An extensive characterization of pristine and oxidized TiCT (T: =O, -OH, -F) MXene showed that exposure of MXene to an anodic potential in the aqueous solution oxidizes the nanomaterial forming TiO layer or TiO domains with subsequent TiO dissolution by F ions, making the resulting nanomaterial less electrochemically active compared to the pristine TiCT. The TiCT could be thus applied for electrochemical reactions in a cathodic potential window i.e. for ultrasensitive detection of HO down to nM level with a response time of approx. 10 s. The manuscript also shows electrochemical behavior of TiCT modified electrode towards oxidation of NADH and towards oxygen reduction reactions.

This review comprehensively covers the most recent achievements (from 2013) in the successful integration of nanomaterials in the field of glycomics. The first part of the paper addresses the beneficial properties of nanomaterials for the construction of biosensors, bioanalytical devices, and protocols for the detection of various analytes, including viruses and whole cells, together with their key characteristics. The second part of the review focuses on the application of nanomaterials integrated with glycans for various biomedical applications, that is, vaccines against viral and bacterial infections and cancer cells, as therapeutic agents, for in vivo imaging and nuclear magnetic resonance imaging, and for selective drug delivery. The final part of the review describes various ways in which glycan enrichment can be effectively done using nanomaterials, molecularly imprinted polymers with polymer thickness controlled at the nanoscale, with a subsequent analysis of glycans by mass spectrometry. A short section describing an active glycoprofiling by microengines (microrockets) is covered as well.

Screening serum for the presence of prostate specific antigen (PSA) belongs to the most common approach for the detection of prostate cancer. This review (with 156 refs.) addresses recent developments in PSA detection based on the use of various kinds of nanomaterials. It starts with an introduction into the field, the significance of testing for PSA, and on current limitations. A first main section treats electrochemical biosensors for PSA, with subsections on methods based on the use of gold electrodes, graphene or graphene-oxide, carbon nanotubes, hybrid nanoparticles, and other types of nanoparticles. It also covers electrochemical methods based on the enzyme-like activity of PSA, on DNA-, aptamer- and biofuel cell-based methods, and on the detection of PSA via its glycan part. The next main section covers optical biosensors, with subsections on methods making use of surface plasmon resonance (SPR), localized SPR and plasmonic ELISA-like schemes. This is followed by subsections on methods based on the use of fiber optics, fluorescence, chemiluminescence, Raman scattering and SERS, electrochemiluminescence and cantilever-based methods. The most sensitive biosensors are the electrochemical ones, with lowest limits of detection (down to attomolar concentrations), followed by mass cantilever sensing and electrochemilumenescent strategies. Optical biosensors show lower performance, but are still more sensitive compared to standard ELISA. The most commonly applied nanomaterials are metal and carbon-based ones and their hybrid composites used for different amplification strategies. The most attractive sensing schemes are summarized in a Table. The review ends with a section on conclusions and perspectives.

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.

Extended AbstractGlycans are complex saccharide moieties covering all cell surfaces -presented on different biomolecules. Almost 75% of all proteins are glycosylated, and these glycans can form thousands of different structures.[1] Moreover, these structures may slightly change during a specific disease progress -depending on the biomarker observed, there is a possibility to distinguish between healthy individuals and people suffering from a specific disease, mostly cancer (prostate cancer using PSA as a biomarker) [2] or autoimmune diseases (rheumatoid arthritis, system sclerosis observing IgG N-glycosylation).[3] Viral adhesion on cell surface and subsequent penetration is also dependent on the glycan epitopes present on a cell surface. [4,5] Using nanoscale manipulation of biorecognition elements (antibodies, lectins as glycan-bindnig proteins or glycans) using self-assembled monolayers (SAMs) allowed to prepare highly sensitive, reproducible and robust biosensors for detection of various analytes -from glycoproteins and whole viral particles to intact cells. Moreover, using SAMs allows to control a biorecognition element´s density, orientation and anti-fouling properties of our surfaces.[6] Using nanomaterials like gold nanoparticles of different size or graphene oxide flakes leads to improved characteristics of prepared deviceselectrochemical and impedimetric biosensors in this case. Electrochemical devices, mainly in combination with different nanostructures, provide cheap, highly reliable and sensitive platform for glycomic analyses. [7] We present here a novel approach for a glycoprofilation of various analytes (antibodies, PSA, viral hemagglutinins and viruses and eukaryotic cell lines) using small, low cost, highly sensitive electrochemical devices based on different platforms compared to standardly used LC, CE or MS methods for the glycan analysis. Beside electrochemical impedance spectroscopy and voltammetry, other methods for the surface characterization were used (quartz crystal microbalance, surface plasmon resonance, atomic force and scanning electron microscopy and x-ray photoelectron spectroscopy) and our results were compared to outputs from other analytical methods (protein microarray, enzyme-linked lectin assay and MALDI-TOF MS).