The two cationic palladium(ii) complexes, [Pd(Len)2][OTf]2 (4) and [Pd(Lphen)2][OTf]2 (5), were synthesized by treatment of bis(benzonitrile)dichloropalladium(ii) with [H2Len][OTf]2 (2) or [H2Lphen][OTf]2 (3), respectively, in the presence of a weak base. The pro-ligands 2 and 3 were synthesized by melt reactions between N-methyl-4-chloropyridinium triflate (1) and the amines ethylenediamine or phenylenediamine, respectively. The water-soluble compounds 2-5 were fully characterized, including by single-crystal X-ray crystal structure determinations for 2-4. UV-Vis and fluorescence spectroscopy were used to study the binding interactions of 2-5 with CT-DNA. The spectroscopic data suggested the presence of intercalative and groove binding modes and this was supported by molecular docking studies. The in vitro cytotoxicity studies (IC50 values) showed that the human breast cancer cell lines MCF-7 and T47D were more sensitive towards 3, 4 and 5 than cisplatin. The cytotoxicity of the new compounds decreased in the order 5 > 4 > 3 > 2. Furthermore, the annexin V-FITC staining method strongly suggested the presence of phosphatidylserine (PS) on the outer membrane of the treated cells, which is a hallmark of apoptosis.
The bidentate N-(1-Alkylpyridin-4(1H)-ylidene)amide (PYA) pro-ligands [H2LBn][Cl]2 (2), and [H2LMe][TfO]2 (3) were prepared by simple alkylation reactions of the known compound, N,N-di(pyridin-4-yl)oxalamide (H2L, 1). The Pd(II) complexes, [Pd(LBn)2][Cl]2 (4), [Pd(LMe)2][Cl][TfO] (5), Pd(LBn)Cl2 (6) and Pd(LMe)Cl2 (7) were synthesized through reactions between these pro-ligands and suitable Pd(II) substrates in the presence of base. The molecular structures of 3 and 6 were obtained by single crystal X-ray structure determinations. Studies of the experimental and computational DNA binding interactions of the compounds 1-7 revealed that overall 4 and 6 have the largest values for the binding parameters Kb and ΔGbo. The results showed a good correlation with the steric and electronic parameters obtained by quantitative structure activity relationship (QSAR) studies. In-vitro cytotoxicity studies against four different cell lines showed that the human breast cancer cell lines MCF-7, T47D and cervical cancer cell line HeLa had either higher or similar sensitivities towards 4, 6 and 2, respectively, compared to cisplatin. In general, the cytotoxicity of the compounds, represented by IC50 values, decreased in the order 4 > 6 > 2 > 5 > 3 > 1 > 7 in cancer cell lines. Apoptosis contributed significantly to the cytotoxic effects of these anticancer agents as evaluated by apoptosis studies.
An amperometric sensor for L-Cys is described which consists of a glassy carbon electrode (GCE) that was modified with reduced graphene oxide placed in a Nafion film and decorated with palladium nanoparticles (PdNPs). The film was synthesized by a hydrothermal method. The PdNPs have an average diameter of about 10 nm and a spherical shape. The modified GCE gives a linear electro-oxidative response to L-Cys (typically at +0.6 V vs. SCE) within the 0.5 to 10 μM concentration range. Other figures of merit include a response time of less than 2 s, a 0.15 μM lower detection limit (at signal to noise ratio of 3), and an analytical sensitivity of 1.30 μA·μM-1·cm-2. The sensor displays selectivity over ascorbic acid, uric acid, dopamine, hydrogen peroxide, urea, and glucose. The modified GCE was applied to the determination of L-Cys in human urine samples and gave excellent recoveries. Graphical abstract Spherical palladium nanoparticles (PdNPs) on reduced graphene oxide-Nafion (rGO-Nf) films were synthesized using a hydrothermal method. This nanohybrid was used for modifying a glassy carbon electrode to develop a sensor electrode for detecting L-cysteine that has fast response (less than 2 s), low detection limit (0.15 μM), and good sensitivity (0.092 μA μM-1 cm-2).
