Metallodendritic Grafted Core–Shell γ‐Fe2O3 Nanoparticles Used as Recoverable Catalysts in Suzuki C?C Coupling Reactions

The use of dendritic structures for the grafting of core–shell γ‐Fe₂O₃/polymer 300 nm superparamagnetic nanoparticles (MNPs) has been performed with four metallodendrons that were functionalized with diphosphinopalladium complexes. The catalytic performance of these nanocatalysts was optimized for the Suzuki C? C cross‐coupling reaction. These results demonstrated the importance of optimizing the catalytic efficiency of grafted MNPs by optimizing the dendritic structures and the nature of the peripheral phosphine ligands. All of these nanocatalysts showed remarkable reactivity towards bromoarenes and they were recovered and efficiently reused by magnetic separation with almost no loss of reactivity, even after 25 cycles.     

Characterization of magnetic nanoparticles modified with thiol functionalized PAMAM dendron for DNA recovery

Magnetic nanoparticles (MNPs) modified with the thiol functionalized polyamidoamine (PAMAM) dendron were synthesized to estimate their DNA recovery capabilities. Aminosilane-modified MNPs and MNPs surrounded by a phospholipid (distearoylphosphatidylethanolamine (DSPE)) bilayer were used as core particles. Cystamine-core PAMAM dendrimers were reduced by dithiothreitol to dendron thiols and chemically conjugated to the core particles. Characterization of the synthesis revealed an increase of the surface amine charge from generation 1 (G1) to G6, starting with an aminosilane initiator. Particle size distribution analysis indicated that G6 PAMAM-modified MNPs exhibited monodispersity in an aqueous solution. G6 PAMAM-MNPs and G6 PAMAM-PE-MNPs synthesized by the proposed method have equivalent DNA recovery abilities to PAMAM-MNPs prepared by the conventional divergent synthesis method. In optimized conditions, 96% of λDNA was recovered using G6 PAMAM-PE-MNPs. Therefore, the method for preparing PAMAM-MNPs and PAMAM-PE-MNPs proposed in this study will be a novel approach for producing DNA carriers for efficient DNA purification by magnetic separation.     

Pd@tetrahedral hollow magnetic nanoparticles coated with N‐doped porous carbon as an efficient catalyst for hydrogenation of nitroarenes

Hollow magnetic nanoparticles (MNPs) with tetrahedral morphology were synthesized and then covered by a shell prepared by coating with melamine–formaldehyde followed by the introduction of glucose‐derived carbon. Subsequently, Pd nanoparticles were immobilized and the core–shell nanocomposite was carbonized. The obtained magnetic catalyst was successfully applied for the hydrogenation of nitroarenes in aqueous media. To investigate the effects of the morphology of MNPs, the nature of carbon shell, and the order of incorporation of Pd nanoparticles, several control catalysts, including the MNPs with different morphologies (disc‐like and cylinder); MNPs coated with different shells (sole glucose‐derived carbon or melamine–formaldehyde carbon shell); and a nanocomposite, in which Pd was immobilized after carbonization, were prepared and examined as catalyst for the model reaction. To justify the observed different catalytic activities of the catalysts, their Pd loadings, leaching, and specific surface areas were compared. The results confirmed that tetrahedral MNPs coated with porous N‐rich carbon shell exhibited the best catalytic activity. The high catalytic activity of this catalyst was attributed to its high surface area and the interaction of N‐rich shell with Pd nanoparticles that led to the higher Pd loading and suppressed Pd leaching.     

