Pd-based nanoparticles: Plant-assisted biosynthesis, characterization, mechanism, stability, catalytic and antimicrobial activities.

Among various metal nanoparticles, palladium nanoparticles (Pd NPs) are one of the most important and fascinating nanomaterials. An important concern about the preparation of Pd NPs is the formation of toxic by-products, dangerous wastes and harmful pollutants. The best solution to exclude and/or minimize these toxic substances is plant mediated biosynthesis of Pd NPs. Biogenic Pd-based NPs from plant extracts have been identified as valuable nanocatalysts in various catalytic reactions because of their excellent activities and selectivity. They have captured the attention of researchers owing to their economical, sustainable, green and eco-friendly nature. This review attempts to cover the recent progresses in the fabrication, characterization and broad applications of biogenic Pd NPs in environmental and catalytic systems. In addition, the stability of biosynthesized Pd NPs and mechanism of their formation are investigated.

Biosynthesis of eco-friendly and recyclable Pd/LDHs catalyst using the withered leaves extract for Suzuki coupling reaction.

The hydrotalcite-supported palladium (Pd) catalyst is prepared with a green and environmentally friendly route, introducing the extract of withered leaves as a dispersant and reducing agent (Pd/LDHs-B). Compared with the as-prepared catalyst (Pd/LDHs-P with the average diameter of 4.3 nm) using a chemical synthesis method with polyvinylpyrrolidone as a dispersant and ascorbic acid (Vc) as a reductant, the results indicate that the size of Pd nanoparticles in Pd/LDHs-B is smaller (ca. 3.6 nm). The Pd-LHDs-B (0.5 mmol‰) exhibits higher activity (98.66%) than Pd/LDHs-P (98.19%) in the Suzuki reaction of 4-bromotoluene and phenylboronic acid at 60°C for 30 min. Also, the reusability of Pd/LDHs-B is confirmed by recycling tests without a significant decrease in activity.

A chemical speciation insight into the palladium(ii) uptake and metabolism by Sinapis alba. Exposure to Pd induces the synthesis of a Pd-histidine complex.

Palladium is recognized as a technologically critical element (TCE) because of its massive use in automobile exhaust gas catalytic converters. The release of Pd into the environment in the form of nanoparticles of various size and chemical composition requires an understanding of their metabolism by leaving organisms. We provide here for the first time a chemical speciation insight into the identity of the ligands produced or used by a plant Sinapis alba L. exposed in hydropony to Pd nanoparticles and soluble Pd (nitrate). The analytical method developed was based on the concept of 2D HPLC with parallel inductively coupled plasma mass spectrometry (ICP MS) and electrospray MS detection. Size exclusion chromatography - ICP MS of the plant extracts showed no difference between the speciation of Pd after the exposure to nanoparticles and after that to Pd2+ which indicated the reactivity and dissolution of Pd nanoparticles. A comparative investigation of the Pd speciation in a control plant extract spiked with Pd2+ and of an extract of a plant having metabolized palladium indicated the response of the Sinapis alba by the formation of a Pd-histidine complex. The complex was identified via Orbitrap MS; the HPLC-MS chromatogram produced two peaks at m/z 415.0341 each corresponding to a Pd-His2 complex. An investigation by ion-mobility MS revealed a difference in their collision cross section indicating that the complexes present varied in terms of spatial conformation. A number of other Pd complexes with different ligands (including nicotianamine) circulating in the plant were detected but these ligands were already observed in a control plant and their concentrations were not affected by the exposure to Pd.

Simple, green approach for the synthesis of solid support-embedded PdNPs for ligand exchange.

Green approaches have the potential to significantly reduce the costs and environmental impact of chemical syntheses. Here, the authors used green tea (GT) leaf extract to synthesise and anchor palladium nanoparticles (PdNPs) to silica. The synthesised PdNPs in GT extract were characterised by ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. PdNPs primarily formed as capped NPs dispersed in GT extract before reduction completed after 24 h. This capped phytochemical solution was employed as a green precursor solution to synthesise PdNP-embedded solid supports. The morphology of PdNPs anchored to silica differed to that of PdNPs in solution. Silica-embedded PdNPs was employed as a new ligand exchanger to isolate trace polycyclic aromatic sulphur heterocycles from a hydrocarbon matrix. The isolation efficiency of the new, greener ligand exchanger was the same as an efficient chemical ligand exchanger and may, therefore, hold promise for future applications.

Effects of noble metal nanoparticles on the hydroxyl radical scavenging ability of dietary antioxidants.

Noble metal nanoparticles (NPs) have been widely used in many consumer products. Their effects on the antioxidant activity of commercial dietary supplements have not been well evaluated. In this study, we examined the effects of gold (Au NPs), silver (Ag NPs), platinum (Pt NPs), and palladium (Pd NPs) on the hydroxyl radical (·OH) scavenging ability of three dietary supplements vitamin C (L-ascorbic acid, AA), (-)-epigallocatechin gallate (EGCG), and gallic acid (GA). By electron spin resonance (ESR) spin-trapping measurement, the results show that these noble metal NPs can inhibit the hydroxyl radical scavenging ability of these dietary supplements.

