Controlled
assembly of mesoscopic structures can bring interesting
phenomena because of their interfaces. Here, carbon nanotubes (CNTs)
are cross-coupled via a C–C bonding through Suzuki reaction
resulting in three-dimensional (3D) CNT sponges, and these 3D CNTs
are studied for their efficacy toward the electrocatalytic hydrogen
evolution reaction (HER) in acidic mediumone of the promising
methods for the production of a renewable energy source, hydrogen.
Both single and multiwall CNTs (SWCNTs and MWCNTs) are studied for
the development of 3DSWCNTs and 3DMWCNTs, and these 3D CNTs are found
to be HER active with small reaction onset potentials and low charge-transfer
resistances unlike their uncoupled counterparts. First-principle density
functional calculations show that the combination of electron acceptor
and donor bonded to the CNT network can provide a unique band structure
modulation in the system facilitating the HER reaction. This study
can provide possibilities for band engineering of CNTs via functionalization
and cross-coupling reactions.
Zinc
and copper are essential metal ions for numerous biological
processes. Their levels are tightly maintained in all body organs.
Impairment of the Zn2+ to Cu2+ ratio in serum
was found to correlate with many disease states, including immunological
and inflammatory disorders. Oxytocin (OT) is a neuropeptide, and its
activity is modulated by zinc and copper ion binding. Harnessing the
intrinsic properties of OT is one of the attractive ways to develop
valuable metal ion sensors. Here, we report for the first time an
OT-based metal ion sensor prepared by immobilizing the neuropeptide
onto a glassy carbon electrode. The developed impedimetric biosensor
was ultrasensitive to Zn2+ and Cu2+ ions at
physiological pH and not to other biologically relevant ions. Interestingly,
the electrochemical impedance signal of two hemicircle systems was
recorded after the attachment of OT to the surface. These two semicircles
suggest two capacitive regions that result from two different domains
in the OT monolayer. Moreover, the change in the charge-transfer resistance
of either Zn2+ or Cu2+ was not similar in response
to binding. This suggests that the metal-dependent conformational
changes of OT can be translated to distinct impedimetric data. Selective
masking of Zn2+ and Cu2+ was used to allow for
the simultaneous determination of zinc to copper ions ratio by the
OT sensor. The OT sensor was able to distinguish between healthy control
and multiple sclerosis patients diluted sera samples by determining
the Zn/Cu ratio similar to the state-of-the-art techniques. The OT
sensor presented herein is likely to have numerous applications in
biomedical research and pave the way to other types of neuropeptide-derived
sensors.
Single molecule detection using graphene can be brought by tuning the interactions via specific dopants. Electrostatic interaction between the most electronegative element fluorine (F) and hydrogen (H) is one of the strong interactions in hydrogen bonding, and here we report the selective binding of ammonia/ammonium with F in fluorographene (FG) resulting to a change in the impedance of the system. Very low limit of detection value of ~0.44 pM with linearity over wide range of concentrations (1 pM–0.1 μM) is achieved using the FG based impedance sensor, andthisscreen printed FG sensor works in both ionized (ammonium) and un-ionized ammonia sensing platforms. The interaction energies of FG and NH3/NH4+ are evaluated using density functional theory calculations and the interactions are mapped. Here FGs with two different amounts of fluorinecontents −~5 atomic% (C39H16F2) and ~24 atomic% (C39H16F12) - are theoretically and experimentally studied for selective, high sensitive and ultra-low level detection of ammonia. Fast responding, high sensitive, large area patternable FG based sensor platform demonstrated here can open new avenues for the development of point-of-care devices and clinical sensors.
Molecularly imprinted polymer (MIP) for sulfanilamide (SN) sensing is prepared through in‐situ electropolymerization of pyrrole (Py) on pencil graphite electrode (PGE). Computational study using density functional theory with B3LYP level is performed to analyze and evaluate the template‐monomer geometry. Among the various functional monomers studied pyrrole is found to have the highest binding interaction energy with SN and it is chosen as a functional monomer. Electropolymerization of pyrrole in the presence of SN on PGE is carried out using cyclic voltammetry. Structural morphology of the imprinted polymer is characterized by field emission scanning electron microscopy (FESEM) studies. Quantitative measurements of MIP based SN detection are performed by using cyclic voltammetry and differential pulse voltammetry studies. Several important kinetic parameters influencing the performance of SN sensor such as limit of detection, linear concentration range and sensitivity etc. are determined and analyzed. Under the optimized conditions, MIP based SN sensor proposed in this work has a very low detection limit of 2.0×10−8 M (S/N=3) and possesses two linear ranges from 5.0×10−8 to 1.1×10−6 M and 1.1×10−6 to 48×10−6 M with a sensitivity value of 1.158 and 0.012 µA/µM respectively. This particular sensor shows a good selectivity towards SN in presence of potential other structural analogue interferences namely sulfamethaxazole, sulfathiazole and sulfadiazine. Furthermore, the fabricated sensor is successfully applied to quantitatively determine and analyze SN present in spiked human serum and ground water samples.
Molecularly imprinted polymer (MIP) for uric acid (UA) was synthesized by thermal polymerization using acrylic acid (AA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as cross linker and 2,2′‐azobis(2‐isobutyro) nitrile (AIBN) as initiator. The noncovalent interactions involved in four possible conformations of pre‐polymer complex were computationally studied by density functional theory. The hydrogen bond formation between UA and AA was confirmed by Fourier transform infrared (FTIR) spectrum of the MIP before extraction of UA. After extraction of the template, the molecularly imprinted polymer based carbon paste electrode (MIPCPE) was fabricated under optimized conditions. A significant enhancement in the electrocatalytic oxidation of UA was found at MIPCPE. The electrochemical behavior of sensor was investigated by cyclic voltammetry (CV) and differential pulse adsorptive stripping voltammetry (DPAdSV). The electrochemical impedance spectroscopy (EIS) studies revealed less charge transfer resistance (Rct) at MIPCPE than NIPCPE. Under optimized conditions, calibration curve was obtained with a linearity range of 0.5 µM to 100 µM and the limit of detection was 0.1 µM. The sensor showed good selectivity towards UA in the presence of interferents and was successfully applied for the determination of UA in spiked serum samples.
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