Biomolecule-nanoparticle hybrid systems for bioelectronic applications

Recent advances in nanobiotechnology involve the use of biomolecule-nanoparticle (NP) hybrid systems for bioelectronic applications. This is exemplified by the electrical contacting of redox enzymes by means of Au-NPs. The enzymes, glucose oxidase, GOx, and glucose dehydrogenase, GDH, are electrically contacted with the electrodes by the reconstitution of the corresponding apo-proteins on flavin adenine dinucleotide (FAD) or pyrroloquinoline quinone (PQQ)-functionalized Au-NPs (1.4 nm) associated with electrodes, respectively. Similarly, Au-NPs integrated into polyaniline in a micro-rod configuration associated with electrodes provides a high surface area matrix with superior charge transport properties for the effective electrical contacting of GOx with the electrode. A different application of biomolecule-Au-NP hybrids for bioelectronics involves the use of Au-NPs as carriers for a nucleic acid that is composed of hemin/G-quadruplex DNAzyme units and a detecting segment complementary to the analyte DNA. The functionalized Au-NPs are employed for the amplified DNA detection, and for the analysis of telomerase activity in cancer cells, using chemiluminescence as a readout signal. Biomolecule-semiconductor NP hybrid systems are used for the development of photoelectrochemical sensors and optoelectronic systems. A hybrid system consisting of acetylcholine esterase (AChE)/CdS-NPs is immobilized in a monolayer configuration on an electrode. The photocurrent generated by the system in the presence of thioacetylcholine as substrate provides a means to probe the AChE activity. The blocking of the photocurrent by 1,5-bis(4-allyldimethyl ammonium phenyl)pentane-3-one dibromide as nerve gas analog enables the photoelectrochemical analysis of AChE inhibitors. Also, the association CdS-NP/double-stranded DNA hybrid systems with a Au-electrode, and the intercalation of methylene blue into the double-stranded DNA, generates an organized nanostructure of switchable photoelectrochemical functions. Electrochemical reduction of the intercalator to the leuco form, -0.4 V vs. SCE, results in a cathodic photocurrent as a result of the transfer of photoexcited conduction-band electrons to O(2) and the transport of electrons to the valance-band holes by the reduced intercalator units. The oxidation of the intercalator, E 0 V (vs. SCE), yields in the presence of triethanolamine, TEOA, as sacrificial electron donor, an anodic photocurrent by the transport of conduction-band electrons, through intercalator units, to the electrodes, and filling the valance-band holes with electrons supplied by TEOA. The systems reveal potential-switchable directions of the photocurrents, and reveal logic gate functions.     

Magnetic iron oxide nanoparticles for biorecognition: evaluation of surface coverage and activity

Modifying the surfaces of magnetic nanoparticles (MNPs) by the covalent attachment of biomolecules will enable their implementation as contrast agents for magnetic resonance imaging or as media for magnetically assisted bioseparations. In this paper we report both the surface coverage and the activity of IgG antibodies on MNPs. The antibodies were immobilized on gamma-Fe2O3 nanoparticles by conventional methods using aminopropyltriethoxy silane and subsequent activation by glutaraldehyde. Novel fluorescence methods were used to provide a quantitative evaluation of this well-known approach. Our results show that surface coverage can be stoichiometrically adjusted with saturated surface coverage occurring at approximately 36% of the theoretical limit. The saturated surface coverage corresponds to 34 antibody molecules bound to an average-sized MNP (32 nm diameter). We also show that the immobilized antibodies retain approximately 50% of their binding capacity at surface-saturated levels.     

Synthesis of double‐hydrophilic block copolymers via combination of oxyanion‐initiated polymerization and polymer reaction for fabricating magnetic target gene carrier

In this work, we have synthesized a polycation and a polyanion via a combination of oxyanion‐initiated polymerization and polymer reaction, and then developed a novel approach to prepare a controlled magnetic target gene carrier with magnetic Fe₃O₄ nanoparticles as core and poly(ethylene glycol) (PEG) segment as corona via layer‐by‐layer (LbL) assembly and shell‐crosslinking. Magnetic nanoparticles (MNPs) were first modified by poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) via radical polymerization. The resulting MNPs were used to compact deoxyribonucleic acid (DNA) through LbL assembly, involving four steps: ( 1 ) the binding of DNA to the polycation PDMAEMA on the surface of MNPs; ( 2 ) the produced particles in Step 1 with negative charge interacting with additional polycation ethoxy group end‐capped PDMAEMA (EtO‐PDMAEMA) homopolymer, leading to a positive charge surface; ( 3 ) using carboxyl group (‐COO^‐) of poly(methacrylic acid) (PMAA) in a diblock copolymer (MePEG2000‐b‐PMAA_SH) as polyanion, which has partial mercapto groups (‐SH) in PMAA segment, to interact with the particles produced in Step 2; ( 4 ) the shell of the composite nanoparticle was crosslinked by oxidizing the ‐SH groups of the MePEG2000‐b‐PMAA_SH to form disulfide linkage (S? S). All the processes of LbL assembly were investigated by agarose gel retardation assay and zeta potential measurements. The in vitro cytotoxicity analysis proves that polyions/DNA MNPs have excellent properties and potential applications as gene carriers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Quinone‐Rich Poly(dopamine) Magnetic Nanoparticles for Biosensor Applications

