A visual photothermal paper sensor for H_2S recognition through rational modulation LSPR wavelength of plasmonics

It is known that the localized surface plasmon resonance(LSPR) wavelength of plasmonics is highly dependent on compositions and geometry of plasmonics as well as the surrounding environments. Here, monodispersed Au@Ag core-shell nanoparticles(Au@Ag NPs) were prepared by carefully optimizing the shell thickness of Au@Ag NPs, and the presence of hydrogen sulfide(H_2 S) would significantly alter the LSPR wavelength. On the basis of this, a photothermal paper sensor for on-site recognition of H_2 S was constructed with a visual detection limit of 12.8 ng/L.     

Protoporphyrin IX‐Functionalized AgSiO2 Core–Shell Nanoparticles: Plasmonic Enhancement of Fluorescence and Singlet Oxygen Production

Metal‐enhanced processes arising from the coupling of a dye with metallic nanoparticles (NPs) have been widely reported. However, few studies have simultaneously investigated these mechanisms from the viewpoint of dye fluorescence and photoactivity. Herein, protoporphyrin IX (PpIX) is grafted onto the surface of silver core silica shell NPs in order to investigate the effect of silver (Ag) localized surface plasmon resonance (LSPR) on PpIX fluorescence and PpIX singlet oxygen (¹O₂) production. Using two Ag core sizes, we report a systematic study of these photophysical processes as a function of silica (SiO₂) spacer thickness, LSPR band position and excitation wavelength. The excitation of Ag NP LSPR, which overlaps the PpIX absorption band, leads to the concomitant enhancement of PpIX fluorescence and ¹O₂ production independently of the Ag core size, but in a more pronounced way for larger Ag cores. These enhancements result from the increase in the PpIX excitation rate through the LSPR excitation and decrease when the distance between PpIX and Ag NPs increases. A maximum fluorescence enhancement of up to 14‐fold, together with an increase in photogenerated ¹O₂ production of up to five times are obtained using 100 nm Ag cores coated with a 5 nm thick silica coating.     

应用于局域表面等离激元共振扫描显微探针的球形Au@Ag纳米粒子的合成及介电敏感性检测

局域表面等离激元共振(LSPR)显微探针的检测灵敏性主要取决于针尖上修饰的纳米粒子的LSPR性质.本文采用阴离子辅助法,在水溶液中通过调节Au核与Ag⁺的物质的量之比,实现Au核上不同厚度的Ag壳层包覆,可控地一步合成均一性好、银壳层较厚(≥10 nm)的核壳比不同的球形Au@Ag纳米粒子.通过扫描电镜(SEM)、透射电镜(TEM)及扫描透射电子显微镜X射线能谱(STM-EDS)线扫描分析对不同核壳比的Au@Ag纳米粒子进行形貌组成表征,证实了所合成核壳结构的可控性.将不同核壳比的Au@Ag纳米粒子置于不同折射率溶液中进行纳米粒子介电敏感性的研究,表明7.5 nm Au@28 nm Ag的纳米结构具有最高的品质因子.同时将不同核壳比的Au@Ag纳米粒子置于不同折射率的非导电性基底上进行单颗纳米粒子散射性质的研究,结果表明7.5 nm Au@28 nm Ag纳米粒子适合作为LSPR显微探针的高检测灵敏性纳米结构之一.     

Color‐Controlled Ag Nanoparticles and Nanorods within Confined Mesopores: Microwave‐Assisted Rapid Synthesis and Application in Plasmonic Catalysis under Visible‐Light Irradiation

Color‐controlled spherical Ag nanoparticles (NPs) and nanorods, with features that originate from their particle sizes and morphologies, can be synthesized within the mesoporous structure of SBA‐15 by the rapid and uniform microwave (MW)‐assisted alcohol reduction method in the absence or presence of surface‐modifying organic ligands. The obtained several Ag catalysts exhibit different catalytic activities in the H₂ production from ammonia borane (NH₃BH₃, AB) under dark conditions, and higher catalytic activity is observed by smaller yellow Ag NPs in spherical form. The catalytic activities are specifically enhanced under the light irradiation for all Ag catalysts. In particular, under light irradiation, the blue Ag nanorod shows a maximum enhancement of more than twice that observed in the dark. It should be noted that the order of increasing catalytic performance is in close agreement with the order of absorption intensity owing to the Ag localized surface plasmon resonance (LSPR) at irradiation light wavelength. Upon consideration of infrared thermal effect, wavelength dependence on catalytic activity, and effect of radical scavengers, it can be concluded that the dehydrogenation of AB is promoted by change of charge density of the Ag NP surface derived from LSPR. The LSPR‐enhanced catalytic activity can be further realized in the tandem reaction consisting of dehydrogenation of AB and hydrogenation of 4‐nitrophenol, in which a similar tendency in the enhancement of catalytic activity is observed.     

