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A simultaneously photo-cleavable and activatable prodrug-backboned block copolymer (BCP) micelle strategy is demonstrated. Without light treatment, the micelles stay silent and inactivated, being biocompatible to normal tissues. Concurrent chain cleavage of BCP micelles and the activation of Pt(IV) prodrug could be temporally and spatially triggered by UV or even visible light for precise anticancer drug delivery. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
Palladium-catalyzed cyanation of aryldiazonium tetrafluoroborate using acetonitrile as a non-metallic cyanide source was achieved in the presence of Ag2O under ambient air, eliminating the involvement of highly toxic CuCN used in the traditional Sandmeyer reaction, in which the CN group comes from metallic cyanides.
Chemotherapy is the most common therapeutic strategy for the treatment of unresectable hepatocellular carcinoma. However, the therapeutic efficacy is limited by the low delivery efficiency of chemotherapeutics and severe toxicity towards healthy tissues. To address these challenges, active-targeting mesoporous silica nanoparticles conjugating a platinum(iv) prodrug were developed as a therapy for liver cancer for the first time. Taking advantage of liver-targeting lactobionic acid (LA), the smart nano-carriers not only enhanced the circulation time, but also effectively concentrated at the liver tumor site. Moreover, the conjugated platinum(iv) could be reduced in the reductive tumor environment for the fast release of active platinum(ii). The novel targeting and self-responsive drug-loading system offers new prospects for liver cancer chemotherapy.
Abstract Bromocresol green (BG) was removed from an aqueous solution by solvent sublation of bromocresol green–hexadecyl‐pyridiumchlorid (HPC) complex (sublate) into 2‐octanol. The effects of many parameters, such as the amount of surfactant, airflow rates, pH, NaCl, and ethanol on the solvent sublation were studied. Different temperatures of the solvent sublation were also investigated. A ratio of surfactant to dye (1.25:1) was the most effective for the removal, with over 99% BG removed from the aqueous solution within 5 min. The removal rate was somewhat enhanced by higher airflow rates and almost independent of the volume of the organic solvent floating on the top of the aqueous column. The effects of electrolytes (e.g. NaCl) and non‐hydrophobic organics (e.g. ethanol) reduce the removal efficiency of solvent sublation. This process followed first order kinetics. A characteristic parameter, apparent activation energy of attachment of the sublate to bubbles, was estimated at a value of 1.3 kJ/mol. Furthermore, the simulation of the mathematical and experimental data was made with good results. Keywords: Solvent sublationmechanismkineticssimulation Acknowledgments This work was supported by the Natural Science Foundation of Guangdong Province (Grant No. 04300883) and the Science and Technology Program of Shenzhen (Grant No. 200502).
Abstract Alkyl‐substituted ferrocenes as ferrocene‐based burning rate (BR) catalysts in composite solid propellants have high migration tendency and strong volatility during processing and long‐time storage of the propellants. For developing low‐migratory alternatives, zinc(II) and cadmium(II) complexes, [Zn(phen) 3 ](FcTz) 2 · 9H 2 O ( 1 ), [Cd(phen) 2 (H 2 O) 2 ](FcTz) 2 ( 3 ), and [Cd(bpy) 2 (FcTz) 2 ] · H 2 O ( 4 ) (bpy = 2, 2′‐bipyridine; phen = 1, 10‐phenanthroline; FcTz = 5‐ferrocenyl‐1H‐tetrazolate), derived from 5‐ferrocenyl‐1H‐tetrazole (HFcTz) were synthesized and structurally characterized. Compound 4 was also studied by density functional theory calculations (DFT). Additionally, a few single‐crystals of [Zn(phen) 2 (H 2 O) 2 ](FcTz) 2 ( 2 ) suitable for single‐crystal X‐ray diffraction formed and therefore only its crystal structure was analyzed. The cyclic voltammetry results suggested that 1 , 3 , and 4 are quasi‐reversible redox systems. The TG analysis showed they are of highly thermal stability when their lattice water molecules are not taken into account. Their catalytic performances for thermal decomposition of ammonium perchlorate (AP), 1, 3,5‐trinitro‐1, 3,5‐triazacyclohexane (RDX), and 1, 2,5, 7‐tetranitro‐1, 3,5, 7‐tetraazacyclooctane (HMX) were accessed by DSC/TG techniques. Their optimum contents in AP, RDX, and HMX are 5 wt‐ %, 5 wt‐ %, and 2 wt‐ %, respectively. They exhibit highly catalytic activities in thermal degradation of AP and RDX.
Graphene oxide has attracted attention due to its excellent catalytic properties, and it is expected to be used in the field of burning rate catalysis. To investigate the synergistic effect of graphene oxide and ferrocene derivatives, graphene oxide–(ferrocenylmethyl) dimethylammonium nitrate composites (GO–FcMANO3) were prepared and characterized by X-ray photoelectron spectroscopy (XPS), Raman analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM), and their thermal stability and catalytic effect on ammonium perchlorate (AP) were studied by thermogravimetry–differential scanning calorimetry (TG–DSC) techniques. Based on interaction region indicator (IRI) analysis, electrostatic potential (ESP) and energy decomposition analysis on the basis of forcefield (EDA-FF), the dispersion effect is the dominant component of interaction energy, and the contribution of electrostatic attraction is small. The frontier molecular orbitals illustrate that a higher highest occupied molecular orbital (HOMO) energy makes GO–FcMANO3 more susceptible to oxidization and is more conducive to catalyzing AP decomposition. The TG data illustrated that the presence of GO in the composites increased the thermal stability of FcMANO3 during AP decomposition. The catalytic effect of GO–FcMANO3 for AP decomposition manifested in two ways: it advanced the peak temperature in the second stage of AP decomposition and reduced the exothermic temperature width between two stages; it also increased the heat released during AP decomposition. Combined kinetic analysis and the Friedman method provided more detailed information about the catalytic behavior of composites for AP thermolysis, and GO–FcMANO3 composites decreased the Ea of the second stage of AP decomposition. The introduction of GO influenced the decomposition physical model of FcMANO3 for AP catalysis. The first stage of AP decomposition transformed from random nucleation and two-dimensional growth of nuclei model (A2) to random nucleation and three-dimensional growth of nuclei model (A3), and the second stage changed from the phase boundary-controlled reaction (R2) to random nucleation and two-dimensional growth of nuclei model (A2).
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