Novel core‐shell quinone‐rich poly(dopamine)–magnetic nanoparticles (MNPs) were prepared by using an in situ polymerization method. Catechol groups were oxidized to quinone by using a thermal treatment. MNPs were characterized by using X‐ray diffraction, X‐ray photoelectron spectroscopy, atomic force microscopy, magnetic force microscopy, UV/Vis, Fourier‐transform infrared spectroscopy, and electrochemical techniques. The hybrid nanomaterial showed an average core diameter of 17 nm and a polymer‐film thickness of 2 nm. The core‐shell nanoparticles showed high reactivity and were used as solid supports for the covalent immobilization of glucose oxidase (Gox) through Schiff base formation and Michael addition. The amount of Gox immobilized onto the nanoparticle surface was almost twice that of the nonoxidized film. The resulting biofunctionalized MNPs were used to construct an amperometric biosensor for glucose. The enzyme biosensor has a sensitivity of 8.7 mA M ^?1 cm^?2, a low limit of detection (0.02 mM ), and high stability for 45 days. Finally, the biosensor was used to determine glucose in blood samples and was checked against a commercial glucometer.     

Preparation of glycopolymer‐coated magnetite nanoparticles for hyperthermia treatment

In this article, magnetite nanoparticles (MNPs) coated with glycopolymer bearing glucose moieties were designed with optimal structural, colloidal, and magnetic properties for biomedical applications. MNPs with an average size of 17 ± 2 nm were synthesized by thermal decomposition process and then their surfaces were modified with active vinyl groups. Two different monomers were immobilized onto the surfaces: dopamine methacrylamide, a monomer with properties inspired on mussels adhesive capacity, or unprotected glycomonomer, 2‐{[(D ‐glucosamin‐2N‐yl)carbonyl]‐oxy}ethyl methacrylate. Afterward, the glycomonomer were polymerized at the interface of both vinyl functionalized MNPs by conventional radical polymerization. The resultant hybrid NPs were water dispersible presenting good stability in aqueous solution for long time periods. Moreover, the high density of carbohydrates at the surface of the magnetic NPs could confer targeting properties to the system as demonstrated by studies of their binding interactions with lectins, where the binding activity is higher as the glycopolymer content augments. The magnetic and magneto‐thermal properties of the synthesized hybrid NPs were evaluated. The magnetization curves reveal superparamagnetic features at 300 K, with high values of saturation magnetization. Furthermore, the hybrid glycoparticles show suitable heat dissipation power when exposed to alternating magnetic field conditions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

共价固定亲和素的磁性纳米粒子用于快速测定蛋白A含量

采用溶剂热法制备了Fe₃O₄磁性纳米粒子(MNPs), 以戊二醛为交联剂, 将亲和素共价固定于MNPs表面. 用透射电子显微镜(TEM)、 X射线衍射(XRD)、 紫外-可见吸收光谱(UV-Vis)、 傅里叶变换红外光谱(FTIR)和荧光光谱等手段对蛋白固定过程进行了监控和表征. 采用荧光光谱法评价了固定亲和素的磁性纳米粒子(Avi-MNPs)的活性, 并将Avi-MNPs应用于分光光度法测定蛋白A的含量. TEM结果表明, 功能化前后MNPs的粒度分布均匀, 粒径大小分别约为30和50 nm. XRD分析结果表明, MNPs与Fe₃O₄的特征衍射峰完全一致, 晶体纯度良好. UV-Vis, FTIR和荧光光谱结果表明, 亲和素已固定在MNPs表面. Avi-MNPs活性评价结果表明, 其结合生物素的活力为4.706 U/mg Avi-MNPs, 低于游离的亲和素活力(14.1 U/mg D-biotin). 该方法用于检测蛋白A含量比传统酶联免疫法省时、 省力, 且对检测仪器要求低.     

