Glutathione modified CdTe quantum dots as a label for studying DNA interactions with platinum based cytostatics

Cisplatin, carboplatin, and oxaliplatin represent three generations of platinum based drugs applied successfully for cancer treatment. As a consequence of the employment of platinum based cytostatics in the cancer treatment, it became necessary to study the mechanism of their action. Current accepted opinion is the formation of Pt‐DNA adducts, but the mechanism of their formation is still unclear. Nanomaterials, as a progressively developing branch, can offer a tool for studying the interactions of these drugs with DNA. In this study, fluorescent CdTe quantum dots (QDs, λ_em = 525 nm) were employed to investigate the interactions of platinum cytostatics (cisplatin, carboplatin, and oxaliplatin) with DNA fragment (500 bp, c = 25 μg/mL). Primarily, the fluorescent behavior of QDs in the presence of platinum cytostatics was monitored and major differences in the interaction of QDs with tested drugs were observed. It was found that the presence of carboplatin (c = 0.25 mg/mL) had no significant influence on QDs fluorescence; however cisplatin and oxaliplatin quenched the fluorescence significantly (average decrease of 20%) at the same concentration. Subsequently, the amount of platinum incorporated in DNA was determined by QDs fluorescence quenching. Best results were reached using oxaliplatin (9.4% quenching). Linear trend (R² = 0.9811) was observed for DNA platinated by three different concentrations of oxaliplatin (0.250, 0.125, and 0.063 mg/mL). Correlation with differential pulse voltammetric measurements provided linear trend (R² = 0.9511). As a conclusion, especially in the case of oxaliplatin‐DNA adducts, the quenching was the most significant compared to cisplatin and nonquenching carboplatin.     

Platinum coordination compounds of thiosemicarbazide derivatives: a new class of platinum blues

Platinum(II) forms blue 1?:?2 coordination compounds with 1-phenylthiosemicarbazide [H(1-PTSC)], 4-phenylthiosemicarbazide [H(4-PTSC)], 1,4-diphenylthiosemicarbazide [H(1,4-DPTSC)] and 4-(2-pyridyl)-thiosemicarbazide [H(4-(2py)-TSC)]. Electronic spectra of these compounds have been studied in different solvents. In all compounds, a band is observed in the 650–750?nm region that appears to be a metal-to-ligand charge transfer band. Infrared and proton NMR studies have been carried out to determine possible coordination sites and the nature of the complexes. IR spectra indicate bonding through sulfur and nitrogen and proton NMR spectra indicate bonding through the N¹nitrogen.     

Platinum Nanoparticles Modified with Perfluorinated Alkylamines as a Model Cathode Catalyst for Fuel Cells

Platinum nanoparticles (NPs) modified with undecafluorohexylamine (UFHA) and octylamine were synthesized as a novel model cathode catalyst for fuel cells. The modified Pt NPs were well characterized by FTIR, X‐ray photoelectron spectroscopy, thermogravimetric analysis, and transmission electron microscopy. These NPs supported on carbon black were applied as electrocatalysts for the oxygen reduction reaction. The UFHA‐modified Pt NP catalyst showed high electrocatalytic activity and durability compared to a commercial catalyst. Besides suppression of undesired oxide formation on the Pt surface, the affinity between the perfluorinated alkyl chains of UFHA and Nafion^® improved the catalyst activity by creating a desirable proton conduction path. Additionally, UFHA modification improved durability by suppressing Pt dissolution and carbon corrosion because of restricted water accessibility. The β ‐oxide formation, which is responsible for Pt dissolution, was significantly attenuated by surface modification.     

X-ray photoelectron spectroscopy and Raman microscopy of a ferroan platinum crystal from the Kondyor Massif,Russian Far East

X-ray Photoelectron Spectroscopy was used to study a ferroan platinum crystal from the Kondyor Massif, Russian Far East. Prior to the X-ray Photoelectron Spectroscopic analyses, the nature of the crystal was confirmed by X-ray diffraction. The survey scan showed mainly the presence of Pt and Fe, with smaller amounts of O and Si. The high resolutions spectra of the Pt 4f and Fe 2p showed 18.3 atom% Fe in the crystal, which puts the composition on the lower boundary for ferroan platinum and confirms earlier analyses using other methods such as Scanning Electron Microscopy-Energy Dispersive X-ray analysis/microprobe. The binding energy of the Pt 4f5/2 was 74.0?eV and Pt 4f7/2 70.5?eV, while the Fe 2p3/2 for metallic Fe was observed at 707.2?eV. The Fe 2p3/2 for metallic Fe was significantly sharper than that of Fe 2p3/2 at 710.7?eV associated with surface material. The Raman spectrum was dominated by the Pt–Pt stretching mode at 253?cm^?1. Changed orientation resulted in the observation of two bands at 127 and 139?cm^?1, interpreted as being due to stretching modes of two Pt–Pt bonds with the third bond to Fe and Pt fixed. The presence of Ca-Fe-Al-Mg-Si-O on the surface was probably associated with the presence of a clinopyroxene. These minerals can be expected since the crystal came originally from a clinopyroxenite-dunite matrix. The spectra showed a variety of interferences, e.g. Al 2p with Pt 4f, Mg 2p with Fe 3p, and Ca 2p1/2 with Mg Auger, making exact determinations of the ratios of these elements difficult.     