Bio-synthesis of palladium nanocubes and their electrocatalytic properties.

The bio-synthesis of palladium nanocubes (PdNCs) was realised using pine needle extract as the reducing agent and cetyl trimethyl ammonium bromide as the capping agent. As an eco-friendly and readily available biomass, pine needle extract avoided the use of highly polluting chemical reducing agents. The growth process of PdNCs was analysed using ultraviolet-vis and Fourier transform infrared spectroscopy. Flavonoids, esters, terpenoids and polyhydric alcohols, which contain reductive groups, were mainly responsible for the transition of Pd2+ ions to PdNCs. The morphology and structure of PdNCs were characterised using transmission electron microscopy (TEM), high-resolution TEM, selected area electron diffraction and X-ray diffraction. It was indicated that the as-prepared PdNCs displayed a relatively high purity and good crystallinity with a face-centred cubic structure and exhibited sizes ranging from 6.11 to 29.51 nm with an average particle size of 11.18 nm. In the methanol electro-oxidation reaction, the PdNCs enclosed by {100} facets exhibited superior electro-catalytic activity to commercial Pd/C, which was rarely reported in other bio-synthesis processes for Pd catalysts. Meanwhile, the PdNCs showed excellent anti-poisoning ability and long-term stability. This study reveals the possibility of preparing shape-controlled PdNCs with a specific structure and excellent electro-catalytic activity.

Pd nanoparticles synthesized in situ with the use of Euphorbia granulate leaf extract: Catalytic properties of the resulting particles.

For the first time the extract of the plant of Euphorbia granulate was used to green synthesis of Pd nanoparticles (NPs) as a heterogeneous catalyst for the phosphine-free Suzuki-Miyaura coupling reaction at room temperature. This method is a facile and eco-friendly way in organic synthesis using the plant extract as biomedia, bioreductant and capping ligand which considerably stabilizes the surface of Pd NPs. The presence of flavonoid and phenolics acids in the extract could be responsible for the reduction of Pd(2+) ions and formation of the corresponding Pd NPs.

Amyloid fibrils enhance transport of metal nanoparticles in living cells and induced cytotoxicity.

Amyloid protein fibrils occur in vivo as pathological agents, in the case of neurodegenerative diseases, or as functional amyloids, when playing biologically vital roles. Here we show how amyloid fibrils generated from a food protein, ß-lactoglobulin, can be used as nanoreactors for the synthesis of metal nanoparticles and demonstrate that the resulting hybrids can play a central role in the internalization of nanoparticles into living cells, with up to 3-fold-enhanced transport properties over pristine nanoparticles. We conjugate gold, silver, and palladium nanoparticles onto amyloid fibrils by chemical reduction, and we study their effect on dendritic and MCF7 breast cancer cells. Transmission electron microscopy indicates localization of nanoparticles inside vesicles of the cells. Flow cytometry reveals that silver nanoparticle-amyloid hybrids are cytotoxic, while gold and palladium nanoparticle-amyloid hybrids produce no notable effect on cell viability and activation status.

Transition metal sensing by Toll-like receptor-4: next to nickel, cobalt and palladium are potent human dendritic cell stimulators.

BACKGROUND: Nickel was recently identified as a potent activator of dendritic cells through ligating with human Toll-like receptor (TLR)-4. OBJECTIVES: Here, we studied an extended panel of transition metals neighbouring nickel in the periodic table of elements, for their capacity to activate human monocyte-derived dendritic cells (MoDCs). METHODS: The panel included chromium, cobalt, and palladium, all of which are known to be frequent clinical sensitizers. MoDC activation was monitored by assessment of release of the pro-inflammatory mediator interleukin (IL)-8, a major downstream result of TLR ligation. Results The data obtained in the present study show that cobalt and palladium also have potent MoDC-activating capacities, whereas copper and zinc, but not iron and chromium, have low but distinct MoDC-activating potential. Involvement of endotoxin contamination in MoDC activation was excluded by Limulus assays and consistent stimulation in the presence of polymyxin B. The critical role of TLR4 in nickel-induced, cobalt-induced and palladium-induced activation was confirmed by essentially similar stimulatory patterns obtained in an HEK293 TLR4/MD2 transfectant cell line. CONCLUSIONS: Given the adjuvant role of costimulatory danger signals, the development of contact allergies to the stimulatory metals may be facilitated by signals from direct TLR4 ligation, whereas other metal sensitizers, such as chromium, may rather depend on microbial or tissue-derived cofactors to induce clinical sensitization.