The Heck cross-coupling reaction is a well-established chemical tool for the synthesis of unsaturated compounds by formation of a new C-C bond. In this study, 1,3-diarylpropene derivatives, designed as structural analogues of stilbenoids and dihydrostilbenoids, were synthesised by the palladium-catalysed reactions of 2-amidoiodobenzene derivatives with either estragole or eugenol. The products were obtained with high (E) stereoselectivity but as two regioisomers. The ratios of isomers were found to be dependent on the nature of the allylbenzene partner and were rationalised by electronic effects exercising a determining influence in the β-hydride elimination step. In addition, the cytotoxic effects of all the Heck reaction products were evaluated against MCF-7 and MDA-MB-231 human breast cancer cells, with unpromising results. Among all, compound 7d exhibited weak cytotoxic activity towards MCF-7 cell lines with IC50 values of 47.92 µM in comparison with tamoxifen and was considered to have general toxicity (SI value < 2).
Exploring the new catalytic systems for the reduction of organic and inorganic pollutants from an indispensable process in chemical, petrochemical, pharmaceutical and food industries, etc. Hence, in the present work, authors motivated to synthesize bare reduced graphene oxide (rGO), polyaniline (PANI), three different ratios of rGO-PANI(80:20,50:50, 10:90) composites and rGO-PANI(80:20,50:50, 10:90) supported mono (Pd) & bimetallic [Pd: Au(1:1,1:2, 2:1)] nanocomposite by a facile chemical reduction method. Also, it investigated their catalytic performances for the reduction of organic/inorganic pollutants and antimicrobial activities. All the freshly prepared bare rGO, PANI, three different ratios of rGO-PANI(80:20, 50:50,10:90) composites and rGO-PANI(80:20, 50:50,10:90)/Pd & Pd: Au(1:1, 1:2,2:1) nanocomposite hybrid catalysts were characterized using UV-Vis, FT-IR, SEM, FE-SEM, EDAX, HR-TEM, XRD, XPS and Raman spectroscopy analysis. Among them, an optimized best composition of rGO-PANI(80:20)/Pd: Au(1:1) bimetallic nanocomposite hybrid catalyst exhibits better catalytic reduction and antimicrobial activities than other composites, as a result of strong electrostatic interactions between rGO, PANI and bimetal (Pd: Au) NPs through a synergistic effect. Hence, an optimized rGO-PANI(80:20)/Pd:Au(1:1) bimetallic nanocomposite catalyst would be considered as a suitable catalyst for the reduction of different nitroarenes, organic dyes, heavy metal ions and also significantly inhibit the growth of S. aureus, S. Typhi as well as Candida albicans and Candida kruesi in wastewater.
A polystyrene (PS)-anchored Pd(II) metal complex was synthesized on cross-linked polymer by heating a mixture of chlorometylated polystyrene with phenyldithiocarbazate and carbon disulfide in the presence of potassium hydroxide (KOH) in dimethylformamide (DMF). The reaction mixture was heated at 80 °C to form the corresponding phenyldithiocarbazate-functionalized polymer. Then, it was treated with bis(benzonitrile)palladium(II) chloride. The properties of dark colored polymer, impregnated with the metal complex was then characterized by various spectroscopic technique such as Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), CHNS elemental analysis, BET surface area, X-ray Diffraction (XRD), Thermogravimetric (TGA) and Inductively Coupled Plasma-Optical Emission (ICP-OES) spectroscopy.
Corn-cobs are an agro-industrial waste and composed of cellulose mostly. In this study cellulose was isolated from the waste corn-cobs and modified to polymeric hydroxamic acid palladium complex 1 and characterized by using a variety of spectroscopic methods such as field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The complex 1 exhibited high catalytic activity towards Suzuki and Heck coupling reactions of activated and deactivated aryl halides to give the respective coupling products with high yield. Moreover, the complex 1 was recovered and recycled five times with no considerable loss of catalytic overall performance.