Characterization of the Insoluble Sludge from the Dissolution of Irradiated Fast Breeder Reactor Fuel

Insoluble sludge is generated in the reprocessing of spent fuel. The sludge obtained from the dissolution of irradiated fuel from the “Joyo” experimental fast reactor was analyzed to evaluate its chemical form. The sludge was collected by the filtration of the dissolved fuel solution, and then washed in nitric acid. The yields of the sludge weight were less than 1% of the total fuel weight. The chemical composition of the sludge was analyzed after decomposition by alkaline fusion. Molybdenum, technetium, ruthenium, rhodium, and palladium were found to be the main constituent elements of the sludge. X-ray diffraction patterns of the sludge were attributable to Mo₄Ru₄RhPd, regardless of the experimental conditions. The concentrations of molybdenum and zirconium in the dissolved fast reactor fuel solutions were low, indicating that zirconium molybdate hydrate is produced in negligible amounts in the process.     

Vibrational Spectrum of a Platinum Complex of Piroxicam

The infrared and Raman spectra of a platinum complex of the antiinflammatory drug piroxicam (Pir) and dimethylsulfoxide (DMSO) of composition [PtCl₂Pir(DMSO)] were recorded and briefly discussed on the basis of its structural characteristics. The metal-to-ligand vibrations are analyzed in detail.     

Pd-Pt loaded graphene aerogel on nickel foam composite as binder-free anode for a direct glucose fuel cell unit

Fabrication of electrocatalyst for direct glucose fuel cell (DGFC) operation involves destructive preparation methods with the use of stabilizer like binder, which may cause activity depreciation. Binder-free electrocatalytic electrode becomes a possible solution to the above problem. Binder-free bimetallic Pd-Pt loaded graphene aerogel on nickel foam plates with different Pd/Pt ratios (1:2.32, 1:1.62, and 1:0.98) are successfully fabricated through a green one-step mild reduction process producing a Pd-Pt/GO/nickel form plate (NFP) composite. Anode with the binder-free electrocatalysts exhibit a strong activity in a batch type DGFC unit under room temperature. The effects of glucose and KOH concentrations, and the Pd/Pt ratios of the electrocatalyst on the DGFC performance are also studied. Maximum power density output of 1.25 mW cm⁻² is recorded with 0.5 M glucose/3 M KOH as the anodic fuel, and Pd₁Pt_0.98/GA/NFP as catalyst, which is the highest obtained so far among other types of electrocatalyst.     

Immobilization of [Pt2(μ-S)2(PPh3)4] on Polymeric Supports by Sulfide Alkylation and Phosphine Exchange Reactions

Abstract

The immobilization of the dinuclear platinum(II) sulfido complex [Pt₂(μ-S)₂ (PPh₃)₄] on solid supports has been investigated. Reaction with haloalkyl functionalized polymers [Merrifield's resin (chloromethylated polystyrene), chloropropyl silica, chloropropyl controlled pore glass, and bromopropyl polysiloxane] gives complexes immobilized through alkylation of one of the sulfide ligands, forming a μ-thiolate ligand acting as an anchor to the polymer support, akin to well-established reactions of [Pt₂(μ-S)₂(PPh₃)₄] with molecular alkylating agents. The model complex [Pt₂(μ-S)(μ-SCH₂SiMe₃)(PPh₃)₄]PF₆ was prepared as the first molecular silicon-containing derivative of [Pt₂(μ-S)₂(PPh₃)₄] and was fully characterized by NMR spectroscopy, electrospray ionization-mass spectrometry, and single-crystal X-ray diffraction. Immobilization of [Pt₂(μ-S)₂(PPh₃)₄] by phosphine exchange reactions was also achieved using commercial polystyrene-grafted triphenylphosphine or a new immobilized phosphine [derived by sequential functionalization of Merrifield's resin with a polyether amine and then Ph₂PCH₂OH].     

Binding of Ionic Pyrene Derivatives to Polyelectrolytes. A Uv Absorption and Fluorescence Study

Abstract

The binding of pyrenesulfonic acid and pyrenebutyric acid to poly(vinyl benzyl trimethylammonium) chloride was investigated by UV and fluorescence spectroscopy. It was found that the binding constant was 7.5 × 10⁴ and 3.5 × 10⁴M^?1, respectively. The addition of the polyelectrolyte quenches the fluorescence of the pyrene group, and at the same time the typical excimer emission appears. This emission originates in pre-formed ground state aggregates of the pyrene derivatives incorporated into the polyion domain. Similar effects were observed when anionic polyelectrolytes, poly(styrene sulfonic), and poly(vinyl sulfonic) acids were added to cationic pyrene derivatives. The binding constants depend on the length of the aliphatic sidechain of the derivatives.     

Evaluation of a platinum electrode modified with hydroxyapatite in the lead(II) determination in a square wave voltammetric procedure

The behavior of a modified carbon platinum electrode (Pt) for lead(II) determination by square wave voltammetry (SWV) was studied. The modified electrode is obtained by electrodeposition of hydroxyapatite (HAP) on the surface of a bare platinum electrode. The new electrode (HAP/Pt) revealed interesting electroanalytical detection of lead(II) based on the adsorption of this metal onto hydroxyapatite under open circuit conditions. After optimization of the experimental and voltammetric conditions, the best voltammetric responses-current intensity and voltammetric profile were obtained in 0.2 mol L^?1 KNO₃ with: 30 min accumulation time, 5 mV pulse amplitude and 1 mV s^?1 scan rate. The observed detection (DL, 3σ) and quantification (DL, 10σ) limits in pure water were 2.01 × 10^?8 and 6.7 × 10^?7 mol L^?1, respectively. The reproducibility of the proposed method was determined from five different measurements in a solution containing 2.2 × 10^?6 mol L^?1 lead(II) with a coefficients of variation of 2.08%.The electrochemical of hydroxyapatite at platinum surfaces was characterized, after calcinations 900 °C, by X-ray diffraction, infrared spectroscopy, chemical and electrochemical analysis.