Department of Chemistry

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https://hdl.handle.net/10919/23842

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Browsing Department of Chemistry by Department "Chemical Engineering"

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    Ammonium Bisphosphonate Polymeric Magnetic Nanocomplexes for Platinum Anticancer Drug Delivery and Imaging with Potential Hyperthermia and Temperature-Dependent Drug Release
    Zhang, Rui; Fellows, Benjamin; Pothayee, Nikorn; Hu, Nan; Pothayee, Nipon; Jo, Ami; Bohórquez, Ana C.; Rinaldi, Carlos; Mefford, Olin Thompson; Davis, Richey M.; Riffle, Judy S. (Hindawi, 2018-08-05)
    Novel magnetite-ammonium bisphosphonate graft ionic copolymer nanocomplexes (MGICs) have been developed for potential drug delivery, magnetic resonance imaging, and hyperthermia applications. The complexes displayed relatively uniform sizes with narrow size distributions upon self-assembly in aqueous media, and their sizes were stable under simulated physiological conditions for at least 7 days. The anticancer drugs, cisplatin and carboplatin, were loaded into the complexes, and sustained release of both drugs was observed. The transverse NMR relaxivities (s) of the complexes were 244 s−1 (mM Fe)−1 which is fast compared to either the commercial T2-weighted MRI agent Feridex IV® or our previously reported magnetite-block ionomer complexes. Phantom MRI images of the complexes demonstrated excellent negative contrast effects of such complexes. Thus, the bisphosphonate-bearing MGICs could be promising candidates for dual drug delivery and magnetic resonance imaging. Moreover, the bisphosphonate MGICs generate heat under an alternating magnetic field of 30 kA·m−1 at 206 kHz. The temperature of the MGIC dispersion in deionized water increased from 37 to 41°C after exposure to the magnetic field for 10 minutes, corresponding to a specific absorption rate of 77.0 W·g−1. This suggests their potential as hyperthermia treatment agents as well as the possibility of temperature-dependent drug release, making MGICs more versatile in potential drug delivery applications.
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    An atomic force microscope tip as a light source
    Lulevich, V.; Honig, Christopher D. F.; Ducker, William A. (AIP Publishing, 2005-12-01)
    We present a simple method for causing the end of a silicon nitride atomic force microscope (AFM) tip to emit light, and we use this emitted light to perform scanning near-field optical microscopy. Illumination of a silicon nitride AFM tip by blue (488 nm) or green (532 nm) laser light causes the sharp part of the tip to emit orange light. Orange light is emitted when the tip is immersed in either air or water; and while under illumination, emission continues for a period of many hours without photobleaching. By careful alignment of the incident beam, we can arrange the scattered light to decay as a function of the tip-substrate separation with a decay length of 100-200 nm. The exponential decay of the intensity means that the emitted light is dominated by contributions from parts of the tip that are near the sample, and therefore the emitted orange light can be used to capture high-resolution near-field optical images in air or water. (c) 2005 American Institute of Physics.
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    Design Of A High-Temperature And High-Pressure Liquid Flow Cell For X-Ray Absorption Fine Structure Measurements Under Catalytic Reaction Conditions
    Kawai, T.; Chun, W. J.; Asakura, K.; Koike, Y.; Nomura, M.; Bando, K. K.; Oyama, Shigeo Ted; Sumiya, H. (AIP Publishing, 2008-01-01)
    The design and performance of a new high-pressure and high-temperature cell for measurement of x-ray absorption fine structure (XAFS) spectra of solid catalysts working in a flowing liquid are presented. The cell has flat, high-purity sintered cubic boron nitride (c-BN) windows which can tolerate high temperature (900 K) and high pressure (10 MPa). The c-BN is a new material which has the highest tensile strength, second only to diamond, and is also chemically and thermally stable. The use of the cell is demonstrated for measurements of PtPd/Al(2)O(3) and Ni(2)P/SiO(2) hydrodesulfurization catalysts at reaction conditions. A technique called delta chi (Delta chi), involving determining the difference between XAFS spectra of the sample at reaction conditions and the bare sample, is introduced. (c) 2008 American Institute of Physics.
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    Fabrication and characterization of PLGA nanoparticles encapsulating large CRISPR–Cas9 plasmid
    Jo, Ami; Ringel-Scaia, Veronica M.; McDaniel, Dylan K.; Thomas, Cassidy A.; Zhang, Rui; Riffle, Judy S.; Allen, Irving C.; Davis, Richey M. (2020-01-20)
    Background The clustered regularly interspaced short palindromic repeats (CRISPR) and Cas9 protein system is a revolutionary tool for gene therapy. Despite promising reports of the utility of CRISPR–Cas9 for in vivo gene editing, a principal problem in implementing this new process is delivery of high molecular weight DNA into cells. Results Using poly(lactic-co-glycolic acid) (PLGA), a nanoparticle carrier was designed to deliver a model CRISPR–Cas9 plasmid into primary bone marrow derived macrophages. The engineered PLGA-based carriers were approximately 160 nm and fluorescently labeled by encapsulation of the fluorophore 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene). An amine-end capped PLGA encapsulated 1.6 wt% DNA, with an encapsulation efficiency of 80%. Release studies revealed that most of the DNA was released within the first 24 h and corresponded to ~ 2–3 plasmid copies released per nanoparticle. In vitro experiments conducted with murine bone marrow derived macrophages demonstrated that after 24 h of treatment with the PLGA-encapsulated CRISPR plasmids, the majority of cells were positive for TIPS pentacene and the protein Cas9 was detectable within the cells. Conclusions In this work, plasmids for the CRISPR–Cas9 system were encapsulated in nanoparticles comprised of PLGA and were shown to induce expression of bacterial Cas9 in murine bone marrow derived macrophages in vitro. These results suggest that this nanoparticle-based plasmid delivery method can be effective for future in vivo applications of the CRISPR–Cas9 system.
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    Photocatalyst-independent photoredox ring-opening polymerization of O-carboxyanhydrides: stereocontrol and mechanism
    Zhong, Yongliang; Feng, Quanyou; Wang, Xiaoqian; Yang, Lei; Korovich, Andrew G.; Madsen, Louis A.; Tong, Rong (2021-03-14)
    Photoredox ring-opening polymerization of O-carboxyanhydrides allows for the synthesis of polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. While powerful, obviating the use of precious metal-based photocatalysts would be attractive from the perspective of simplifying the protocol. Herein, we report the Co and Zn catalysts that are activated by external light to mediate efficient ring-opening polymerization of O-carboxyanhydrides, without the use of exogenous precious metal-based photocatalysts. Our methods allow for the synthesis of isotactic polyesters with high molecular weights (>200 kDa) and narrow molecular weight distributions (M-w/M-n < 1.1). Mechanistic studies indicate that light activates the oxidative status of a Co-III intermediate that is generated from the regioselective ring-opening of the O-carboxyanhydride. We also demonstrate that the use of Zn or Hf complexes together with Co can allow for stereoselective photoredox ring-opening polymerizations of multiple racemic O-carboxyanhydrides to synthesize syndiotactic and stereoblock copolymers, which vary widely in their glass transition temperatures.