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        Synthesis and Characterization of Nitric Oxide-Releasing Platinum(IV) Prodrug and Polymeric Micelle Triggered by Light

        Pramanick, Swapan,Kim, Jihoon,Kim, Jinhwan,Saravanakumar, Gurusamy,Park, Dongsik,Kim, Won Jong American Chemical Society 2018 Bioconjugate chemistry Vol.29 No.4

        <P>Herein, we report the proof of concept of photoresponsive chemotherapeutics comprising nitric oxide-releasing platinum prodrugs and polymeric micelles. Photoactivatable nitric oxide-releasing donors were integrated into the axial positions of a platinum(IV) prodrug, and the photolabile hydrophobic groups were grafted in the block copolymers. The hydrophobic interaction between nitric oxide donors and the photolabile groups allowed for the loading of platinum drugs and nitric oxide-releasing donors in the photolabile polymeric micelles. After cellular uptake of micelles, light irradiation induced the release of nitric oxide, which sensitized the cancer cells. Simultaneously, photolabile hydrophobic groups were cleaved from micelles, and the nitric oxide-releasing donor was altered to be more hydrophilic, resulting in the rapid release of platinum(IV) prodrugs. The strategy of using platinum(IV) prodrugs and nitric oxide led to enhanced anticancer effects.</P> [FIG OMISSION]</BR>

      • Human hair-derived hollow carbon microfibers for electrochemical sensing

        Pramanick, B.,Cadenas, L.B.,Kim, D.M.,Lee, W.,Shim, Y.B.,Martinez-Chapa, S.O.,Madou, M.J.,Hwang, H. Pergamon Press ; Elsevier Science Ltd 2016 Carbon Vol.107 No.-

        <P>Glassy carbon has been widely used for various applications including electrochemical sensors and energy storage devices. Here we introduce a novel way to fabricate glassy carbon microfibers based on human hairs. The coaxial structure of hair shafts results in long hollow glassy carbon structures upon pyrolysis at 900 degrees C in a N-2 atmosphere. The morphology of human hair samples before and after pyrolysis was characterized using scanning electron microscopy. The chemical composition of natural and pyrolyzed human hairs was also characterized using Raman spectroscopy and energy-dispersive X-ray spectroscopy. Screen printed carbon electrodes were modified with the hair-derived carbons and applied for electrochemical sensing of dopamine and ascorbic acid. The hair-derived carbons significantly improved the performance of the electrochemical sensors compared to the unmodified sensors. This method provides an easy, simple, and inexpensive way to fabricate hollow 3D glassy carbon microelectrodes. (C) 2016 Elsevier Ltd. All rights reserved.</P>

      • Nitric oxide-activatable gold nanoparticles for specific targeting and photo-thermal ablation of macrophages

        Park, J.,Pramanick, S.,Kim, J.,Lee, J.,Kim, W. Royal Society of Chemistry 2017 Chemical communications Vol.53 No.81

        <P>In this study, we designed NO-activatable gold nanoparticles (NAM-AuNPs) for specific targeting and photo-thermal ablation of macrophages. The gold nanoparticles showed aggregation behavior in response to NO solution as well as endogenous NO secreted from activated macrophages. Following NIR irradiation, significant cytotoxicity was observed in activated RAW 264.7 cells treated with NAM-AuNPs.</P>

      • Polymeric biomaterials for the delivery of platinum-based anticancer drugs

        Kim, Jihoon,Pramanick, Swapan,Lee, Duhwan,Park, Hansoo,Kim, Won Jong The Royal Society of Chemistry 2015 Biomaterials Science Vol.3 No.7

        <▼1><P>This review discusses the recent research trends in the polymeric delivery systems for platinum-based anticancer drugs.</P></▼1><▼2><P>Since cisplatin, <I>cis</I>-diamminedichloroplatinum(ii), received FDA approval for use in cancer treatment in 1978, platinum-based drugs have been one of the most widely used drugs for the treatment of tumors in testicles, ovaries, head and neck. However, there are concerns associated with the use of platinum-based anticancer drugs, owing to severe side effects and drug resistance. In order to overcome these limitations, various drug-delivery systems have been developed based on diverse organic and inorganic materials. In particular, the versatility of polymeric materials facilitates the tuning of drug-delivery systems to meet their primary goals. This review focuses on the progress made over the last five years in the application of polymeric nanoparticles for the delivery of platinum-based anticancer drugs. The present article not only describes the fundamental principles underlying the implementation of polymeric nanomaterials in platinum-based drug delivery, but also summarizes concepts and strategies employed in the development of drug-delivery systems.</P></▼2>

