Optical Interference-Free Surface-Enhanced Raman Scattering CO-Nanotags for Logical Multiplex Detection of Vascular Disease-Related Biomarkers.

Matrix metalloproteinases (MMPs), specifically MMP-2, MMP-7, and MMP-9, have been discovered to be linked to many forms of vascular diseases such as stroke, and their detection is crucial to facilitate clinical diagnosis. In this work, we prepared a class of optical interference-free SERS nanotags (CO-nanotags) that can be used for the purpose of multiplex sensing of different MMPs. Multiplex detection with the absence of cross-talk was achieved by using CO-nanotags with individual tunable intrinsic Raman shifts of CO in the 1800-2200 cm-1 region determined by the metal core and ligands of the metal carbonyl complex. Boolean logic was used as well to simultaneously probe for two proteolytic inputs. Such nanotags offer the advantages of convenient detection of target nanotags and high sensitivity as validated in the ischemia rat model.

[1]  M. Olivo,et al.  Sensitive surface enhanced Raman scattering multiplexed detection of matrix metalloproteinase 2 and 7 cancer markers. , 2015, Biomedical optics express.

[2]  W. Leong,et al.  Osmium Carbonyl Clusters: A New Class of Apoptosis Inducing Agents , 2008, ChemMedChem.

[3]  Chun-Qiang Lu,et al.  Role of P38 MAPK on MMP Activity in Photothrombotic Stroke Mice as Measured using an Ultrafast MMP Activatable Probe , 2015, Scientific Reports.

[4]  H. Lamb,et al.  C- and O-Bonded Carbon Monoxide on Surfaces: Interactions of [CpW(CO)3]- with Cations on Magnesia, Alumina, and Potassium-Modified Alumina , 1994 .

[5]  M. Olivo,et al.  Metal carbonyl-gold nanoparticle conjugates for live-cell SERS imaging. , 2012, Angewandte Chemie.

[6]  T. Ueland,et al.  Matrix Metalloproteinase 7 Is Associated with Symptomatic Lesions and Adverse Events in Patients with Carotid Atherosclerosis , 2014, PloS one.

[7]  Jeffrey N. Anker,et al.  Biosensing with plasmonic nanosensors. , 2008, Nature materials.

[8]  T. S. Alstrøm,et al.  Surface-enhanced Raman spectroscopy based quantitative bioassay on aptamer-functionalized nanopillars using large-area Raman mapping. , 2013, ACS nano.

[9]  D. Ohlberg,et al.  Study of molecular trapping inside gold nanofinger arrays on surface-enhanced Raman substrates. , 2011, Journal of the American Chemical Society.

[10]  S. Snow Stroke and t-PA--Triggering New Paradigms of Care. , 2016, The New England journal of medicine.

[11]  S. Rampino,et al.  How π back-donation quantitatively controls the CO stretching response in classical and non-classical metal carbonyl complexes , 2015, Chemical science.

[12]  R. Alberto,et al.  Chemistry and biological activities of CO-releasing molecules (CORMs) and transition metal complexes. , 2007, Dalton transactions.

[13]  J. Steed,et al.  Transition metal complexes of the weakly coordinating carborane anion [CB11H12]−: the first isolation and structural characterisation of an intermediate in a silver salt metathesis reaction , 2000 .

[14]  Jörg Hübner,et al.  Large Area Fabrication of Leaning Silicon Nanopillars for Surface Enhanced Raman Spectroscopy , 2012, Advanced materials.

[15]  S. Schlücker Surface-enhanced Raman spectroscopy: concepts and chemical applications. , 2014, Angewandte Chemie.

[16]  M. Marcos,et al.  Stabilization of 17-electron metal-centered species. Electrochemical study of [WX(CO)3(η5-C5H5)] (X=Cl, Br, I) and [WI(CO)2(PCy3)(η5-C5H5)] , 1998 .

[17]  D. Wakefield,et al.  Ultrasensitive and specific measurement of protease activity using functionalized photonic crystals. , 2015, Analytical chemistry.

[18]  P. Tighe,et al.  Development and Validation of Protein Microarray Technology for Simultaneous Inflammatory Mediator Detection in Human Sera , 2014, Mediators of inflammation.

[19]  Ruo Yuan,et al.  An electrochemical peptide cleavage-based biosensor for matrix metalloproteinase-2 detection with exonuclease III-assisted cycling signal amplification. , 2016, Chemical communications.

[20]  Cheng Zong,et al.  Label-free surface-enhanced Raman spectroscopy detection of DNA with single-base sensitivity. , 2015, Journal of the American Chemical Society.

[21]  K. Barnett,et al.  Isomerically pure cyclopentadienyl-molybdenum and -tungsten carbonyl halide complexes , 1975 .

