30 research outputs found

    Multishape Memory Effect of Norbornene-Based Copolymers with Cholic Acid Pendant Groups

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    Multishape memory copolymers were prepared through copolymerization of two norbornene derivatives: one based on cholic acid and the other on triethylene glycol monomethyl ether. The glass transition temperature (<i>T</i><sub>g</sub>) of the copolymers can be tuned over a temperature range from −58 to 176 °C. Most of these copolymers displayed a very broad <i>T</i><sub>g</sub> over a 20 °C range which can allow a multishape memory effect. The shape memory properties of the copolymer incorporating an equal molar amount of both monomers have been studied in detail. The multishape memory effect was investigated by dynamic mechanical analysis using a thermomechanical programming process, in which multiple steps created two, three, and four temporary shapes. The polymer displayed good shape fixing and recovery in different thermal processing stages over the broad glass transition range. This series of copolymers with broad and tunable <i>T</i><sub>g</sub>’s may be useful as functional materials with multishape memory effect

    Unified Mechanism for the Generation of Isolated and Clustered DNA Damages by a Single Low Energy (5–10 eV) Electron

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    Clustered DNA damages are the most detrimental modifications induced by ionizing radiation in cells and several mechanisms have been proposed for their formation. We report measurements of such damages induced by a single low energy electron via the formation of the two major core-excited resonances of DNA located at 4.6 and 9.6 eV. Cross-links and single and double strand breaks (SSBs and DSBs) are analyzed by gel electrophoresis. Treatment of irradiated samples with Esherichia coli base excision repair endonucleases reveals base damages (BDs). DSBs resulting from such treatments arise from clustered damages consisting of at least two BDs or one BD accompanied by a SSB. The total DNA damages induced by 4.6 and 9.6 eV electrons are 132 ± 32 and 201 ± 36 × 10<sup>–15</sup> electron<sup>–1</sup> molecule<sup>–1</sup>, comprising 43% and 52% BDs, respectively. We propose a unifying mechanism to account for these clustered damages, DSBs, and single BDs, as well as all previously measured isolated lesions

    Molecular efficacy of radio- and chemotherapy sequences from direct DNA damage measurements

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    <p><b>Purpose:</b> To investigate the molecular aspects of the synergy between ionizing radiation and platinum (Pt) chemotherapeutic agents in cancer treatment with chemoradiation therapy (CRT) by measuring damages induced by low-energy electrons (LEE) to DNA bound to cisplatin. LEE are produced abundantly by any type of ionizing radiation and cisplatin represents a typical Pt-chemotherapeutic agents.</p> <p><b>Materials and methods:</b> Our strategy involves two parallel administrations of cisplatin and irradiation with a 4.6 and 9.6 eV electron fluence of 1.1 × 10<sup>12</sup>: (1) LEE bombardment of supercoiled DNA and its subsequent reaction with cisplatin; (2) the reaction of DNA with cisplatin followed by LEE irradiation. The damage yields for the loss of supercoiled (LS), single-strand breaks (SSB) and double-strand breaks (DSB) were obtained from gel electrophoresis analysis. Base modifications were revealed by treating the samples with <i>Escherichia coli</i> base excision repair endonuclease (Nth and Fpg).</p> <p><b>Results:</b> The yields were deduced from the respective time–response for the reaction of DNA with cisplatin. The results show that binding cisplatin to DNA followed by LEE irradiation, consistently yields more DNA damages than the reverse order. In comparison to non-treated DNA, administration (2) results in an increase of LS and SSB of 1.4–3.3 folds and of DSB by more than an order of magnitude. Furthermore, after enzyme treatment, the yields of DSB rise by factors of 5.3–15.4, indicating a large increase of clustered damages, which should at least partially translate into an increase of lethal damages in cancer cells during the CRT.</p> <p><b>Conclusions:</b> Our results demonstrate that a strong synergy between radiation and cisplatin can only be achieved at the molecular level, if the drug is present at the time of irradiation. Furthermore, this work confirms the LEE mechanism previously proposed to explain the synergy between radiation and Pt drugs in CRT. It involves chemical sensitization of DNA prior to irradiation, to facilitate strand breaks and clustered damages induced by the highly reactive LEE.</p

    Active sp<sup>3</sup> C–H Bond Oxidation Initiated sp<sup>3</sup>–sp<sup>2</sup> Consecutive C–H Functionalization of <i>N</i>‑Arylglycine Amides: Construction of Isatins

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    In the presence of catalytic triarylamine radical cation, an sp<sup>3</sup>–sp<sup>2</sup> consecutive C–H functionalization of <i>N</i>-arylglycine amides was achieved, providing a series of isatin derivatives in high yields. In this transformation, the initial aerobic oxidation of the relatively active sp<sup>3</sup> C–H bonds triggered the following intramolecular cyclization, in which the aniline group was employed as a removable auxiliary group to enable the consecutive process

    Photo and Redox Dual Responsive Reversibly Cross-Linked Nanocarrier for Efficient Tumor-Targeted Drug Delivery

