Surface Tailoring-Modulated Bifunctional Oxygen Electrocatalysis with CoP for Rechargeable Zn-Air Battery and Water Splitting.

The transition metal phosphide (TMP)-based functional electrocatalysts are very promising for the development of electrochemical energy conversion and storage devices including rechargeable metal-air batteries and water electrolyzer. Tuning the electrocatalytic activity of TMPs is one of the vital steps to achieve the desired performance of these energy devices. Herein, we demonstrate the modulation of the bifunctional oxygen electrocatalytic activity of nitrogen-doped carbon-encapsulated CoP (CoP@NC) nanostructures by surface tailoring with ultralow amount (0.56 atomic %) of Ru nanoparticles (2.5 nm). The CoP at the core and the Ru nanoparticles on the shell have a facile charge transfer interaction with the encapsulating NC. The strong coupling of Ru with CoP@NC boosts the electrocatalytic performance toward oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution (HER) reactions. The surface-tailored catalyst requires only 35 mV to deliver the benchmark current density of 10 mA·cm-2 for HER. A small potential gap of 620 mV between ORR and OER is achieved, making the catalyst highly suitable for the development of rechargeable zinc-air batteries (ZABs). The homemade ZAB delivers a specific capacity of 780 mA·hgZn-1 and peak power density of 175 mW·cm-2 with a very small voltaic efficiency loss (1.1%) after 300 cycles. The two-electrode water splitting cell (CoP@NC-Ru||CoP@NC-Ru) delivers remarkably low cell voltage of 1.47 V at the benchmark current density. Stable current density of 25 mA·cm-2 for 25 h without any significant change is achieved. Theoretical studies support the charge transfer interaction-induced enhanced electrocatalytic activity of the surface-tailored nanostructure.

Defect Engineered Ternary Spinel: An Efficient Cathode for an Aqueous Rechargeable Zinc-Ion Battery of Long-Term Cyclability.

The rational defect engineering of Mn-based spinel cathode materials by metal-ion doping and vacancy creation fosters reversible intercalation/deintercalation of charge carriers and boosts the charge storage performance of an aqueous rechargeable zinc-ion battery (ZIB). Herein, we demonstrate the Zn2+ ion storage performance of a defect-engineered ternary spinel cathode based on Zn, Ni, and Mn. The defect engineering of ZnMn2O4 is achieved by Ni2+ doping and creating a cation (Mn3+ and Zn2+) deficiency. The engineered cathode material has cubic spinel structure in contrast to the defect-free ZnMn2O4. The DFT studies show that the defect engineering modifies the electronic structure and improves the electronic conductivity. An aqueous rechargeable ZIB is fabricated by using the spinel cathode, and its performance is evaluated in terms of charge-discharge cycling stability, specific capacity, and so on. The ternary spinel-based ZIB has a very long charge-discharge cycling stability with a specific capacity as high as 265 mAh g-1 (at 100 mA g-1). A 2-fold enhancement in the specific capacity is observed after 5000 cycles. Ni doping affords ultralong cycling stability. The self-discharge studies for a year show that the device retains 63% of the initial performance.

Heteroatom-Doped Carbon-Encapsulated FeP Nanostructure: A Multifunctional Electrocatalyst for Zinc-Air Battery and Water Electrolyzer.

