Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity.
Hydroxylammonium nitrate (HAN) is a promising green propellant because of its low toxicity, high volumetric specific impulse, and reduced development cost. Electrolytic decomposition of HAN is an efficient approach to prepare it for further ignition and combustion. This paper describes the investigation of a co-electrolysis effect on electrolytic decomposition of HAN-fuel mixtures using stainless steel-platinum (SS-Pt) electrodes. For the first time, different materials were utilized as electrodes to alter the cathodic reaction, which eliminated the inhibition effect and achieved a repeatable and consistent electrolytic decomposition of HAN solution. Urea and methanol were added as fuel components in the HAN-fuel mixtures. When the mass ratio of added urea ≥20%, the electrolytic decomposition of a HAN-urea ternary mixture achieved 67% increment in maximum gas temperature (Tgmax) and 185% increment in overall temperature increasing rate over the benchmark case of HAN solution. The co-electrolysis of urea released additional electrons into the mixtures and enhanced the overall electrolytic decomposition of HAN. In contrast, the addition of methanol did not improve the Tgmax but only increased the overall temperature increasing rate. This work has important implications in the development of an efficient and reliable electrolytic decomposition system of HAN and its mixtures for propulsion applications.
Newly discovered two-dimensional (2D) atomic crystals (nanosheet) of platinum diselenide (PtSe2) have progressively attracted attention due to their expected high performance in catalysis, sensing, electronics, and optoelectronics applications. Further extraordinary physicochemical properties are expected if these nanosheets of platinum diselenide can possess mesoporosity as this may enable a high range of molecular adsorption, enhancing their functionalities in catalysis, batteries, supercapacitors, and sensing. Here, we present for the first time a straightforward, aqueous-phase synthetic strategy for the preparation of scalable nanosheets of platinum diselenide with mesoporous structure via a surfactant-templated self-assembly followed by a thermal annealing phase-transformation process. We used hexamethylenetetramine as a hexagonal honeycomb (sp2-sp3 orbital) scaffold for assembling the Pt and Se organic complexes to form the nanosheet structure, which is stable, preserving the 2D structure and mesoporosity during a thermal annealing at 500 °C. Density functional theory analysis then indicated that the mesoporous nanosheets of platinum diselenide exhibit a high free-energy and large density of π electrons crossing the Fermi level, inferring a high-catalytic performance. This effortless strategy is currently being extended to the synthesis of other transition metal dichalcogenides, including the preparation of multi-metal atomic dichalcogenide nanosheets, for a wide variety of scientific and technological applications.
The bidentate N-cyclohexyl-2-(3-hydroxy-4-methoxybenzylidene)hydrazine-1-carbothioamide Schiff base ligand (HL) was coordinated to divalent nickel, palladium and platinum ions to form square planar complexes. The nickel and palladium complexes, [NiL2 ], [PdL2 ] form square planar complexes with 2:1 ligand to metal ratio. The platinum complex, [PtL(dmso)Cl] formed a square planar complex with 1:1 ligand to metal ratio. Platinum undergoes in situ reaction with DMSO before complexing with the ligand in solution. The cytotoxicity of HL, [NiL2 ], [PdL2 ], and [PtL(dmso)Cl] were evaluated against human colon cancer cell line (HCT-116), human cervical cancer (Hela) cell line, melanoma (B16F10) cells, and human normal endothelial cell lines (Eahy926) by MTT assay. The [NiL2 ] complex displayed selective cytotoxic effect against the HCT 116 cancer cell line with IC50 of 7.9 ± 0.2 μM. However, HL, [PdL2 ], and [PtL(dmso)Cl] only exhibited moderate cytotoxic activity with IC50 = 75.9 ± 2.4, 100.0 ± 1.8, and 101.0 ± 3.6 μM, respectively. The potent cytotoxicity of [NiL2 ] was characterized using Hoechst and Rhodamine assays. The nickel complex, [NiL2 ], caused remarkable nuclear condensation and reduction in mitochondrial membrane potential. In addition, molecular docking studies confirms that [NiL2 ] possesses significant binding efficiency with Tyrosine kinase. Altogether, the results revealed that [NiL2 ] exhibits cytotoxicity against the cancer cells via Tyrosine kinase-induced proapoptosis pathway. This study demonstrates that the [NiL2 ] complex could be a promising therapeutic agent against colorectal carcinoma.
This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I₃(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.