      • A Pt(iv)-mediated polymer architecture for facile and stimuli-responsive intracellular gene silencing with chemotherapy

        Jung, Sungjin,Kim, Jinhwan,Pramanick, Swapan,Park, Hyeongmok,Lee, Hyori,Lee, Junseok,Kim, Won Jong The Royal Society of Chemistry 2018 Biomaterials science Vol.6 No.12

        <P>Conventional chemotherapy has been impeded by the inherent characteristics of cancer including fast mutagenesis and drug resistance; thus a combination therapy consisting of multiple therapeutic strategies has attracted much attention. However, the loading processes of multiple therapeutic molecules affect each other; thus the development of a nanocarrier that enables independent loading of the cargo molecules has been demanded. Herein, we report an ingeniously designed Pt(iv)-mediated polymeric architecture (Pt-PA) for combinatorial gene and chemotherapy to address the issue, prepared by crosslinking a cationic polymer (polyethylenimine, PEI) with a Pt(iv) prodrug. Therapeutic siRNA (anti-BCL2) was simply loaded by electrostatic interaction to form a stable nanocomplex. In the cellular study, the simultaneous release of both the active Pt(ii) drug and siRNA was monitored under the intracellular reducing environment, driven by dissociation of the polymer architecture due to an inherent characteristic of the Pt(iv) crosslinker. Therefore, an enhanced gene silencing effect and an anticancer effect were observed. Furthermore, in the animal study, an improved therapeutic effect of the nanocomplex was observed, which can be explained by tumor targeting <I>via</I> the EPR effect, and enhanced drug and siRNA release at the intracellular environment simultaneously. Taken together, the overall results from <I>in vitro</I> and <I>in vivo</I> studies strongly suggest the therapeutic potential of our precisely designed Pt(iv)-mediated polymer architecture.</P>

      • KCI등재

        Effect of Strain Induced Melt Activation Process on the Microstructure and Mechanical Properties of Al-5Ti-1B Treated Al-7Si Alloy

        Chandan Choudhary,H. N. Bar,A. K. Pramanick,K. L. Sahoo,Durbadal Mandal 대한금속·재료학회 2022 METALS AND MATERIALS International Vol.28 No.10

        In this study, simultaneous effects of modified strain induced melt activation (M-SIMA) process and addition of Al-5Ti-1Bchemical grain refiner on the casting defects, microstructural features, and mechanical properties of hypoeutectic Al-7Sialloys are investigated. The traditional melting and casting techniques were used to develop cast ingots of unrefined andgrain refined structures of Al-7Si alloy. Addition of chemical refiner Al-5Ti-1B to Al-7Si melt could significantly changethe secondary dendritic arm spacing and eutectic Si particle size to 31% and 28%, respectively. In the M-SIMA process, castingots were 60% warm deformed and heat-treated at mushy zone at temperature 585 °C for 30 min. Spherical morphology ofα-Al grain and fine fibrous type eutectic Si are observed after M-SIMA process. Grain size of α-Al and eutectic Si are furtherreduced to 56% and 40% after M-SIMA process of grain refined Al-7Si alloy. Porosity and micro-cracks are also minimizedafter M-SIMA process. Microstructural features of cast and M-SIMA processed alloys were characterized through opticaland scanning electron microscopy. X-ray diffraction techniques reveal the different phases present in the developed alloy. TEM analysis further confirms the presence of TiAl3and Ti7Al5Si14precipitates in grain refined Al-7Si alloy. A significantimprovement of 132% in hardness (HV), 76% in yield strength, 120% in ultimate tensile strength, 125% in elongation tofracture, and 116% in specific ultimate tensile strength are obtained in M-SIMA processed grain refined Al-7Si alloy. Fractographyanalysis reveals the mixed mode of fracture in M-SIMA processed Al-7Si alloy with refined structure comparedto brittle fracture of unrefined cast alloy.