Nitrite (NO2-) is widely used as an additive to extend the shelf life of food products. Excessive nitrite intake not only causes blood-related diseases but also has the potential risk of causing cancers. A disposable screen-printed electrode was modified with nano‑palladium decorated bismuth sulfide microspheres (nanoPd@Bi2S3MS/SPE), and integrated with a smartphone-interfaced potentiostat to develop a portable, electrochemical nitrite sensor. NanoPd@Bi2S3MS was prepared by the hydrothermal reduction of a Bi2S3MS and Pd2+ dispersion and drop cast on the SPE. The nanoPd@Bi2S3MS/SPE was coupled with a smartphone-controlled portable potentiostat and applied to determine nitrite in food samples. The linear range of the sensor was 0.01-500 μM and the limit of detection was 0.0033 μM. The proposed system showed good repeatability, reproducibility, catalytic stability, and immunity to interferences. The proposed electrode material and a smartphone-based small potentiostat created a simple, portable, fast electrochemical sensing system that accurately measured nitrite in food samples.
Metal nanoparticles having interesting shapes can be prepared in aqueous solutions through simple reductions of metal ions with the presence of some additive reagents, such as cetyltrimethylammonium bromide and hexamethylenetetramine. In this review, some successful results for shape-controlled synthesis of metal nanoparticles in our group are summarized, which includes the synthesis of palladium nanocubes, palladium nanobricks, gold nanotripods. In addition, combining with indium tin oxide electrode surfaces, shape-controlled growth is shown to be possible to form gold nanoplates and copper oxide nanowires. Even in relatively mild synthetic conditions, interesting shape-controlled synthesis of metal nanoparticles is possible.
This study investigated the in vivo antileukemic activity of palladium nanoparticles (Pd@W.tea-NPs) mediated by white tea extract in a murine model. The cell viability effect of Pd@W.tea-NPs, "blank" Pd nanoparticles, and white tea extract alone was determined in murine leukemia WEHI-3B cells and normal mouse fibroblasts (3T3 cells). Apoptotic and cell cycle arrest effects of Pd@W.tea-NPs in WEHI-3B cells were evaluated. The effects of Pd@W.tea-NPs administered orally to leukemic mice at 50 and 100 mg/kg daily over 28 days were evaluated. Pd@W.tea-NPs reduced the viability of WHEI-3B cells with IC50 7.55 μg/ml at 72 h. Blank Pd nanoparticles and white tea extract alone had smaller effects on WHEI-3B viability and on normal fibroblasts. Pd@W.tea-NPs increased the proportion of Annexin V-positive WHEI-3B cells and induced G2/M cell cycle arrest. Leukemic cells in the spleen were reduced by Pd@W.tea-NPs with an increase in Bax/Bcl-2 and cytochrome-C protein and mRNA levels indicating the activation of the mitochondrial apoptotic pathway. These effects replicated the effects of ATRA and were not observed using blank Pd nanoparticles. Pd@W.tea-NPs afford therapeutic efficacy against leukemia likely to pivot on activation of the mitochondrial pathway of apoptotic signaling and hence appear attractive potential candidates for development as a novel anticancer agent.
Cupric oxide (CuO) thin films were prepared on a glass and silicon (Si) substrates by radio frequency magnetron sputtering system. The structural, optical and electrical properties of CuO films were characterized by X-ray diffraction (xRD), atomic force microscopy (AFM), Fourier transform infrared spectrometer, ultra-violet visible spectrophotometer, respectively, four point probe techniques and Keithley 4200 semiconductor characterization system. The xRD result showed that single phase CuO thin films with monoclinic structure were obtained. AFM showed well organized nano-pillar morphology with root mean square surface roughness for CuO thin films on glass and Si substrates were 3.64 and 1.91 nm, respectively. Infrared reflectance spectra shown a single reflection peak which is corresponding to CuO optical phonon mode and it confirmed that only existence of CuO composition on both substrates. The optical direct band gap energy of the CuO film grown on glass substrate, which is calculated from the optical transmission measurement was 1.37 eV. Finally, it was found that the deposited CuO films are resistive and the palladium formed ohmic contact for CuO on glass and schottky contact for CuO on Si.