Metallodendritic grafted core-shell γ-Fe2O3 nanoparticles used as recoverable catalysts in Suzuki C-C coupling reactions

The use of dendritic structures for the grafting of core-shell γ-Fe(2)O(3)/polymer 300 nm superparamagnetic nanoparticles (MNPs) has been performed with four metallodendrons that were functionalized with diphosphinopalladium complexes. The catalytic performance of these nanocatalysts was optimized for the Suzuki C-C cross-coupling reaction. These results demonstrated the importance of optimizing the catalytic efficiency of grafted MNPs by optimizing the dendritic structures and the nature of the peripheral phosphine ligands. All of these nanocatalysts showed remarkable reactivity towards bromoarenes and they were recovered and efficiently reused by magnetic separation with almost no loss of reactivity, even after 25 cycles.     

Sulfamic acid immobilized on amino‐functionalized magnetic nanoparticles: A new and active magnetically recoverable catalyst for the synthesis of N‐heterocyclic compounds

Sulfamic acid immobilized on amino‐functionalized magnetic nanoparticles (MNPs/DETA‐SA) was successfully fabricated and characterized using various techniques. Diameters of approximately 15 nm for the MNPs/DETA‐SA were observed from scanning electron microscopy images. The as‐fabricated nanocomposite was applied as an efficient and magnetically reusable catalyst for the synthesis of 2,3‐dihydroquinazoline‐4(1H)‐one and polyhydroquinoline derivatives. All products were obtained in good to excellent yields. Recovery tests confirm that the catalyst can be readily recovered using an external magnet and reused many times without significant loss of its catalytic activity.     

Towards a fluorescent molecular switch for nucleic acid biosensing

A novel fluorescent molecular switch for the detection of nucleic acid hybridization has been explored in relation to the development of a structure that would be amenable for operation when immobilized for solid-phase analyses. The structure was prepared by self-assembly, and used Neutravidin as the central multivalent docking molecule, a newly synthesized biotinylated long-chain linker for intercalating dye that was modified with thiazole orange (TO) at one end, and a biotinylated probe oligonucleotide. Self-assembly of the biotinylated components on adjacent Neutravidin binding sites allowed for physical placement of an oligonucleotide probe molecule next to tethered TO. The TO located at the end of the flexible linker chain was available to intercalate, and could report if a duplex structure was formed by a probe–target interaction by means of fluorescence intensity. Subsequently, regeneration of the single-stranded probe was possible without loss of the intercalator to solution. The switch constructs were assembled in solution and subsequently immobilized onto biotin functionalized optical fibers to complete the sensor design. Solution-phase fluorescence lifetime data showed a biexponential behavior for switch constructs, suggesting intercalation as well as a significant secondary binding mode for the immobilized TO. It was found that the secondary binding mechanism for the dye to DNA could be decreased, thus shifting the dye to intercalative binding modes, by adjusting the solution conditions to a pH below the pI of Neutravidin, and by increasing the ionic strength of the buffer. Preliminary work demonstrated that it was possible to achieve up to a fivefold increase in fluorescence intensity on hybridization to the target.     

Green tea-synthesized magnetic nanoparticles accelerate the microwave digestion of proteins analyzed by MALDI-TOF-MS

In present work, green tea is used for the synthesis of magnetic nanoparticles. During synthesis of MNPs, no additional reducing agents required because green tea extract itself contains polyphenols reducing agent, comparatively other reported methods. Surface of the green tea-synthesized nanoparticles is functionalized with tetraethyl orthosilicate and 3-aminopropyltriethoxysilane. Functionalized MNPs are applied for the microwave digestion of protein molecules. Functionalized MNPs contain negative charge, and thus adsorb peptide fragments after microwave digestion of protein molecules. The functionalized MNPs can assist, accelerate and effectively enhance the digestion efficiency, sequence coverage and detection sensitivity of peptides for the microwave-assisted tryptic digestion of proteins in matrix assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS). The reason is attributed to the fact that proteins or partially digested proteins are easily attracted or concentrated onto the surface of functionalized MNPs, resulting in higher efficiency of digestion reactions in the microwave experiments. Besides, the functionalized MNPs could act as a microwave absorber to accelerate and enrich the protein fragments in a short period of time (30–50 s). Various experimental conditions such as enzyme-to-protein ratio 1:30, MNPs concentration 600 µg, heating time 40 s and incubation time 15 min were investigated in the MALDI-TOF-MS. Thus, the current technique proves the suitability, cheapness and ecofriendly nature of MNPs and its utility for various biotechnological and proteome research in near future.     

