Fabrication of low-cost sustainable electrocatalyst: a diagnostic tool for multifunctional disorders in human fluids.

In purine metabolism, the xanthine oxidoreductase enzyme converts hypoxanthine (HXN) to xanthine (XN) and XN to uric acid (UA). This leads to the deposition of UA crystals in several parts of the body and the serum UA level might be associated with various multifunctional disorders. The dietary intake of caffeine (CF) and ascorbic acid (AA) decreases the UA level in the serum, which leads to cellular damage. Hence, it is highly needed to monitor the UA level in the presence of AA, XN, HXN, and CF and vice versa. Considering this sequence of complications, the present paper reports the fabrication of an electrochemical sensor using low-cost N-doped carbon dots (CDs) for the selective and simultaneous determination of UA in the presence of AA, XN, HXN, and CF at the physiological pH. The colloidal solution of CDs was prepared by the pyrolysis of asparagine and fabricated on a GC electrode by cycling the potential from -0.20 to +1.2 V in a solution containing CDs and 0.01 M H2SO4. Here, the surface -NH2 functionalities of CDs were used to make a thin film of CDs on the GC electrode. FT-IR spectroscopy confirmed the involvement of the -NH2 group in the formation of the CD film. HR-TEM analysis depicts that the formed CDs showed spherical particles with a size of 1.67 nm and SEM analysis exhibits the 89 nm CD film on the GC electrode surface. The fabricated CD film was successfully used for the sensitive and selective determination of UA. The determination of UA was achieved selectively in a mixture consisting of AA, XN, HXN, and CF with 50-fold high concentration. The CDs-film fabricated electrode has several benefits over the bare electrode: (i) well-resolved oxidation peaks for five analytes, (ii) boosted sensitivity, (iii) shifted oxidation as well as on-set potentials toward less positive potentials, and (iv) high stability. The practical utility of the present sensor was tested by simultaneously determining the multifactorial disorders-causing agents in human fluids. The electrocatalyst developed in the present study is sustainable and can be used for multiple analyses; besides, the electrochemical method used for the fabrication of the CD film is environmentally benign.

Carbon dots stabilized silver-lipid nano hybrids for sensitive label free DNA detection.

Carbon dots have been extensively used for the development of fluorescent based molecular affinity sensors. However, label free DNA sensing by electrochemical method is not reported so far. Herein, we report carbon dots stabilized silver nanoparticles (CD-AgNPs) lipid nano hybrids as a sensitive and selective platform for label free electrochemical DNA sensing. The CD-AgNPs were synthesized by wet chemical method and then characterized by UV-visible, Fourier-transform Infra-red (FT-IR), dynamic light scattering (DLS) and high resolution transmission electron microscopy (HR-TEM) techniques. These CD-AgNPs were used for decorating the binary lipid 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) and N-[1-(2,3-Dioleoyloxy)propyl]-N,N,N-trimethylammonium chloride (DOTAP) surface (named as lipid) and tethered on self-assembled monolayer of 3-mercaptopropionic acid (MPA) (MPA-lipid-CD-AgNPs). The formation of array of MPA-lipid-CD-AgNPs on Au electrode was confirmed by atomic force microscopy (AFM). Electrochemical behavior of MPA- lipid-CD-AgNPs was monitored in the presence of 1 mM potassium ferri/ferrocyanide (K3/K4 [Fe(CN)6]). The formation of layer-by-layer MPA-lipid-CD-AgNPs is indicated by increased anodic and cathodic peak (ΔEp) separation with decreased redox peak current of K3/K4 [Fe(CN)6]. Short chain DNA (30 mer oligonucleotide, representing the lung cancer) was used as a model system for label free DNA sensing. Un-hybridized (single stranded DNA), hybridized (complementary hybridized), single, double and triple base mismatched target DNA hybridized surfaces were efficiently discriminated at 1 µM target DNA concentration at the Au/MPA-lipid-CD-AgNPs electrode by change in the charge transfer resistance from impedance technique. Further, the modified electrode was successfully used to determine target DNA in a wide linear range from 10-16 to 10-11 M. The present work open doors for the utilization of CDs in molecular affinity based electrochemical sensor design and development.

Fabrication of nitrogen-doped carbon dots for screening the purine metabolic disorder in human fluids.

Fabrication of nitrogen-doped carbon dots (N-CDs) electrode for the screening of purine metabolic disorder was described in this paper. Peroxynitrite is a short-lived oxidant species that is a potent inducer of cell death. Uric acid (UA) can scavenge the peroxynitrite to avoid the formation of nitrotyrosine, which is formed from the reaction between peroxynitrite and tyrosine (Try). Scavenging the peroxynitrite avoids the inactivation of cellular enzymes and modification of the cytoskeleton. Reduced level of UA decreases the ability of the body from preventing the peroxynitrite toxicity. On the other hand, the abnormal level of UA leads to gout and hyperuricemia. Allopurinol (AP) is administered in UA lowering therapy. Thus, the simultaneous determination of UA, Try and AP using N-CDs modified glassy carbon (GC) electrode was demonstrated for the first time. Initially, N-CDs were prepared from L-asparagine by pyrolysis and characterized by different spectroscopic and microscopic techniques. The HR-TEM image shows that the average size of the prepared N-CDs was 1.8±0.03nm. Further, the N-CDs were directly attached on GC electrode by simple immersion, follows Micheal's nucleophilic addition. XPS of N-CDs shows a peak at 285.3eV corresponds to the formation of C-N bond. The GC/N-CDs electrode shows higher electrocatalytic activity towards UA, Tyr and AP by not only shifting their oxidation potentials toward less positive potential but also enhanced their oxidation currents in contrast to bare GC electrode. The GC/N-CDs electrode shows the limit of detection of 13×10-10M (S/N=3) and the sensitivity of 924µAmM-1cm-2 towards the determination of UA. Finally, the N-CDs modified electrode was utilized for the determination of UA, Tyr and AP in human blood serum and urine samples.