The rational design and synthesis of efficient multifunctional electrocatalysts for renewable energy technologies is of significant interest. Herein, we demonstrate a novel approach for the synthesis of a nitrogen and phosphorus dual-doped mesoporous carbon-encapsulated iron phosphide (FeP@NPC) nanostructure and its multifunctional electrocatalytic activity toward an oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction for zinc-air battery (ZAB) and alkaline water-splitting applications. FeP@NPC is obtained by the carbothermal reduction of the precursor complex [Fe(bpy)3](PF6)2 in the presence of melamine without any traditional phosphidating agent. The PF6- counteranion is used for the phosphidation of Fe. FeP@NPC obtained at 900 °C (FeP@NPC-900) exhibits excellent bifunctional oxygen electrocatalytic performance with a very low potential gap (ΔE = E1/2ORR - Ej10OER) of 670 mV. The ZAB device delivers a peak power density of 190.15 mW cm-2 (iR-corrected), specific capacity of 785 mA h gZn-1, and energy density of 706.5 Wh kgZn-1 at 50 mA cm-2. The ZAB exhibits excellent charge-discharge cycling stability for over 35 h with negligible voltaic efficiency loss (0.9%). Three CR2032 coin-cell-based ZABs made of an FeP@NPC-900 air cathode connected in series power 81 LEDs for 15 min. FeP@NPC-900 also has promising electrocatalytic activity toward water splitting in acidic as well as in alkaline pH. The benchmark current density of 10 mA cm-2 is achieved with a two-electrode alkaline water electrolyzer at a cell voltage of 1.65 V. ZAB-powered water electrolyzer is made by integrating two rechargeable ZABs connected in series with the two-electrode water electrolyzer. The ZAB powers the electrolyzer for 24 h without a significant loss in the open-circuit voltage. The catalyst retains its initial structural integrity even after continuous water electrolysis for 24 h.

Advanced Oxygen Electrocatalyst for Air-Breathing Electrode in Zn-Air Batteries.

The electrochemical reduction of oxygen to water and the evolution of oxygen from water are two important electrode reactions extensively studied for the development of electrochemical energy conversion and storage technologies based on oxygen electrocatalysis. The development of an inexpensive, highly active, and durable nonprecious-metal-based oxygen electrocatalyst is indispensable for emerging energy technologies, including anion exchange membrane fuel cells, metal-air batteries (MABs), water electrolyzers, etc. The activity of an oxygen electrocatalyst largely decides the overall energy storage performance of these devices. Although the catalytic activities of Pt and Ru/Ir-based catalysts toward an oxygen reduction reaction (ORR) and an oxygen evolution reaction (OER) are known, the high cost and lack of durability limit their extensive use for practical applications. This review article highlights the oxygen electrocatalytic activity of the emerging non-Pt and non-Ru/Ir oxygen electrocatalysts including transition-metal-based random alloys, intermetallics, metal-coordinated nitrogen-doped carbon (M-N-C), and transition metal phosphides, nitrides, etc., for the development of an air-breathing electrode for aqueous primary and secondary zinc-air batteries (ZABs). Rational surface and chemical engineering of these electrocatalysts is required to achieve the desired oxygen electrocatalytic activity. The surface engineering increases the number of active sites, whereas the chemical engineering enhances the intrinsic activity of the catalyst. The encapsulation or integration of the active catalyst with undoped or heteroatom-doped carbon nanostructures affords an enhanced durability to the active catalyst. In many cases, the synergistic effect between the heteroatom-doped carbon matrix and the active catalyst plays an important role in controlling the catalytic activity. The ORR activity of these catalysts is evaluated in terms of onset potential, number of electrons transferred, limiting current density, and durability. The bifunctional oxygen electrocatalytic activity and ZAB performance, on the other hand, are measured in terms of potential gap between the ORR and OER, ΔE = Ej10OER - E1/2ORR, specific capacity, peak power density, open circuit voltage, voltaic efficiency, and charge-discharge cycling stability. The nonprecious metal electrocatalyst-based ZABs are very promising and they deliver high power density, specific capacity, and round-trip efficiency. The active site for oxygen electrocatalysis and challenges associated with carbon support is briefly addressed. Despite the considerable progress made with the emerging electrocatalysts in recent years, several issues are yet to be addressed to achieve the commercial potential of rechargeable ZAB for practical applications.

Hierarchical Hollow MOF-Derived Bamboo-like N-doped Carbon Nanotube-Encapsulated Co0.25Ni0.75 Alloy: An Efficient Bifunctional Oxygen Electrocatalyst for Zinc-Air Battery.