Three-layer composite magnetic nanoparticle probes for DNA

A method for synthesizing composite nanoparticles with a gold shell, an Fe3O4 inner shell, and a silica core has been developed. The approach utilizes positively charged amino-modified SiO2 particles as templates for the assembly of negatively charged 15 nm superparamagnetic water-soluble Fe3O4 nanoparticles. The SiO2-Fe3O4 particles electrostatically attract 1-3 nm Au nanoparticle seeds that act in a subsequent step as nucleation sites for the formation of a continuous gold shell around the SiO2-Fe3O4 particles upon HAuCl4 reduction. The three-layer magnetic nanoparticles, when functionalized with oligonucleotides, exhibit the surface chemistry, optical properties, and cooperative DNA binding properties of gold nanoparticle probes, but the magnetic properties of the Fe3O4 inner shell.     

Intercalator-DNA interactions revealed by NIR surface-enhanced Raman spectroscopy

Using 1064 nm excited surface-enhanced Raman spectroscopy (SERS) a well known intercalator, ethidium bromide (EB), and a structurally related compound, 4-methyl-2,7-diamino-5,10-diphenyl-4,9-diazapyrenium hydrogensulfate (ADAP), have been studied. Concentration dependent SERS spectra of both aromatic species (1 × 10⁻⁷-5 × 10⁻⁵ M) indicated existence of dimeric associates at high concentration and an equilibrium shift towards monomers with a concentration decrease. Interactions of the intercalating molecules with DNA have been studied for various intercalator/DNA (base pair) molar ratios ranging from 10/1 to 1/10. In colloidal samples containing an intercalator in excess relative to DNA binding sites (from 10/1 to 2/1) enhancement of the Raman scattering gradually weakened, indicating a decrease in a number of free molecules adsorbed on the metal surface due to binding with DNA. At the drug/DNA ratios of 1/2 and 1/5 weaker but observable SERS bands indicated insertion of the drug molecules between the base pairs (intercalation strongly diminished interaction of the drug molecules with metal surface) as well as non-intercalative binding of the drug molecules able to stay in closer contact with a metal surface. A total intercalation of EB and ADAP molecules (intercalator/DNA of 1/7 and 1/10) resulted in almost complete loss of the SERS signal. Intensity of the SERS spectra of the intercalator/DNA complexes relative to the SERS intensity of the free intercalating molecules diminished to a lesser degree for ADAP/DNA than for EB/DNA. The obtained difference was attributed to a larger aromatic surface of the ADAP molecules which, although intercalated, could be positioned near the enhancing nanoparticles, unlike the smaller EB molecules which were deeply inserted within the DNA helix.     

The Use of Voltammetry for Sorption Studies of Arsenic (III) Ions by Magnetic Beads Functionalized with Nucleobase Hydrazide Derivatives

In this work the interaction characteristics of nucleobases with As(III) are studied. Novel materials consisting of magnetic nanoparticles (MNPs) functionalized with adenine hydrazide (AH), guanine hydrazide (GH) and uracil hydrazide (UH) were elaborated. The adsorption isotherms were investigated electrochemically and it was shown that the adsorption capacity of the nanoparticles towards arsenic (III) increased in the following order: AH<UH<GH. The electrochemical detection of As(III) using the GH functionalized MNPs offered better results compared with the other functionalizations, with a sensitivity of 1.92 μA μg⁻¹ L and a limit of detection of 1.6 μg/L (21 nM).     

Cationic copolymer-mediated DNA immobilization: interfacial structure and composition as determined by ellipsometry, dual polarization interferometry, and neutron reflection

