging from 7 to 133 MPa as a function of hard segment (HS) content, and stress at break values approached 10 MPa for 50 wt % HS segmented click polyesters. Dynamic mechanical analysis demonstrated an increased rubbery plateau modulus with increased HS content, and the T_g's of both the SS and HS did not vary with composition, confirming microphase separation. Atomic force microscopy also indicated microphase separated and semicrystalline morphologies for the segmented click polyesters. This is the first report detailing the preparation of segmented copolyesters using click chemistry for the formation of ductile membranes with excellent thermomechanical response. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Fluorescent Carbon Dots as Cost-Effective and Facile Probes for Caffeic Acid Sensing via a Fluorescence Quenching Process

Caffeic acid (CA), a familiar color stabilizing reagent, has aroused general concern due to its uncontrolled addition, and thus the detection of CA is increasingly important. In our report, the bright carbon dots (CDs) were prepared via hydrothermal treatment with urea and citric acid act as raw material and their characteristics were discussed through X-ray diffraction (XRD), transmission electron microscopy (TEM) and so on. Impressively, the strong emission of the as-prepared CDs (Quantum Yield: 24.3%) decreased sharply upon a full reaction with the added CA. Hence, we first present an improved strategy for determining CA based upon the quenching of the strong emission of CDs. In this strategy, 0.79–100.0 µmol L^??1 caffeic acid could be simply detected, and a detection limit of 0.24 µmol L^??1 was allowed. Additionally, CA in red wine samples can be successfully detected by this method and the exploration of the quenching mechanism of the CA-CDs system was done.