Platinum nanoparticles were synthesized in graphene oxide aqueous solution using a laser ablation technique to investigate the effect of optical linear, nonlinear and thermal properties of platinum-graphene oxide nanocomposite solution. The samples were prepared with different ablation times. The platinum nanoparticles that formed a spherical shape on the surface of graphene oxide solution were authenticated using UV-visible spectrum and transmission electron microscopy patterns. The particle size decreased with increasing ablation time, and the concentration and volume fraction of samples were increased. To obtain the optical linear, nonlinear and thermal properties of platinum-graphene oxide nanocomposite solution, UV-visible spectroscopy, Z-scan, thermal lens and photoacoustic techniques were used. Consequently, the linear and nonlinear refractive indices increased with an increase in the volume fraction of platinum nanoparticles. It was observed from the spatial self-phase modulation patterns that, the optical nonlinear property of the graphene oxide was enhanced in the presence of platinum nanoparticles, and the nonlinearity increased with an increase in the volume fraction of platinum nanoparticles inside the graphene oxide solution. The thermal diffusivity and thermal effusivity of platinum nanoparticles graphene oxide were measured using a thermal lens and photoacoustic methods, respectively. The thermal diffusivity and thermal effusivity of samples were in the range of 0.0341 × 10-5 m2/s to 0.1223 × 10-5 m2/s and 0.163 W s1/2 cm-2 K-1 to 0.3192 W s1/2 cm-2 K-1, respectively. Consequently, the platinum enhanced the optical and thermal properties of graphene oxide.
Oxidation of o-xylene was performed using alkaline battery-based catalyst doped with platinum to investigate the properties and activities. O-xylene was selected as the model of volatile organic compound (VOC) in this work. Physicochemical properties of the selected catalysts were characterized by FE/TEM (field emission transmission electron microscopy), BET (Brunauer-Emmett-Teller) analysis, XRD (X-ray powder diffraction), SEM/EDX (scanning electron microscopy/energy dispersive X-ray spectroscopy), and H2-TPR (hydrogen temperature programmed reduction). Major elements of the spent alkaline battery-based catalyst treated with sulfuric acid solution [SAB (400) catalyst] were manganese, zinc, iron, oxygen, carbon, chlorine, aluminum, sodium, silicon, and potassium. Increasing the doping amount of platinum on SAB (400) catalyst from 0.1 to 1 wt% increased particle size of platinum and lowered the temperature of TPR (TTP) for SAB (400) catalyst. Better redox properties were achieved with an increase in the o-xylene conversion according to the doping amount of platinum. When GHSV (gas hourly space velocity) was 40,000 h-1, o-xylene was oxidized completely over SAB (400) catalyst and 1.0 wt% Pt/SAB(400) catalyst at temperatures of 400 °C and 280 °C, respectively.
Platinum based adjuvant chemotherapy is generally recommended for ovarian cancer to improve the survival rate. Intravenous route is commonly used, easily administered and less associated complications. However, intraperitoneal route is gaining its popularity as a single procedure or adjunctive to the intravenous route. Numerous questions on its eligibility and safety are still perplexed. A case review on a patient with non optimal debulking surgery of advanced ovarian cancer was studied. Intravenous platinum based chemotherapy combined with paclitaxel failed to bring her to clinical remission. Second line chemotherapy, gemcitabin rendered her to poor response with unresolved debilitating ascites needing recurrent drainage. Surprisingly, a trial of intraperitoneal chemotherapy with cisplatin revealed a great response with a complete clinical remission.
Background. Diurnal rhythms of protein synthesis controlled by the biological clock underlie the rhythmic physiology in the fruit fly, Drosophila melanogaster. In this study, we conducted a proteome-wide investigation of rhythmic protein accumulation in D. melanogaster. Materials and Methods. Total protein collected from fly samples harvested at 4 h intervals over the 24 h period were subjected to two-dimensional gel electrophoresis, trypsin digestion and MS/MS analysis. Protein spots/clusters were identified with MASCOT search engine and Swiss-Prot database. Expression of proteins was documented as percentage of volume contribution using the Image Master 2D Platinum software. Results. A total of 124 protein spots/clusters were identified using MS/MS analysis. Significant variation in the expression of 88 proteins over the 24-h period was observed. A relatively higher number of proteins was upregulated during the night compared to the daytime. The complexity of temporal regulation of the D. melanogaster proteome was further reflected from functional annotations of the differently expressed proteins, with those that were upregulated at night being restricted to the heat shock proteins and proteins involved in metabolism, muscle activity, protein synthesis/folding/degradation and apoptosis, whilst those that were overexpressed in the daytime were apparently involved in metabolism, muscle activity, ion-channel/cellular transport, protein synthesis/folding/degradation, redox homeostasis, development and transcription. Conclusion. Our data suggests that a wide range of proteins synthesized by the fruit fly, D. melanogaster, is under the regulation of the biological clock.
