Highly Efficient Solid‐Phase Labeling of Saccharides within Boronic Acid Functionalized Mesoporous Silica Nanoparticles

Abstract

Labeling is critical for the detection, quantitation, and structural identification of saccharides.H owever,conventional liquid-phase labeling suffers from apparent disadvantages,s uch as time-consuming,t he presence of excessive labeling reagent, and high applicable saccharide concentration. As olid-phase approachi sp resented for highly efficient labeling of saccharides,u sing boronic acid functionalized mesoporous silica nanoparticles (MSNs) as as elective extraction sorbent and nanoscale reactor.T he solid-phase labeling approach exhibited several significant advantages,i ncluding: muchf aster reaction speed (taking only 2min), high product purity,a nd muchl ower applicable saccharidec oncentration (four orders of magnitude lower than that of liquid-phase labeling). Thus,t his labeling approach opens up new avenues to the facile and efficient labeling of saccharides.Saccharides,asessential components of all living systems, are the major compounds of interest in many fields such as biochemistry,b iomedicine,g lycomics,a nd glycobiology.S accharides have no fluorescence,l imited UV/Vis absorbance, and ap oor mass spectrometry (MS) signal, and therefore labeling with an appropriate signal-producing reagent is thereby ac ritical step prior to their detection, quantitative analysis,and structural identification. [1] Thelabeling is usually carried out in the liquid phase. [2] However,itisassociated with apparent disadvantages,i ncluding time-consuming,t he presence of excessive labeling reagent, and higher concentration requirement of the saccharide to be labeled. Therefore,n ew labeling approaches that can overcome these drawbacks are of significant importance. Mesoporous materials, [3] which possess highly ordered mesopores and high specific surface areas,h ave exhibited great potentials for applications in av ariety of important areas,s uch as catalysis, [4] sensing, [5] sorption, [6] separation, [7] and drug delivery. [8] In the last decade,mesoporous materials, and particularly mesoporous silica nanoparticles (MSNs) MCM-41, [9] have been important sorbents for sample pretreatment. [10] They allowed for size-selective extraction and effective enrichment. [10d-f] Besides,e nzyme-encapsulated mesoporous materials have been used as nanoscale reactors for enzymatic digestion of proteins and it was found that the digestion speed was significantly enhanced. [11] Moreover,i t was revealed that intermolecular interactions within mesoporous materials can be significantly enhanced due to nanoscale confinement effect. [12] However,t he merits of mesoporous materials as nanoscale reactors for solid-phase labeling have not yet been well exploited.In this study,u sing boronic acid functionalized MSNs as as elective extraction sorbent and nanoscale reactor, we present for the first time as olid-phase labeling approach for the highly efficient derivatization of saccharides.T he principle and procedure of this approach are illustrated in Scheme 1. Thec ore for the highly efficient labeling is the pH-controlled capture/r...

Analysis of Carbohydrates and Glycoconjugates by Matrix‐assisted Laser Desorption/Ionization Mass Spectrometry: An Update for 2015–2016

“…Conventional liquid‐phase labelling of carbohydrates frequently suffers from the presence of excessive labelling reagent which has to be removed before glycan analysis. A solid‐phase approach has been developed by Pan et al (2015a) using boronic acid functionalized mesoporous silica nanoparticles as selective extraction sorbents at the nanogram scale. The method exhibited several significant advantages over traditional methods, including a much faster reaction time, in the order of 2 min for the preparation of 1‐phenyl‐3‐methyl‐5‐pyrazolone (PMP 5/7 ) derivatives and higher product purity.…”

Fabrication of Surface Protein-Imprinted Biofuel Cell for Sensitive Self-Powered Glycoprotein Detection

“…The miniaturized printed carbon electrode chips with two electrodes were prepared on the plastic plates by using a standard microfabrication technique . The MIP/HRP­(AFP)/APBA/BOD/CNT electrode was applied as the biocathode.…”

“…Molecularly imprinted polymers (MIPs) with the specific binding affinity for biological receptors are of great interest for the development of highly selective sensors. Based on the reversible covalent binding between boronic acid and sugar, MIPs have been designed to specifically recognize proteins through Raman, fluorescence, chemiluminiscence, etc. ,− The boronate-affinity MIPs can offer a greater stability, lower cost, and better engineering opportunity than traditional biological receptors, such as antibody and aptamer, thus making them appealing alternatives to antibodies or aptamer for bioassays. , In this regard, the combination of MIPs with BFCs may generate new analytical approaches that outperform the conventional immunoassays.…”

Efficient Enrichment and Analysis of Vicinal-Diol-Containing Flavonoid Molecules Using Boronic-Acid-Functionalized Particles and Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry

“…The use of MALDI–TOF MS as an analytical tool for small molecules offers many advantages over other conventional methods in terms of easy sample preparation, rapidity, high sensitivity, low background signals, and no false-positive signals. − In addition, mass spectrometry (MS) analysis has excellent multiplexing capability because it provides molecular weights of analytes and, thus, distinctively discriminates multiple analytes, despite structural similarity. In our strategy, boronic-acid-functionalized polyacrylamide particles (BAPs) were harnessed for selective isolation of vicinal-diol-containing flavonoid molecules, where boronic acids dominantly form boronate monoester complexes with vicinal diols at basic pH, while decomplexation occurs in the acidic environment, resulting in the recovery of boronic acid and vicinal diol functionality. − Using this characteristic, boronic-acid-functionalized materials have been widely used for the analysis of vicinal-diol-containing hydrophilic biomolecules, mostly saccharides, − nucleosides, glycopeptides, and glycoproteins, − and for various applications, including drug delivery systems, enzymatic inhibitions, and cell-capture/release systems. ,− However, very few examples have been reported for the study of hydrophobic molecules, such as flavonoids, because of its low water solubility and interference of other vicinal-diol-containing biomolecules existing in biological systems in high abundance. , As a typical example, Zhang et al introduced boronate affinity adsorption of cis -diol-containing hydrophobic molecules in non-aqueous solvents, such as methanol, acetonitrile, and ethyl acetate …”