[22]  Marc D Porter,et al.  Toward development of a surface-enhanced Raman scattering (SERS)-based cancer diagnostic immunoassay panel. , 2013, The Analyst.

[23]  Eng H. Lo,et al.  Neurological diseases: Mechanisms, challenges and opportunities in stroke , 2003, Nature Reviews Neuroscience.

[24]  F. Barone,et al.  Matrix metalloproteinase expression increases after cerebral focal ischemia in rats: inhibition of matrix metalloproteinase-9 reduces infarct size. , 1998, Stroke.

[25]  William S. Striejewske,et al.  HALIDE EXCHANGE REACTIONS BETWEEN CpW(CO)3 − AND CpMo(CO)3X , 1996 .

[26]  Manuel Hidalgo,et al.  Matrix metalloproteinase-2 contributes to cancer cell migration on collagen. , 2005, Cancer research.

[27]  H. Tian,et al.  Monitoring of Endogenous Hydrogen Sulfide in Living Cells Using Surface-Enhanced Raman Scattering. , 2015, Angewandte Chemie.

[28]  A. Wojcicki,et al.  Sulfur dioxide insertion. VI. S-sulfinatopentacarbonyl complexes of Group VI and VII transition metals , 1968 .

[29]  Wee Chew,et al.  Bioimaging in the mid-infrared using an organometallic carbonyl tag. , 2007, Bioconjugate chemistry.

[30]  Zhe Wang,et al.  Poly(m-phenylenediamine)-based fluorescent nanoprobe for ultrasensitive detection of matrix metalloproteinase 2. , 2014, Analytical chemistry.

[31]  Erqun Song,et al.  A graphene oxide-based FRET sensor for rapid and sensitive detection of matrix metalloproteinase 2 in human serum sample. , 2013, Biosensors & bioelectronics.

[32]  A. Furlan,et al.  Endovascular therapy for stroke--it's about time. , 2015, The New England journal of medicine.

[33]  J. Bielewicz,et al.  The significance of matrix metalloproteinase (MMP)-2 and MMP-9 in the ischemic stroke , 2014, The International journal of neuroscience.

[34]  RyosukeTakahashi,et al.  Matrix Metalloproteinase-2 Plays a Critical Role in the Pathogenesis of White Matter Lesions After Chronic Cerebral Hypoperfusion in Rodents , 2006 .

[35]  W. Leong,et al.  Osmium carbonyl clusters containing labile ligands hyperstabilize microtubules. , 2009, Chemical research in toxicology.

[36]  M. Olivo,et al.  A transition metal carbonyl probe for use in a highly specific and sensitive SERS-based assay for glucose. , 2013, Journal of the American Chemical Society.

[37]  J. Zink,et al.  Synthesis and luminescence spectroscopy of a series of [eta(5)-CpFe(CO)2] complexes containing 1,12-dicarba-closo-dodecaboranyl and -ylene ligands. , 2001, Inorganic chemistry.

[38]  Yu-Ning Song,et al.  MMP-9, a Potential Target for Cerebral Ischemic Treatment , 2009, Current neuropharmacology.

[39]  C. A. Tolman,et al.  Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis , 1977 .

[40]  Younan Xia,et al.  Quantifying the coverage density of poly(ethylene glycol) chains on the surface of gold nanostructures. , 2012, ACS nano.

[41]  A. Sakthivel,et al.  In situ grafting of cyclopentadienyl-molybdenum complexes on mesoporous materials: The reaction of [η5-CpMo(CO)3]−Na+ with surface fixed iodo-benzyl siloxane , 2005 .

[42]  N. Koshikawa,et al.  Matrilysin (MMP-7) induces homotypic adhesion of human colon cancer cells and enhances their metastatic potential in nude mouse model , 2003, Oncogene.

[43]  M. Olivo,et al.  Sensitive SERS-pH sensing in biological media using metal carbonyl functionalized planar substrates. , 2014, Biosensors & bioelectronics.

[44]  R. Jin Nanoparticle clusters light up in SERS. , 2010, Angewandte Chemie.

[45]  A. Vessières,et al.  Use of Fourier transform infrared spectroscopy for the simultaneous quantitative detection of metal carbonyl tracers suitable for multilabel immunoassays. , 1993, Analytical Biochemistry.

[46]  K. Mogensen,et al.  Wafer-Scale Leaning Silver Nanopillars for Molecular Detection at Ultra-Low Concentrations , 2015 .

[47]  Chunya Li,et al.  Upconversion fluorescence resonance energy transfer based biosensor for ultrasensitive detection of matrix metalloproteinase-2 in blood. , 2012, Analytical chemistry.

[48]  Z. Werb,et al.  New functions for the matrix metalloproteinases in cancer progression , 2002, Nature Reviews Cancer.