DNA immobilization onto support surfaces is required in biotechnological applications such as microarrays and gene delivery. This important interfacial molecular process can be mediated from a preadsobred cationic polymer. There is, however, a lack of understanding over the control of the interfacial composition and structural distribution of the DNA immobilized. We have used a combined approach of spectroscopic ellipsometry (SE), dual polarization interferometry (DPI) and neutron reflection (NR) to determine the interfacial polymer adsorption and the subsequent DNA binding. Cationic diblock copolymers incorporating 30 phosphorylcholine (PC) groups and different diethylaminoethyl groups, referred to as MPC30-DEAn, were chosen because of their well-defined molecular architecture. While our studies revealed different effects of surface charge and hydrophobicity, the amount of copolymers adsorbed on both model surfaces showed a broad trend of increase with solution pH, indicating a strong effect arising from pH-dependent charge density on the copolymers. In contrast, the copolymer structure and solution concentration showed a weak effect under the conditions studied. The subsequent DNA binding at pH 7 showed that on both surfaces the amount of DNA immobilized followed an approximate 1:1 charge interaction for all different DNA samples studied, irrespective of single or double strand, or different DNA size, indicating the dominant effect of electrostatic interaction between the two species. Both DPI and NR revealed consistent thickness increase upon DNA binding. Furthermore, with increasing DNA size, the interfacial layer became much thicker, and charge interaction drove more extensive interfacial mixing between the two species. Our results show that the amount of DNA immobilized is controlled by the amount of cationic copolymer preadsorbed that is in turn controlled by the solution pH and surface chemistry but that is barely affected by the type and concentration of DNA or cationic copolymer.     

Immobilized manganese porphyrin on functionalized magnetic nanoparticles via axial ligation: efficient and recyclable nanocatalyst for oxidation reactions

Magnetic nanoparticles (MNPs), Fe₃O₄@SiO₂, have been prepared and functionalized by 3-(chloropropyl)trimethoxysilane and then by imidazole to synthesize Fe₃O₄@SiO₂-Im. The functionalized Fe₃O₄ nanoparticles were used as a support to anchor manganese porphyrin via axial ligation. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, UV–vis spectroscopy, and scanning electron microscopy. Application of immobilized manganese porphyrin as a heterogeneous catalyst in oxidation of alkenes and sulfides was explored. To find suitable reaction conditions, effect of different parameters such as solvent and temperature on immobilization process and also various reaction parameters (oxidant, solvent, and time) on oxidation reactions has been investigated. The results showed that the immobilized Mn-porphyrin on functionalized MNPs is an efficient and reusable catalyst for oxidation of substrates.     

A spatially resolved nucleic acid biochip based on a gradient of density of immobilized probe oligonucleotide

The potential for a new biochip design based on a continuous gradient of density of immobilized single-stranded DNA oligonucleotide probes (ssDNA) is explored. This gradient resolved information platform (GRIP) can provide sequence identification based on the spatial location and extent of hybridization by a target sequence. Surfaces based on indium-tin oxide (ITO) on glass were first functionalized by 3-aminopropyltriethoxysilane (APTES) followed by attachment of glutaraldehyde, prior to immobilization of oligonucleotide probe that was terminated with amine. The use of Cy₃ and Cy₅ dye-labelled ssDNA probes and targets allowed estimation of density and correlation of the location of binding of labelled targets. Probe molecules of 20 mer lengths were loaded to produce density gradients in the range of 1.0-200 ng/mm². The biochips could resolve a mixture of fully complementary five base-pair mismatched targets by the location of binding on the surface. Thermal control provided additional selectivity. Thermal cycling and washing provided for regeneration of the surface, and the fluorescence intensities showed no deterioration in at least five cycles of hybridization reactions.     

Preconcentration and separation of ultra-trace palladium ion using pyridine-functionalized magnetic nanoparticles

We present a study on the application of magnetic nanoparticles (MNPs) prepared from Fe₃O₄ and functionalized with pyridine as an adsorbent for the solid-phase extraction of trace quantities of Pd(II) ion. The pyridine group was immobilized on the surface of the MNPs by covalent bonding of isonicotinamide. The modified MNPs can be readily separated from an aqueous solution by applying an external magnetic field. Effects of pH, the amount of functionalized MNPs, extraction time, type and quantity of eluent, desorption time, break-through volume and interfering ions on the extraction efficiency were optimized. The amount of Pd(II) was then determined using FAAS. Under the optimized conditions, the detection limit and preconcentration factor are 0.15?μg?L^-1 and 196, respectively, and the relative standard deviation (at 20?μgL^?1; for n?=?10) is 3.7?%. The method had a linear analytical range from 1 to 80?μg?L^-1 and was applied to determine Pd(II) in spiked tape water and soil.