      • SCISCIESCOPUS

        Andrographolide-loaded polymerized phenylboronic acid nanoconstruct for stimuli-responsive chemotherapy

        Kim, Jinhwan,Lee, Junseok,Lee, Yeong Mi,Pramanick, Swapan,Im, Sooseok,Kim, Won Jong Elsevier 2017 Journal of controlled release Vol.259 No.-

        <P><B>Abstract</B></P> <P>Along with the successful discovery of paclitaxel as an anticancer drug, natural products have drawn great attention in drug discovery. Recently, andrographolide (AND) from <I>Andrographis paniculata</I> was reported to provide several benefits, including an anticancer effect. However, the extremely low solubility of the compound in an aqueous medium was an obstacle to overcome for the systemic administration and clinical application of AND. Based on our previous report, we formulated a water-soluble nanoconstruct by forming a boronic ester between the <I>cis</I>-1,3-diol of AND with hydrophilically polymerized phenylboronic acid (pPBA). The release of loaded AND was controlled by intracellular conditions, specifically, by low pH and high ATP concentrations, due to the pH- and diol-dependent affinity of the boronic ester. Because of the intrinsic property of the PBA moiety, the pPBA-AND nanoconstruct exhibited an excellent tumor targeting ability both <I>in vitro</I> and <I>in vivo</I>. Finally, a significant inhibition of tumor growth was observed <I>in vivo</I>. Taken together, our strategy, which is based on the formulation of a soluble nanoconstruct using hydrophilically polymerized PBA and a <I>cis</I>-diol, is plausible and provides a delivery system for a wide variety of chemotherapeutics. This strategy has applications not only in cancer therapy but also broader fields such as anti-inflammation or immunotherapy.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

      • Miktoarm Amphiphilic Block Copolymer with Singlet Oxygen-Labile Stereospecific β-Aminoacrylate Junction: Synthesis, Self-Assembly, and Photodynamically Triggered Drug Release

        Saravanakumar, Gurusamy,Park, Hyeongmok,Kim, Jinhwan,Park, Dongsik,Pramanick, Swapan,Kim, Dae Heon,Kim, Won Jong American Chemical Society 2018 Biomacromolecules Vol.19 No.6

        <P>Incorporation of a desired stimuli-responsive unit in a stereospecific manner at the specific location within a nonlinear block copolymer architecture is a challenging task in synthetic polymer chemistry. Herein, we report a facile and versatile method to synthesize AB<SUB>2</SUB> miktoarm block copolymers bearing a singlet oxygen (<SUP>1</SUP>O<SUB>2</SUB>)-labile regio and stereospecific β-aminoacrylate linkage with 100% <I>E</I>-configuration at the junction via a combination of amino-yne click chemistry and ring opening polymerization. Using this strategy, a series of <SUP>1</SUP>O<SUB>2</SUB>-responsive AB<SUB>2</SUB> amphiphilic miktoarm (MA) copolymers composed of hydrophilic polyethylene glycol (PEG) as the A constituent and hydrophobic polycaprolactone (PCL) as the B constituent (MA-PEG-<I>b</I>-PCL<SUB>2</SUB>) was synthesized by varying the block length of PCL. The self-assembly characteristics of these well-defined MA-PEG-<I>b</I>-PCL<SUB>2</SUB> copolymers in an aqueous condition were studied by solvent displacement and thin-film hydration method, and their morphologies were investigated using transmission electron microscopy. The copolymers formed spherical, cylindrical, or lamella morphologies, depending on the chain length and preparation conditions. A hydrophobic photosensitizer chlorin e6 (Ce6) and anticancer drug doxorubicin (DOX) were efficiently encapsulated into the hydrophobic core of MA-PEG-<I>b</I>-PCL<SUB>2</SUB> copolymer micelles. These coloaded micelles were taken up by human breast cancer (MDA-MB-231) cells. Upon red laser light irradiation, the <SUP>1</SUP>O<SUB>2</SUB>-generated by the Ce6 induced photocleavage of the β-aminoacrylate moiety, leading to the dissociation of the micellar structure and triggered intracellular drug release for effective therapy. Overall, rapid disassembly upon <SUP>1</SUP>O<SUB>2</SUB> generation and subsequent controlled intracellular drug release suggested that these micelles bearing β-aminoacrylate linkage have a huge potential for on-demand drug delivery.</P> [FIG OMISSION]</BR>

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