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    To develop a feasible and efficient nanocarrier for potential clinical application, a series of photo and redox dual responsive reversibly cross-linked micelles have been developed for the targeted anticancer drug delivery. The nanocarrier can be cross-linked efficiently via a clean, efficient, and controllable coumarin photodimerization within the nanocarrier, which simplify the formulation process and quality control prior clinical use and improve the in vivo stability for tumor targeting. At the same time, cross-linking of nanocarrier could be cleaved via the responsiveness of the built-in disulfide cross-linkage to the redox tumor microenvironment for on-demand drug release. Coumarin and disulfide bond was introduced into a linear-dendritic copolymer (named as telodendrimer) precisely via peptide chemistry. The engineered nanocarrier possesses good drug loading capacity and stability, and exhibits a safer profile as well as similar anticancer effects compared with free drug in cell culture. The in vivo and ex vivo small animal imaging revealed the preferred tumor accumulation and the prolonged tumor residency of the payload delivered by the cross-linked micelles compared to the non-cross-linked micelles and free drug surrogate because of the increased stability

    Block and Random Copolymers Bearing Cholic Acid and Oligo(ethylene glycol) Pendant Groups: Aggregation, Thermosensitivity, and Drug Loading

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    A series of block and random copolymers consisting of oligo­(ethylene glycol) and cholic acid pendant groups were synthesized via ring-opening metathesis polymerization of their norbornene derivatives. These block and random copolymers were designed to have similar molecular weights and comonomer ratios; both types of copolymers showed thermosensitivity in aqueous solutions with similar cloud points. The copolymers self-assembled into micelles in water as shown by dynamic light scattering and transmission electron microscopy. The hydrodynamic diameter of the micelles formed by the block copolymer is much larger and exhibited a broad and gradual shrinkage from 20 to 54 °C below its cloud point, while the micelles formed by the random copolymers are smaller in size but exhibited some swelling in the same temperature range. Based on <i>in vitro</i> drug release studies, 78% and 24% paclitaxel (PTX) were released in 24 h from micelles self-assembled by the block and random copolymers, respectively. PTX-loaded micelles formed by the block and random copolymers exhibited apparent antitumor efficacy toward the ovarian cancer cells with a particularly low half-maximal inhibitory concentration (IC<sub>50</sub>) of 27.4 and 40.2 ng/mL, respectively. Cholic acid-based micelles show promise as a versatile and potent platform for cancer chemotherapy

    Linear regression for prediction of the ribozyme activity (as measured by (1-Su3600) for the amount of substrate cleaved at 1 hr) for 13 "normally behaving" ribozymes

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    <p><b>Copyright information:</b></p><p>Taken from "A structural analysis of catalytic activities of hammerhead ribozymes"</p><p>http://www.biomedcentral.com/1471-2105/8/469</p><p>BMC Bioinformatics 2007;8():469-469.</p><p>Published online 30 Nov 2007</p><p>PMCID:PMC2238771.</p><p></p> () For Δas the predictor, the for the regression is 0.4677, and the -value is 0.0099. () For Δas the predictor, the for the regression is 0.6242, and the -value is 0.0013. Also plotted are the two outliers (GUC11 and GUC3) that were not included in the regression analysis (see Results, Figures 4 and 5 for explanations of the outliers)

    Structuring β‑Ga<sub>2</sub>O<sub>3</sub> Photonic Crystal Photocatalyst for Efficient Degradation of Organic Pollutants

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    Coupling photocatalysts with photonic crystals structure is based on the unique property of photonic crystals in confining, controlling, and manipulating the incident photons. This combination enhances the light absorption in photocatalysts and thus greatly improves their photocatalytic performance. In this study, Ga<sub>2</sub>O<sub>3</sub> photonic crystals with well-arranged skeleton structures were prepared <i>via</i> a dip-coating infiltration method. The positions of the electronic band absorption for Ga<sub>2</sub>O<sub>3</sub> photonic crystals could be made to locate on the red edge, on the blue edge, and away from the edge of their photonic band gaps by changing the pore sizes of the samples, respectively. Particularly, the electronic band absorption of the Ga<sub>2</sub>O<sub>3</sub> photonic crystal with a pore size of 135 nm was enhanced more than other samples by making it locate on the red edge of its photonic band gap, which was confirmed by the higher instantaneous photocurrent and photocatalytic activity for the degradation of various organic pollutants under ultraviolet light irradiation. Furthermore, the degradation mechanism over Ga<sub>2</sub>O<sub>3</sub> photonic crystals was discussed. The design of Ga<sub>2</sub>O<sub>3</sub> photonic crystals presents a prospective application of photonic crystals in photocatalysis to address light harvesting and quantum efficiency problems through manipulating photons or constructing photonic crystal structure as groundwork

    Evidence for the Active Species Involved in the Photodegradation Process of Methyl Orange on TiO<sub>2</sub>

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    Active species such as holes, electrons, hydroxyl radicals (•OH), and superoxide radicals (O<sub>2</sub><sup>•–</sup>) involved in the photodegradation process of methyl orange (MO) over TiO<sub>2</sub> photocatalyst were detected by several techniques. Using different types of active species scavengers, the results showed that the MO oxidation was driven mainly by the participation of O<sub>2</sub><sup>•–</sup>, holes and •OH radicals. Characterized by the liquid chromatography/mass spectrometry, the transversion of the degradation products with the light irradiation time was first analyzed. Combined with the measurement of oxidation reduction potential, dissolved oxygen, conductivity, and pH values, the degradation process of MO on TiO<sub>2</sub> under the effect of the active species was revealed. This was the first time that electrodes were introduced to track the degradation process in situ, and these parameters would be helpful to explain the degradation processes of other organic pollutants
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