Rhodinol is a mixture of geraniol and citronellol. It is the second fraction in fractional distillation of commercially grown Cymbopogon nardus. The physical and chemical similarities of these two compounds made them inseparable. The individual use of each compound is of great importance. A selective oxidation (hydrogen peroxide activated by platinum black) of geraniol (in rhodinol) to geranial was done while remaining citronellol intact in order to separate the two compounds into different chemical functionality. A yield of 81% geranial achieved while minimizing citronellal formation from citronellol to 17%. Chemical separation using sodium hydrogen sulfite (NaHSO3) was done to separate the aldehydes from the unreacted citronellol. Purification using fractional distillation was done to obtain pure geraniol and remove minor fraction of citronellal.
WO₃-decorated TiO₂ nanotube arrays were successfully synthesized using an in situ anodization method in ethylene glycol electrolyte with dissolved H₂O₂ and ammonium fluoride in amounts ranging from 0 to 0.5 wt %. Anodization was carried out at a voltage of 40 V for a duration of 60 min. By using the less stable tungsten as the cathode material instead of the conventionally used platinum electrode, tungsten will form dissolved ions (W(6+)) in the electrolyte which will then move toward the titanium foil and form a coherent deposit on the titanium foil. The fluoride ion content was controlled to determine the optimum chemical dissolution rate of TiO₂ during anodization to produce a uniform nanotubular structure of TiO₂ film. Nanotube arrays were then characterized using FESEM, EDAX, XRD, as well as Raman spectroscopy. Based on the FESEM images obtained, nanotube arrays with an average pore diameter of up to 65 nm and a length of 1.8 µm were produced. The tungsten element in the samples was confirmed by EDAX results which showed varying tungsten content from 0.22 to 2.30 at%. XRD and Raman results showed the anatase phase of TiO₂ after calcination at 400 °C for 4 h in air atmosphere. The mercury removal efficiency of the nanotube arrays was investigated by photoirradiating samples dipped in mercury chloride solution with TUV (Tube ultraviolet) 96W UV-B Germicidal light. The nanotubes with the highest aspect ratio (15.9) and geometric surface area factor (92.0) exhibited the best mercury removal performance due to a larger active surface area, which enables more Hg(2+) to adsorb onto the catalyst surface to undergo reduction to Hg⁰. The incorporation of WO₃ species onto TiO₂ nanotubes also improved the mercury removal performance due to improved charge separation and decreased charge carrier recombination because of the charge transfer from the conduction band of TiO₂ to the conduction band of WO₃.
Platinum drugs are heavily used first-line chemotherapeutic agents for many solid tumours and have stimulated substantial interest in the biological activity of DNA-binding metal complexes. These complexes generate DNA lesions which trigger the activation of DNA damage response (DDR) pathways that are essential to maintain genomic integrity. Cancer cells exploit this intrinsic DNA repair network to counteract many types of chemotherapies. Now, advances in the molecular biology of cancer has paved the way for the combination of DDR inhibitors such as poly (ADP-ribose) polymerase (PARP) inhibitors (PARPi) and agents that induce high levels of DNA replication stress or single-strand break damage for synergistic cancer cell killing. In this review, we summarise early-stage, preclinical and clinical findings exploring platinum and emerging ruthenium anti-cancer complexes alongside PARPi in combination therapy for cancer and also describe emerging work on the ability of ruthenium and gold complexes to directly inhibit PARP activity.
Gamma radiolytic synthesis was used to produce size-controlled spherical platinum nanoparticles from an aqueous solution containing platinum tetraammine and polyvinyl pyrrolidone. The structural characterizations were performed using X-ray diffraction, and transmission electron microscopy. The transmission electron microscopy was used to determine the average particle diameter, which decreased from 4.4nm at 80kGy to 2.8nm at 120kGy. The UV-visible absorption spectrum was measured and found that platinum nanoparticles exhibit two steady absorption maxima in UV regions due to plasmonic excitation of conduction electrons, which blue shifted to lower wavelengths with a decrease in particle size. We consider the conduction electrons of platinum nanoparticles to follow Thomas-Fermi-Dirac-Weizsacker atomic model that they are not entirely free but weakly bounded to particles at lower-energy states {n = 5, l = 2 or 5d} and {n = 6, l = 0 or 6s}, which upon receiving UV photon energy the electrons make intra-band quantum excitations to higher-energy states allowed by the principles of quantum number that results the absorption maxima. We found an excellent agreement between the experimental and theoretical results, which suggest that the optical absorption of metal nanoparticles could be fundamentally described by a quantum mechanical interpretation, which could be more relevant to photo-catalysis and heterogeneous catalysis.