The synthesis of nonprecious electrocatalysts for oxygen electrocatalysis is of considerable interest for the development of electrochemical energy devices. Herein, we demonstrate a facile approach for the synthesis of bamboo-like nitrogen-doped carbon nanotube-encapsulated Co0.25Ni0.75 alloy electrocatalyst (Co0.25Ni0.75@NCNT) and its bifunctional oxygen electrocatalytic performance toward oxygen reduction and oxygen evolution reactions. The Co0.25Ni0.75 alloy wrapped with NCNT is obtained by a one-step carbothermal reduction approach using dicyandiamide and NiCo-MOF precursors. Dicyandiamide acts as a nitrogen source, and the in situ generated Co0.25Ni0.75 alloy nanoparticles catalyze the growth of bamboo-like NCNTs. The hollow NiCo-MOF plays a sacrificial role in providing a suitable environment for the controlled growth of Co0.25Ni0.75 alloy and NCNT. Co0.25Ni0.75@NCNT efficiently catalyzes both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) at a favorable overpotential. It shows a low potential gap (ΔE) of ∼0.8 V between the two reactions, and it qualifies for the development of air cathode in metal-air batteries. The enhanced bifunctional activity and excellent durability stem from the chemical composition and the synergistic effect between Co0.25Ni0.75 alloy and encapsulating NCNT. The original phase and morphology of the catalyst is preserved after an extensive durability test. Aqueous rechargeable Zn-air battery (ZAB) is fabricated using a Co0.25Ni0.75@NCNT-based air cathode. The battery has high open-circuit voltage (1.53 V) and a maximum peak power density of 167 mW cm-2 with only 1.6% loss in the voltaic efficiency after 36 h charge-discharge cycles. As a proof-of-concept demonstration, the as-fabricated ZAB is successfully used for the electrochemical water splitting in alkaline solution.

Aqueous Rechargeable Zn-ion Batteries: Strategies for Improving the Energy Storage Performance.

The growing demand for the renewable energy storage technologies stimulated the quest for efficient energy storage devices. In recent years, the rechargeable aqueous zinc-based battery technologies are emerging as a compelling alternative to the lithium-based batteries owing to safety, eco-friendliness, and cost-effectiveness. Among the zinc-based energy devices, rechargeable zinc-ion batteries (ZIBs) are drawing considerable attention. However, they are plagued with several issues, including cathode dissolution, dendrite formation, etc.. Despite several efforts in the recent past, ZIBs are still in their infant stages and have yet to reach the stage of large-scale production. Finding stable Zn2+ intercalation cathode material with high operating voltage and long cycling stability as well as dendrite-free Zn anode is the main challenge in the development of efficient zinc-ion storage devices. This Review discusses the various strategies, in terms of the engineering of cathode, anode and electrolyte, adopted for improving the charge storage performance of ZIBs and highlights the recent ZIB technological innovations. A brief account on the history of zinc-based devices and various cathode materials tested for ZIB fabrication in the last five years are also included. The main focus of this Review is to provide a detailed account on the rational engineering of the electrodes, electrolytes, and separators for improving the charge storage performance with a future perspective to achieving high energy density and long cycling stability and large-scale production for practical application.

A Self-Healing Metal-Organic Hydrogel for an All-Solid Flexible Supercapacitor.

A zinc containing metal-organic gel (Zn-MOG) with embedded free ions, which exhibits self-healing properties, has been synthesized for application in supercapacitors. The activated carbon-based flexible supercapacitor device with the MOG electrolyte has a broad potential window of 2.1 V, with high retention of specific capacitance compared to the traditional polyvinyl alcohol (PVA)-based gel. The Zn-MOG does not require an additional electrolyte. The sodium and sulphate ions embedded in the MOG are sufficient enough for the charge storage.

Electrochemical Dealloying-Assisted Surface-Engineered Pd-Based Bifunctional Electrocatalyst for Formic Acid Oxidation and Oxygen Reduction.

