Mixed Zwitterion-Based Self-Assembled Monolayer Interface for Impedimetric Glycomic Analyses of Human IgG Samples in an Array Format.

An impedimetric lectin biosensor for the detection of changes in the glycan structure of antibodies isolated from human serum is here correlated with the progression of rheumatoid arthritis (RA). The biosensor was built up from a mixed self-assembled monolayer (SAM) on gold consisting of two different thiolated zwitterionic derivatives, carboxybetaine and sulfobetaine, to resist nonspecific interactions. The carboxyl-terminated one was applied also for the covalent immobilization of lectin Ricinus communis agglutinin I (RCA-I). The process of building a bioreceptive layer was optimized and characterized using a diverse range of techniques. Impedimetric assays were integrated on a chip consisting of eight gold working electrodes, which is an important step toward the achievement of a moderate level of multiplexing for the analysis of human serum samples. At the end, the results obtained by the impedimetric analysis of immunoglobulins G (IgGs) isolated from serum samples were compared with those of two other standard bioanalytical methods employing lectins, that is, lectin microarrays (MAs) and enzyme-linked lectin binding assays (ELLBAs). The impedimetric results agreed very well with the DAS28 index (RA disease activity score 28), suggesting that impedimetric assays could be used for the development of a new diagnostic procedure sensitive to glycosylation changes in human IgGs and thus RA progression.

[1]  J. Tkáč,et al.  Are glycan biosensors an alternative to glycan microarrays? , 2014, Analytical methods : advancing methods and applications.

[2]  Pauline M Rudd,et al.  Glycans as cancer biomarkers. , 2012, Biochimica et biophysica acta.

[3]  Jason J. Davis,et al.  Immittance electroanalysis in diagnostics. , 2015, Analytical chemistry.

[4]  D. Hobara,et al.  Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111). , 2005, Langmuir : the ACS journal of surfaces and colloids.

[5]  S. Svarovsky,et al.  Cancer glycan biomarkers and their detection – past, present and future , 2014 .

[6]  A. Silman,et al.  UvA-DARE (Digital Academic Repository) 2010 Rheumatoid arthritis classification criteria: an American College of Rheumatology/European League Against Rheumatism collaborative initiative Aletaha, , 2010 .

[7]  M. Aldissi,et al.  New multispecific array as a tool for electrochemical impedance spectroscopy-based biosensing. , 2010, Biosensors & bioelectronics.

[8]  Jin Wang,et al.  Three-dimensional electrochemical immunosensor for sensitive detection of carcinoembryonic antigen based on monolithic and macroporous graphene foam. , 2015, Biosensors & bioelectronics.

[9]  Jason J. Davis,et al.  An optimised electrode pre-treatment for SAM formation on polycrystalline gold , 2008 .

[10]  J. Tkáč,et al.  Can glycoprofiling be helpful in detecting prostate cancer? , 2015, Chemical Papers.

[11]  J. Szechiński,et al.  Galactosylation of IgG from rheumatoid arthritis (RA) patients – changes during therapy , 2006, Glycoconjugate Journal.

[12]  Song Zhang,et al.  Protein-inorganic hybrid nanoflowers as ultrasensitive electrochemical cytosensing interfaces for evaluation of cell surface sialic acid. , 2015, Biosensors & bioelectronics.

[13]  Sanjeeva Srivastava,et al.  Protein microarrays and novel detection platforms , 2011, Expert review of proteomics.

[14]  Raymond A. Dwek,et al.  Emerging Principles for the Therapeutic Exploitation of Glycosylation , 2014, Science.

[15]  C. Franceschi,et al.  N-glycomic biomarkers of biological aging and longevity: A link with inflammaging , 2013, Ageing Research Reviews.

[16]  J. Paulson,et al.  Siglec-mediated regulation of immune cell function in disease , 2014, Nature Reviews Immunology.

[17]  Shaoyi Jiang,et al.  Molecular Understanding and Design of Zwitterionic Materials , 2015, Advanced materials.

[18]  Iraida Loinaz,et al.  Nanostructured disposable impedimetric sensors as tools for specific biomolecular interactions: sensitive recognition of concanavalin A. , 2011, Analytical chemistry.

[19]  Jui-Che Lin,et al.  Improving the surface biocompatibility with the use of mixed zwitterionic self-assembled monolayers prepared by a proper solvent. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[20]  Yong Duan,et al.  A review of impedance measurements of whole cells. , 2016, Biosensors & bioelectronics.

[21]  Jan Tkac,et al.  Ultrasensitive impedimetric lectin biosensors with efficient antifouling properties applied in glycoprofiling of human serum samples. , 2013, Analytical chemistry.

[22]  M. Roque-Barreira,et al.  Impedance-derived electrochemical capacitance spectroscopy for the evaluation of lectin-glycoprotein binding affinity. , 2014, Biosensors & bioelectronics.

[23]  J. Tkáč,et al.  Glycoprofiling as a novel tool in serological assays of systemic sclerosis: a comparative study with three bioanalytical methods. , 2015, Analytica chimica acta.