One-pot synthesis of benzo[f]indole-4,9-diones from 1,4-naphthoquinones and terminal acetylenes.

In this paper, a concise one-pot method for the construction of benzo[f]indole-4,9-dione motifs is described. These transformations proceed via a sequential palladium- and copper-catalyzed coupling reaction of 1,4-naphthoquinones with terminal acetylenes, followed by a copper-catalyzed intramolecular cyclization reaction of the resulting coupling product.

Characterization of Pt-, Pd-spermine complexes for their effect on polyamine pathway and cisplatin resistance in A2780 ovarian carcinoma cells.

We have previously showed that platinum drugs up-regulate SSAT and SMO and down-regulate ODC and SAMDC in the polyamine pathway. Several studies including our own established that platinum drugs combined with polyamine analog DENSPM produces synergistic increase in SSAT activity with polyamine depletion. Since polyamine pathway is an important therapeutic target, we investigated whether agents containing both platinum and polyamines have similar effects on the polyamine pathway. Two complexes i) Pt-spermine with two cisplatin molecules linked to a spermine in the center and ii) Pd-spermine with similar structure i, but Pd (II) substituted for Pt (II) were analyzed with respect to their effect on the expression of genes in polyamine pathway, SSAT and SMO protein expression, SSAT activity and polyamine pools. Pt-, Pd-spermine complexes induced significant down-regulation of SMO, arginase 2 and NRF-2, with no change in SSAT, while cisplatin as a single agent or in combination with DENSPM induced significant up-regulation of SSAT and SMO. The SSAT activity was not induced by either Pt- or Pd-spermine in A2780 cells; SMO protein levels were significantly elevated compared to the no-drug control and to a similar extent as cisplatin/DENSPM. The Pd-spm treatment induced a fall in putrescine levels to 33%, spermidine to 62% and spermine to 72% while Pt-spm did not induce such a decline. Comparative cytotoxicity studies in A2780 cells indicated the potency to be cisplatin> Pd-Spm>Pt-Spm. Although both complexes exhibit a lower potency, the degree of resistance itself is much lower for Pt-spermine and Pd-spermine in that order (2.5 and 7.5, respectively) compared to cisplatin ( approximately 12) as tested in cisplatin resistant A2780/CP cells. These studies suggest that Pd (II)-polyamine complexes may constitute a promising group of inorganic compounds for further studies in the development of novel chemotherapy/adjuvant chemotherapy strategies.

The biosynthesis of palladium nanoparticles by antioxidants in Gardenia jasminoides Ellis: long lifetime nanocatalysts for p-nitrotoluene hydrogenation.

Gardenia jasminoides Ellis' water crude extract was used for the bioreduction of palladium chloride in this paper. The UV-vis spectrum, x-ray diffraction spectrum measurement, the Fourier transform infrared spectroscopy and TEM technique confirmed the formation of palladium nanoparticles and identified antioxidants including geniposide, chlorogenic acid, crocins and crocetin were reducing and stabilizing agents for synthesizing palladium nanoparticles in water crude extract. The particle size and dispersity were temperature-dependent. The particle sizes ranged from 3 to 5 nm and revealed the best dispersity at 70 degrees C. Catalytic performance of the biosynthetic Pd nanoparticles with good dispersity was investigated by hydrogenation of p-nitrotoluene. The catalysts showed a conversion of 100% under conditions of 5 MPa, 150 degrees C for 2 h. The selectivity of p-methyl-cyclohexylamine achieved 26.3%. The catalyst was recycled five times with no agglomeration and maintained activity, which was attributed to the appropriate protection of the antioxidants. On the basis of the study, it appears to be a new promising biosynthetic nanocatalyst for the development of an industrial process.

Metal binding by bacteria from uranium mining waste piles and its technological applications.

Uranium mining waste piles, heavily polluted with radionuclides and other toxic metals, are a reservoir for bacteria that have evolved special strategies to survive in these extreme environments. Understanding the mechanisms of bacterial adaptation may enable the development of novel bioremediation strategies and other technological applications. Cell isolates of Bacillus sphaericus JG-A12 from a uranium mining waste pile in Germany are able to accumulate high amounts of toxic metals such as U, Cu, Pb, Al, and Cd as well as precious metals. Some of these metals, i.e. U, Cu, Pd(II), Pt(II) and Au(III), are also bound by the highly orderd paracrystalline proteinaceous surface layer (S-layer) that envelopes the cells of this strain. These special capabilities of the cells and the S-layer proteins of B. sphaericus JG-A12 are highly interesting for the clean-up of uranium contaminated waste waters, for the recovery of precious metals from electronic wastes, and for the production of metal nanoclusters. The fabricated nanoparticles are promising for the development of novel catalysts. This work reviews the molecular biology of the S-layer of the strain JG-A12 and the S-layer dependent interactions of the bacterial cells with metals. It presents future perspectives for their application in bioremediation and nanotechnology.