Synthesis of non-Pt bifunctional electrocatalyst for the anodic oxidation of liquid fuel and cathodic reduction of oxygen is of great interest in the development of energy conversion devices. We demonstrate a facile room-temperature synthesis of surface-engineered trimetallic alloy nanoelectrocatalyst based on Co, Cu, and Pd by thermodynamically favorable transmetallation reaction and electrochemical dealloying. The quasi-spherical Co xCu yPd z trimetallic catalysts were synthesized by the thermodynamically favorable reaction of K2PdCl4 with sheetlike Co mCu n bimetallic alloy nanostructure. The surface engineering of Co xCu yPd z was achieved by electrochemical dealloying. The surface-engineered alloy electrocatalyst exhibits excellent bifunctional activity toward formic acid oxidation reaction (FAOR) and oxygen reduction reaction (ORR) at same pH. The elemental composition and lattice strain control the electrocatalytic performance. The elemental composition-dependent compressive strain weakens the adsorption of oxygen-containing species and favors the facile electron transfer for FAOR and ORR. The engineered alloy electrocatalyst of Co0.02Cu13.8Pd86.18 composition is highly durable and delivers high mass-specific activity for ORR and FAOR. It delivers mass-specific activities of 1.50 and 0.202 A/mgPd for FAOR and ORR, respectively, in acidic pH. The overall performance is superior to that of as-synthesized Pd and dealloyed bimetallic Co2.7Pd97.3 and Cu5.61Pd94.39 nanoelectrocatalysts.

Unzipping of Single-Walled Carbon Nanotube for the Development of Electrocatalytically Active Hybrid Catalyst of Graphitic Carbon and Pd Nanoparticles.

We demonstrate a new approach for the unzipping of single-walled carbon nanotube (SWCNT) in an aqueous solution using the transition metal complex PdCl4 2- as a sacrificial chemical scissor and the growth of graphitic-carbon-coated Pd nanoparticles for the electrocatalytic oxidation of formic acid. The chemical unzipping and the growth of Pd nanoparticles involve the spontaneous electron transfer between SWCNT and the metal complex in an aqueous solution at room temperature. The redox potential for SWCNT and PdCl4 2- favors the spontaneous electron transfer reaction. The metal complex, in situ generated Pd nanoparticle, and oxygen play vital role in the oxidative unzipping of SWCNT. The Pd nanoparticles have an average size of 11 nm and are coated with the graphitic carbon layer of unzipped SWCNT (UzCNT-Pd). The Pd nanoparticle of the UzCNT-Pd hybrid material has a large electrochemically active surface area of 2.14 cm2. The hybrid material exhibits excellent electrocatalytic activity toward the oxidation of formic acid. The area and mass specific activity are significantly higher than those of the traditional carbon-supported Pd nanoparticle. The synergistic effect of graphitic carbon and the metal nanoparticles controls the catalytic activity. The confinement of Pd particles inside the graphitic carbon enhances the overall performance of the catalyst.

Electrochemical Decoration of Carbon Nanotubes with Au Nanostructure for the Electroanalysis of Biomolecules.

An electrochemical route for the decoration of multiwalled carbon nanotubes (MWCNTs) with anisotropic Au nanostructures and the electroanalytical application of decorated MWCNTs are described. MWCNTs were electrochemically decorated with flowers and buds-like Au nanostructures in aqueous solution in the presence of KI. The flowers and buds-like nanostructures had an average size of 80 nm with a predominant Au(111) plane. The analytical application of the decorated MWCNTs in the electroanalysis of biologically important analytes, such as uric acid (UA), epinephrine (EN) and ascorbic acid (AA), was studied. The nanoparticles of flower-like morphology efficiently catalyze the oxidation of the bioanalytes at a less-positive potential. Simultaneous electroanalysis of AA, UA and EN have been achieved. Well separated individual voltammetric peaks were obtained in their coexistence. The decorated MWCNT modified electrode is very stable and highly sensitive towards UA and EN. It could detect micromolar levels of bioanalytes without any interference. The catalytic property of the nanostructures is superior to that of the conventional spherical nanoparticle. The morphology of the nanoparticle controls the electrocatalytic activity.

A Rationally Designed Thymidine-Based Self-Assembled Monolayer on a Gold Electrode for Electroanalytical Applications.

A self-assembled monolayer (SAM) of 1-(3,5-epidithio-2,3,5-trideoxy-ß-D-threo-pentofuranosyl)thymine (EFT) on a gold electrode was prepared and characterized by Raman spectral and electrochemical measurements. Voltammetric and electrochemical impedance measurements show that the SAM of EFT on a Au electrode impedes the electron-transfer reaction. The SAM of EFT was successfully used for the voltammetric sensing of urate in neutral solution. The coexisting ascorbate anion does not interfere and therefore the EFT-based electrode was able to quantify urate at the micromolar level in the presence of a large excess amount of ascorbate. To demonstrate the practical applications, the amount of urate in two different human serum samples was quantified by using the EFT-based electrode; the results are in good agreement with those determined by the clinical method. DFT calculations show that both ascorbate and urate have noncovalent interactions including hydrogen-bonding interactions with EFT.