[24]  G. Whitesides,et al.  Self-Assembled Monolayers That Resist the Adsorption of Proteins and the Adhesion of Bacterial and Mammalian Cells , 2001 .

[25]  René Kizek,et al.  Ultrasensitive detection of influenza viruses with a glycan-based impedimetric biosensor. , 2016, Biosensors & bioelectronics.

[26]  E. Paleček,et al.  Electrochemistry of Nonconjugated Proteins and Glycoproteins. Toward Sensors for Biomedicine and Glycomics , 2015, Chemical reviews.

[27]  Peng Zhang,et al.  Stealth surface modification of surface-enhanced Raman scattering substrates for sensitive and accurate detection in protein solutions. , 2015, ACS nano.

[28]  G. Whitesides,et al.  Self-assembled organic monolayers: model systems for studying adsorption of proteins at surfaces , 1991, Science.

[29]  N. Zimmermann,et al.  Role of siglecs and related glycan-binding proteins in immune responses and immunoregulation. , 2015, The Journal of allergy and clinical immunology.

[30]  Clinical diagnostics and therapy monitoring in the congenital disorders of glycosylation , 2016, Glycoconjugate Journal.

[31]  J. Švitel,et al.  CORRIGENDUM: Glycan and lectin microarrays for glycomics and medicinal applications , 2010 .

[32]  S. Pinho,et al.  Glycosylation in cancer: mechanisms and clinical implications , 2015, Nature Reviews Cancer.

[33]  J. Tkáč,et al.  Carboxybetaine Modified Interface for Electrochemical Glycoprofiling of Antibodies Isolated from Human Serum , 2015, Langmuir : the ACS journal of surfaces and colloids.

[34]  J. Homola,et al.  Functionalizable surface platform with reduced nonspecific protein adsorption from full blood plasma--material selection and protein immobilization optimization. , 2009, Biosensors & bioelectronics.

[35]  Shaoyi Jiang,et al.  Inhibition of bacterial adhesion and biofilm formation on zwitterionic surfaces. , 2007, Biomaterials.

[36]  Shaoyi Jiang,et al.  Blood compatibility of surfaces with superlow protein adsorption. , 2008, Biomaterials.

[37]  F. Batteux,et al.  Impact of autoantibody glycosylation in autoimmune diseases. , 2014, Autoimmunity reviews.

[38]  G M Whitesides,et al.  A strategy for the generation of surfaces presenting ligands for studies of binding based on an active ester as a common reactive intermediate: a surface plasmon resonance study. , 1999, Analytical chemistry.

[39]  J. Emnéus,et al.  A steady-state and flow-through cell for screen-printed eight-electrode arrays , 2005 .

[40]  T. Stehle,et al.  The sweet spot: defining virus–sialic acid interactions , 2014, Nature Reviews Microbiology.

[41]  Robert M. Anthony,et al.  Recapitulation of IVIG Anti-Inflammatory Activity with a Recombinant IgG Fc , 2008, Science.

[42]  Jason J. Davis,et al.  Peptide aptamers in label-free protein detection: 2. Chemical optimization and detection of distinct protein isoforms. , 2009, Analytical chemistry.

[43]  Richard D Cummings,et al.  The challenge and promise of glycomics. , 2014, Chemistry & biology.

[44]  P. Seeberger,et al.  Simply better glycoproteins , 2014, Nature Biotechnology.

[45]  G. Whitesides,et al.  Adsorption of proteins onto surfaces containing end-attached oligo(ethylene oxide): a model system using self-assembled monolayers , 1993 .

[46]  L. Joshi,et al.  Microarray evaluation of the effects of lectin and glycoprotein orientation and data filtering on glycoform discrimination , 2014 .

[47]  S. Rexhepi,et al.  Comparison of seronegative and seropositive rheumatoid arthritis with regard to some clinical characteristics. , 2009, Reumatizam.

[48]  J. Tkáč,et al.  Electrochemical lectin based biosensors as a label-free tool in glycomics , 2012, Microchimica Acta.

[49]  J. Tkáč,et al.  Sensitive detection and glycoprofiling of a prostate specific antigen using impedimetric assays. , 2016, The Analyst.

[50]  Valtencir Zucolotto,et al.  Disposable biosensors for clinical diagnosis. , 2014, Journal of nanoscience and nanotechnology.

[51]  Shaoyi Jiang,et al.  Cross-linked carboxybetaine SAMs enable nanoparticles with remarkable stability in complex media. , 2014, Langmuir.

[52]  Shuichi Takayama,et al.  Zwitterionic SAMs that Resist Nonspecific Adsorption of Protein from Aqueous Buffer. , 2001, Langmuir : the ACS journal of surfaces and colloids.

[53]  J. Katrlik,et al.  An ultrasensitive impedimetric glycan biosensor with controlled glycan density for detection of lectins and influenza hemagglutinins. , 2015, Chemical communications.

[54]  Jui-Che Lin,et al.  Solvent and concentration effects on the surface characteristics and platelet compatibility of zwitterionic sulfobetaine-terminated self-assembled monolayers. , 2013, Colloids and surfaces. B, Biointerfaces.