Small sized electrocatalysts, which can be obtained by rapid nucleation and high supersaturation are imperative for outstanding methanol oxidation reaction (MOR). Conventional microwave synthesis processes of electrocatalysts include ultrasonication, stirring, pH adjustment, and microwave irradiation of the precursor mixture. Ethylene glycol (EG), which serves as a reductant and solvent was added during the ultrasonication or stirring stage. However, this step and pH adjustment resulted in unintended multi-stage gradual nucleation. In this study, the microwave reduction approach was used to induce rapid nucleation and high supersaturation in order to fabricate small-sized reduced graphene oxide-supported palladium (Pd/rGO) electrocatalysts via the delayed addition of EG, elimination of the pH adjustment step, addition of sodium carbonate (Na₂CO₃), prior microwave irradiation of the EG mixed with Na₂CO₃, and addition of room temperature precursor mixture. Besides its role as a second reducing agent, the addition of Na₂CO₃ was primarily intended to generate an alkaline condition, which is essential for the high-performance of electrocatalysts. Moreover, the microwave irradiation of the EG and Na₂CO₃ mixture generated highly reactive free radicals that facilitate rapid nucleation. Meanwhile, the room temperature precursor mixture increased supersaturation. Results showed improved electrochemically active surface area (78.97 m² g-1, 23.79% larger), MOR (434.49 mA mg-1, 37.96% higher) and stability.
In the present study, 2-bromo-4-chlorophenyl-2-bromobutanoate (3) was synthesized via the reaction of 2-bromo-4-chlorophenol with 2-bromobutanoyl bromide in the presence of pyridine. A variety of 2-bromo-4-chlorophenyl-2-bromobutanoate derivatives (5a-f) were synthesized with moderate to good yields via a Pd-catalyzed Suzuki cross-coupling reaction. To find out the reactivity and electronic properties of the compounds, Frontier molecular orbital analysis, non-linear optical properties, and molecular electrostatic potential studies were performed.
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.
Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4-10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity.
The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR) using supercritical carbon dioxide (scCO2) as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer.
Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraaza[14]annulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.
The syntheses of fourteen unusual o-carboxamido stilbenes by the Heck protocol revealed surprising complexity related to intriguing substituent effects with mechanistic implications. The unexpected cytotoxic and chemopreventive properties also seem to be substituent dependent. For example, although stilbene 15d (with a 4-methoxy substituent) showed cytotoxicity on HT29 colon cancer cells with an IC(50) of 4.9 μM, the 3,4-dimethoxy derivative (15c) is inactive. It is interesting to observe that the 3,5-dimethoxy derivative (15e) showed remarkable chemopreventive activity in WRL-68 fetal hepatocytes, surpassing the gold standard, resveratrol. The resveratrol concentration needed to be 5 times higher than that of 15e to produce comparable elevation of NQO1.
A new cobalt(II) ion selective electrode based on palladium(II) dichloro acetylthiophene fenchone azine(I) has been developed. The best membrane composition is found to be 10:60:10:21.1 (I)/PVC/NaTPB/DOP (w/w). The electrode exhibits a Nerstian response in the range of 1.0 × 10(-1)-1.0 × 10(-6)M with a detection limit and slope of 8.0 × 10(-7)M and 29.6 ± 0.2 mV per decade respectively. The response time is within the range of 20-25s and can be used for a period of up to 4 months. The electrode developed reveals good selectivity for cobalt(II) and could be used in pH range of 3-7. The electrode has been successfully used in the determination of cobalt(II) in water samples.
The present study reports the synthesis of various new derivatives based on 5-aryl-2-bromo-3-hexylthiophene with moderate-to-good yields via a palladium-catalyzed Suzuki cross-coupling reaction. This coupling method involved the reaction of 2,5-dibromo-3-hexylthiophene with several arylboronic acids in order to synthesize corresponding thiophene derivatives under controlled and optimal reaction conditions. The different substituents (CH3, OCH3, Cl, F etc.) present on arylboronic acids are found to have significant electronic effects on the overall properties of new products. The synthesized thiophene molecules were studied for their haemolytic, biofilm inhibition and anti-thrombolytic activities, and almost all products showed potentially good properties. The compound 2-bromo-5-(3-chloro-4-fluorophenyl)-3-hexylthiophenein particular exhibited the highest values for haemolytic and bio-film inhibition activities among all newly synthesized derivatives. In addition, the compound 2-bromo-3-hexyl-5-(4-iodophenyl)thiophene also showed high anti-thrombolytic activity, suggesting the potential medicinal applications of these newly synthesized compounds.