Enzyme-integrated cholesterol biosensing scaffold based on in situ synthesized reduced graphene oxide and dendritic Pd nanostructure.

A new approach for the one-pot synthesis of reduced graphene oxide-dendritic Pd nanoparticle (rGO-nPd) hybrid material and the development of biosensing scaffold for the amperometric sensing of H2O2 and total cholesterol in human serum are described. In situ reduction of both graphene oxide (GO) and PdCl4(2-) in acidic solution was achieved with Zn to obtain rGO-nPd hybrid material. The oxygen containing functionalities of GO were reduced by the liberated atomic hydrogen in 20 min. The formal potential of Zn/Zn(2+) and PdCl4(2-)/Pd couples favor the facile reduction of PdCl4(2-). The in situ produced Pd nanoparticles behave like hydrogen sponge and increase the local concentration of atomic hydrogen. Biosensing platforms for H2O2 and cholesterol in human serum and butter sample were developed using the hybrid material. Amperometric sensing of H2O2 at 0.2 nM level without any redox mediator or enzymes in neutral pH is demonstrated. The cholesterol biosensing platform was developed by integrating cholesterol oxidase and cholesterol esterase with the hybrid material. The biosensor is highly sensitive (5.12±0.05 µA/µM cm(2)) and stable with a fast response time of 4 s; it could detect cholesterol ester as low as 0.05 µM (S/N=3). The biosensor is successfully used for the analysis of total cholesterol in human serum and butter.

Facile single-step synthesis of nitrogen-doped reduced graphene oxide-Mn(3)O(4) hybrid functional material for the electrocatalytic reduction of oxygen.

Development of efficient electrocatalyst based on non-precious metal that favors the four-electron pathway for the reduction of oxygen in alkaline fuel cell is a challenging task. Herein, we demonstrate a new facile route for the synthesis of hybrid functional electrocatalyst based on nitrogen-doped reduced graphene oxide (N-rGO) and Mn3O4 with pronounced electrocatalytic activity towards oxygen reduction reaction (ORR) in alkaline solution. The synthesis involves one-step in situ reduction of both graphene oxide (GO) and Mn(VII), growth of Mn3O4 nanocrystals and nitrogen doping onto the carbon framework using a single reducing agent, hydrazine. The X-ray photoelectron (XPS), Raman and FTIR spectral, and X-ray diffraction measurements confirm the reduction of GO and growth of nanosized Mn3O4. The XPS profile reveals that N-rGO has pyridinic (40%), pyrrolic (53%), and pyridine N oxide (7%) types of nitrogen. The Mn3O4 nanoparticles are single crystalline and randomly distributed over the wrinkled N-rGO sheets. The hybrid material has excellent ORR activity and it favors the 4-electron pathway for the reduction of oxygen. The electrocatalytic performance of the hybrid catalyst is superior to the N-rGO, free Mn3O4 and their physical mixture. The hybrid material shows an onset potential of -0.075 V, which is 60-225 mV less negative than that of the other catalyst tested. It has excellent methanol tolerance and high durability. The catalytic current density achieved with the hybrid material at 0.1 mg cm(-2) is almost equivalent to that of the commercial Pt/C (10%). The synergistic effect of N-rGO and Mn3O4 enhances the overall performance of the hybrid catalyst. The nitrogen in N-rGO is considered to be at the interface to bridge the rGO framework and Mn3O4 nanoparticles and facilitates the electron transfer.

Redox-functionalized graphene oxide architecture for the development of amperometric biosensing platform.