The process of etching is the most crucial part of the work of manufacturing printed circuit boards (PCB). In the etching process by nitric acid, a spent etching waste solution of composition 250 g/L HNO3, 30-40 g/L Cu, 30-40 g/L Sn, 30-40 g/L Pb and 20-25 g/L Fe is produced. High metal concentrations in the spent etching waste solution make it a viable candidate for the recovery of metals. Recovery of metals from spent etching waste solution is a significant concern as the recent growth in production of printed circuit boards has generated a drastic increase of spent etching waste solution each year. This study concerns itself with the recovery of metals from spent etching waste. In this study a dilution was made in order to increase the pH of the solution as spent etching waste solution has high acidity, and the electrowinning method was performed to recover metals from the spent etching waste solution. Glassy carbon and platinum were used as cathode and anode in order to investigate the electrodeposition of metals and cyclic voltammetry investigation suggests that the deposition of metals on glassy carbon electrodes occurs at four different overpotentials mainly at -0.15 V, -0.35 V, -0.45 V and -0.75 V. Microscopy observation demonstrates that there is a deposition of metals by applying the potentials in a set of current-time transient study for a duration of 60 seconds and the metals recovered formed as aggregates.
Platinum is the most commonly used catalyst in fuel cell application. However, platinum is very expensive, thus limits the commercialisation of fuel cell system due to the cost factor. This study introduces a biosynthesis platinum from plant extracts that can reduce the cost of platinum production compared to the conventional method and the hazardous during the production of the catalyst. The biogenic platinum was tested on a Direct Methanol Fuel Cell. Advanced biogenic of Pt nano-cluster was synthesized through a novel and facile of one-pot synthesis bio-reduction derived from natural source in the form of plant extracts as reducing agent. Several selected plant extracts drawn from agricultural waste such as banana peel, pineapple peels and sugarcane bagasse extracts were comparatively evaluated on the ability of phytochemical sources of polyphenols rich for the development of single-step synthesis for Pt NPs. Notably, the biogenic Pt NPs from sugar cane bagasse has superior electro-catalytic activity, the enhanced utilization efficiency of Pt and appreciable stability towards methanol oxidation reaction, whose ECSA value approximates 94.58 m2g-1, mass activity/specific activity (398.20 mAmg-1/0.8471 mA/cm2Pt) which greater than commercial Pt black (158.12 mAmg-1/1.41 mA/cm2Pt).
Background: Cochleotoxicity following the treatment with platinum-based chemotherapy is well documented. The potential for vestibulotoxicity is still unclear. This scoping review examined the extent of current research literature, summarized research findings and identified research gaps regarding vestibular-related adverse effects associated with platinum-based chemotherapy in survivors of cancer. Methods: Inclusion criteria followed the PICO principles: Participants, adult, and pediatric cancer patients of any cancer type; Intervention, platinum-based chemotherapy (such as cisplatin, carboplatin, and oxaliplatin); Control, none or any; Outcomes, vestibular-related adverse effects. English language articles published since 1978 were retrieved. Seventy-five eligible studies were identified from a systematic literature search, and relevant data were charted, collated, and summarized. Results: Testing for vestibulotoxicity predominately featured functional evaluation of the horizontal semicircular canal using the caloric and rotational tests. The rate of abnormal vestibular function test results after chemotherapy administration varied from 0 to 50%. The results of objective testing did not always correspond to patient symptoms. There is tentative support for patients with pre-existing loss of vestibular function to be more likely to experience vestibular toxicity after dosing with cisplatin. Conclusions: A number of studies reported significant evidence of vestibular toxicities associated with platinum-based chemotherapy, especially cisplatin. This scoping review emphasizes that vestibular toxicity needs more attention and comprehensive evaluation. Specifically, studies that analyse cumulative dose of platinum-based chemotherapy, affected sites of lesion in vestibular end organs, and the correlation and temporal patterns of cochlear and vestibular toxicity are needed.