We describe the redox functionalization of graphene oxide (GO) and the development of versatile amperometric biosensing platforms for clinically important analytes such as cholesterol ester, uric acid and glucose. Ferrocene (Fc) redox units were covalently tethered onto the GO backbone using diamine sigma spacers of different chain lengths (C3-, C6-, and C9-diamines). The functionalized GO (Fc-GO) displays a pair of redox peak corresponding to Fc/Fc(+) redox couple at ~0.225 V. The surface coverage and heterogeneous electron transfer rate constant of Fc-GO depends on the length of sigma spacer. Amperometric biosensors for cholesterol (total), uric acid and glucose have been developed by integrating Fc-GO and the respective redox enzymes with screen printed electrode. Fc-GO efficiently mediates the bioelectrocatalytic oxidation of the substrates in the presence of the redox enzymes. The spacer length of Fc-GO controls the bioelectrocatalytic response of the biosensing platforms. The sensitivity of the biosensors based on C9 sigma spacer is significantly higher than the others. The detection limit (S/N = 3) of the biosensors for cholesterol and uric acid was 0.1 µM and for glucose it was 1 µM. Excellent stability, reproducibility, selectivity and fast response time were achieved. Biosensing of cholesterol, uric acid and glucose in human serum sample is successfully demonstrated with the biosensors, and the results are validated with the clinical laboratory measurement.

Pt-Pd alloy nanoparticle-decorated carbon nanotubes: a durable and methanol tolerant oxygen reduction electrocatalyst.

We describe the decoration of multiwalled carbon nanotubes (MCNTs) with Pt-Pd alloy nanoelectrocatalysts of three different compositions and their electrocatalytic performance toward the oxygen reduction reaction (ORR). The decoration of the MCNTs involves polymer-assisted impregnation of metal precursors PtCl(6)(2-) and PdCl(6)(2-) and the subsequent reduction of the impregnated precursors by a modified polyol route. The composition of the catalyst was controlled by tuning the molar ratio of the precursors during their impregnation. Electron probe microscopic analysis shows that the catalysts have compositions of Pt(46)Pd(54,) Pt(64)Pd(36) and Pt(28)Pd(72). The Pt(46)Pd(54) and Pt(64)Pd(36) catalysts have truncated octahedral and icosahedral shapes with a size ranging from 8 to 10 nm. On the other hand, the catalyst of Pt(28)Pd(72) composition has a spherical/quasispherical shape with a size distribution of 1-2 nm. The XPS measurement confirms the signature of metallic Pt and Pd. The Pt(46)Pd(54) catalyst has a pronounced electrocatalytic activity toward the ORR with a specific and mass activity of 378 µA cm(Pt-Pd)(-2) and 64 µA µg(Pt-Pd)(-1), respectively at 0.8 V. Moreover, the Pt(46)Pd(54) nanoelectrocatalyst is highly durable and it retains its initial catalytic activity even after 1000 extensive cycles. Interestingly, this catalyst has a very high tolerance toward methanol and it does not favor the oxidation of methanol in the potential window of 0.1-1.4 V. The electrocatalytic activity of the alloy electrocatalyst is compared with commercially available Pt black and MCNT-supported spherical Pt nanoparticles. The catalytic activity of the Pt(46)Pd(54) nanoelectrocatalyst is higher than the other catalysts. The Pt(46)Pd(54) catalyst outperforms the electrocatalytic activity of all other catalysts.

A rapid room temperature chemical route for the synthesis of graphene: metal-mediated reduction of graphene oxide.

A rapid and facile route for the synthesis of reduced graphene oxide sheets (rGOs) at room temperature by the chemical reduction of graphene oxide using Zn/acid in aqueous solution is demonstrated.

Polyelectrolyte-functionalized gold nanoparticle scaffold for the sensing of heparin and protamine in serum.

We describe a shape-controlled synthesis of polyelectrolyte-functionalized flowerlike and polyhedral Au nanoparticles and the development of a nanoarchitectured platform for the selective and highly sensitive detection of protamine and heparin by voltammetric, impedimetric, and microgravimetric techniques. The functionalized Au nanoparticles were chemically synthesized in aqueous solution at room temperature in the presence of the polyelectrolyte (either protamine or heparin). The charge on the polyelectrolyte controlled the shape and surface morphology of the nanoparticles. The negatively charged heparin-functionalized Au nanoparticles have multiple branched flowerlike shapes with an average size of 50 nm, whereas the cationic protamine-functionalized nanoparticles are of polyhedral shape with an average size of 25 nm. Both flowerlike and polyhedral nanoparticles have (111), (200), (220), and (311) planes of a face-centered cubic lattice of Au. Voltammetric, impedimetric, and microgravimetric sensing platforms based on functionalized Au nanoparticles have been developed for the sensing of heparin and protamine. The sensing platforms are developed by self-assembling the functionalized nanoparticles on a thiol-functionalized three-dimensional silicate network. The microgravimetric sensing platform shows very high sensitivity and it can detect heparin and protamine at concentrations as low as 0.05 µg mL(-1). The selectivity of the sensing platform towards heparin was examined with potential interferents such as hyaluronic acid (HA) and chondroitin-4-sulfate (CS). Both HA and CS did not interfere with the measurement of heparin. The practical application of the sensing platform was demonstrated by measuring the concentration of heparin and protamine in human serum samples. The sensing platform could successfully quantify the concentration of heparin and protamine in the real serum samples with excellent recovery. The sensing platform was robust and could be used for repeated measurement without compromising the sensitivity.

Enzyme-free colorimetric assay of serum uric acid.

A nonenzymatic method for the selective detection and quantification of serum uric acid (UA) using 2-thiouracil (2-TU) tailored Au nanoparticles is developed. The H-bonding interaction of UA with functionalized Au nanoparticles brings instantaneous visible color change and paves the way for the visible sensing of UA.

Naked eye sensing of melamine using rationally tailored gold nanoparticles: hydrogen-bonding and charge-transfer recognition.

A highly sensitive analytical method based on Au nanoparticles rationally tailored with recognition elements uracil-5-carboxylic acid (UCA) and 2,4,6-trinitrobenzenesulfonic acid (TNBS) for the visual sensing of melamine at the parts-per-billion (ppb) level is described. The tailored Au nanoparticles function as an excellent color indicating reporter and it recognizes the target analytes by triple hydrogen-bonding or charge-transfer interaction in aqueous solution. The interaction of melamine with UCA- or TNBS-tailored reporters induces a rapid visible color change due to the aggregation of reporters. The color change was spectrally monitored to precisely quantify the amount of melamine. The charge-transfer interaction of melamine with TNBS-tailored reporter brings a remarkable change in the spectral signature even at the ppb level. Such an interaction paves the way for the detection of melamine at the 5 ppb level, which is well below the safety limit set by UN food standard commission. This method is highly selective and the common interfering analytes such as cyanuric acid, cytosine, glucose, thymine, uracil, etc., do not interfere in the sensing of melamine. The practical utility of the method is demonstrated by quantifying the amount melamine in real samples.

Rapid room temperature synthesis of electrocatalytically active Au nanostructures.

We describe a facile route for the one-pot room temperature synthesis of anisotropic Au nanostructures in aqueous solution in the absence of seeds or surfactants and their electrocatalytic activity. The Au nanostructures were synthesized using piperazine derivatives 1-(2-hydroxyethyl)piperazine and 1,4-Bis(2-hydroxyethyl)piperazine as reducing agents. The Au nanostructures were characterized by spectral, transmission electron microscopic (TEM), X-ray diffraction and electrochemical measurements. The absorption spectrum of colloidal nanoparticles displays two bands ~580 and ~930 nm, corresponding to the dipole and quadrupole plasmon resonance, respectively. TEM measurements show that the Au nanostructures have penta-twined polyhedral shape with an average size of 52 nm. X-ray and selected area electron diffraction patterns reveal the existence of face centered cubic nanocrystalline Au. The concentration of Au(III) controls the stability of the nanoparticles. The nanoparticles were immobilized on 3-D silicate network pre-assembled on a conducting support to examine their electrocatalytic activity. The nanoparticle-based electrochemical interface was characterized by spectral, voltammetric and impedance measurements. The nanoparticle shows high catalytic activity in the oxidation of NADH and reduction of oxygen. Unique inverted 'V' shape voltammogram was obtained for the oxidation of NADH at less positive potential. The nanoparticle-based interface favors two-step four-electron reduction of oxygen to water in neutral pH. Significant decrease in the overpotential for the oxidation of NADH and reduction of oxygen with respect to the polycrystalline Au electrode was observed. The electrocatalytic performance of the polyhedral nanoparticle is compared with the conventional citrate stabilized spherical nanoparticles.