The formation of nano pores on aluminum at 30oC- 38oC, employing a one step anodization technique which does not require removing the oxide layer formed is presented. A 20% phosphoric acid electrolyte (concentration higher than the normal anodization concentration of 5 to 10%) at a cell potential of 60 volts was used. A platinum electrode was used as the cathode electrode while the aluminum substrate as the anode electrode. A dc powered electrochemical cell to provide the required amount of current density (without the use of temperature controlled water bath) suitable or necessary for pore formation at room temperature was employed. The results obtained show that pore formation at room temperature is achievable and the pore diameter ranged between 80-120 nm.
Platinum nanoparticles were synthesized using the gamma radiolytic technique in an aqueous solution containing Platinum tetraammine chloride in presence of poly vinyl pyrrolidone, isopropanol, tetrahydrofuran and deionized water. The gamma irradiation was carried out in a60Co gamma source chamber and the particle size was found to decrease from 4.88 to 3.14 nm on increasing the gamma radiation dose from 80 to 120 kGy. UV-visible absorption spectra were measured and revealed two steady absorption maxima at 216 and 264 nm in the UV region, which was blue shifted (i.e. toward lower wavelength) with decreasing particle size. By taking the conduction electrons of an isolated particle that are not entirely free, but instead bound to their respective quantum levels, the optical absorption of platinum nanoparticles can be calculated via intra-band quantum excitation for particle sizes similar to those measured experimentally. We found that the calculated absorption maxima of electronic excitations matched the measured absorption maxima well. This finding suggests that the optical absorption of metal nanoparticles commonly applied in nanoscience and nanotechnology can be described accurately by the quantum excitation of conduction electrons.
The study presents the synthesis of polypyrrole-coated palladium platinum/nitrogen-doped reduced graphene oxide nanocomposites (PdPt-PPy/N-rGO NC) via direct the reduction of Pd(II) and Pt(II) in the presence of pyrrole monomer, N-rGO and L-cysteine as the reducing agent. X-ray diffraction confirmed the presence of metallic Pd and Pt from the reduction of Pd and Pt cations. Transmission electron microscopy images revealed the presence of Pd, Pt and PPy deposition on N-rGO. Impedance spectroscopy results gave a decreased charge transfer resistance due to the presence of N-rGO. The nanocomposites were synthesized with different Pd/Pt ratios (2:1, 1:1 and 1:2). A glassy carbon electrode (GCE) modified with the nanocomposite showed enhanced electrochemical sensing capability for formaldehyde in 0.1 M sulfuric acid solution. Cyclic voltammetry showed an increase in the formaldehyde oxidation peak current at the GCE modified with Pd2Pt1 PPy N-rGO. At a typical potential of 0.45 V (vs. SCE), the sensitivity in the linear segment was 345.8 μA.mM -1. cm-2. The voltammetric response was linear between 0.01 and 0.9 mM formaldehyde concentration range, with a 27 µM detection limit (at S/N = 3). Graphical abstract Schematic presentation of formaldehyde detection by Pd2Pt1-PPy/nitrogen-doped reduced Graphene Oxide Nanocomposite (Pd2Pt1-PPy /N-Gr NC). The decrease of charge transfer resistance and the agglomeration of deposited metals in the presence of N-rGO enhance the current response of the electrochemical sensor.
The aim of this study was to prepare, characterize, and determine the in vitro anticancer effects of platinum-doped magnesia (Pt/MgO) nanoparticles. The chemical compositions, functional groups, and size of nanoparticles were determined using X-ray diffraction, Fourier transform infrared spectroscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and scanning electron microscopy. Pt/MgO nanoparticles were cuboid and in the nanosize range of 30-50 nm. The cytotoxicity of Pt/MgO nanoparticles was determined via the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay on the human lung and colonic cancer cells (A549 and HT29 respectively) and normal human lung and colonic fibroblasts cells (MRC-5 and CCD-18Co repectively). The Pt/MgO nanoparticles were relatively innocuous to normal cells. Pt/MgO nanoparticles downregulated Bcl-2 and upregulated Bax and p53 tumor suppressor proteins in the cancer cells. Pt/MgO nanoparticles also induced production of reactive oxygen species, decreased cellular glutathione level, and increased lipid peroxidation. Thus, the anticancer effects of Pt/MgO nanoparticles were attributed to the induction of oxidative stress and apoptosis. The study showed the potential of Pt/MgO nanoparticles as an anti-cancer compound.