In-situ growth of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The paper describes a nonenzymatic amperometric H₂O₂ sensor that uses a nanocomposite consisting of Co₃O₄ nanoparticles (NPs) and mesoporous carbon nanofibers (Co₃O₄-MCNFs). The Co₃O₄ NPs were grown in situ on the MCNFs by a solvothermal procedure. The synergetic combination of the electrocatalytic activity of the Co₃O₄ NPs and the electrical conductivity of MCNFs as an immobilization matrix enhance the sensing ability of the hybrid nanostructure. The oxidation current, best measured at 0.2 V (vs. SCE) is linear in the 1 to 2580 μM H₂O₂ concentration range, with a 0.5 μM lower detection limit (at an S/N ratio of 3). The sensor is highly selective even in the presence of common electroactive interferents. It was applied to the determination of H₂O₂ in spiked milk samples.

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Graphical abstract Schematic of the synthesis of a nanocomposite consisting of Co₃O₄ nanoparticles (NPs) and mesoporous carbon nanofibers (Co₃O₄-MCNFs) by a solvothermal procedure. It was used as electrocatalyst for direct oxidation of H₂O₂.

     

Photocatalytic intercalated material based on HLaNb<Subscript>2</Subscript>O<Subscript>7</Subscript> as host and Cd<Subscript>0.8</Subscript>Zn<Subscript>0.2</Subscript>S as guest

A novel photocatalytic material (Pt,Cd0.8Zn0.2S)/HLaNb2O7 was fabricated by successive intercalation and exchange reactions. The (Pt,Cd0.8Zn0.2S)/HLaNb2O7 possessed a gallery height less than 0.5 nm and showed a broad absorption with wavelength over 370-500 nm. Using (Pt,Cd0.8Zn0.2S)/HLaNb2O7 as catalyst, the photocatalytic H2 evolution was more than 160 cm3·h-1·g-1 in the presence of Na2S as a sacrificial agent under irradiation with wavelength more than 290 nm from a 100-W mercury lamp. Furthermore, the catalyst showed photocatalytic activity even under visible light irradiation.     

Sulfur Precursor Reactivity Affecting the Crystal Phase and Morphology of Cu2−xS Nanoparticles

For plasmonic copper-deficient Cu_2−xS nanoparticles (NPs), accurate control of the crystal phase and morphology is highly desirable as both of which are known to determine the localized surface plasmon resonance (LSPR) wavelength and amplitude. Here, how the sulfur precursor reactivity in the synthesis of Cu_2−xS NPs affects the resulting crystal phase and morphology is examined. Djurleite Cu_1.94S, roxbyite Cu_1.8S, digenite Cu_1.8S as well as covellite CuS nanodisks were synthesized by using 1-dodecanethiol, N,N-dibutylthiourea, and crystal sulfur 1-octadecene/oleylamine solutions and their crystal phase dependent LSPR properties were exhaustively discussed. In addition, crystal phase interconversion between covellite CuS and djurleite/roxbyite Cu_2−xS was realized in the presence of the above sulfur precursors. On the other hand, djurleite Cu_1.94S nanorods rather than nanodisks were prepared by replacing 1-dodecanethiol with more reactive tert-dodecanethiol. The structural and morphological Cu_2−xS NPs here holds great promise in the application of photothermal therapy, photocatalysis, surface-enhanced Raman scattering (SERS), and many others.     

SiO2/TiO2 Hollow Nanoparticles Decorated with Ag Nanoparticles: Enhanced Visible Light Absorption and Improved Light Scattering in Dye‐Sensitized Solar Cells

Hollow SiO₂/TiO₂ nanoparticles decorated with Ag nanoparticles (NPs) of controlled size (Ag@HNPs) were fabricated in order to enhance visible‐light absorption and improve light scattering in dye‐sensitized solar cells (DSSCs). They exhibited localized surface plasmon resonance (LSPR) and the LSPR effects were significantly influenced by the size of the Ag NPs. The absorption peak of the LSPR band dramatically increased with increasing Ag NP size. The LSPR of the large Ag NPs mainly increased the light absorption at short wavelengths, whereas the scattering from the SiO₂/TiO₂ HNPs improved the light absorption at long wavelengths. This enabled the working electrode to use the full solar spectrum. Furthermore, the SiO₂ layer thickness was adjusted to maximize the LSPR from the Ag NPs and avoid corrosion of the Ag NPs by the electrolyte. Importantly, the power conversion efficiency (PCE) increased from 7.1 % with purely TiO₂‐based DSSCs to 8.1 % with HNP‐based DSSCs, which is an approximately 12 % enhancement and can be attributed to greater light scattering. Furthermore, the PCEs of Ag@HNP‐based DSSCs were 11 % higher (8.1 vs. 9.0 %) than the bare‐HNP‐based DSSCs, which can be attributed to LSPR. Together, the PCE of Ag@HNP‐based DSSCs improved by a total of 27 %, from 7.1 to 9.0 %, due to these two effects. This comparative research will offer guidance in the design of multifunctional nanomaterials and the optimization of solar‐cell performance.     

SERS based aptasensor for ochratoxin A by combining Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@Au magnetic nanoparticles and Au-DTNB@Ag nanoprobes with multiple signal enhancement

A SERS-based aptasensor for ochratoxin A (OTA) is described. It is making use of Fe₃O₄@Au magnetic nanoparticles (MGNPs) and of Au@Ag nanoprobes modified with the Raman reporter 5,5-dithiobis-(2-nitrobenzoic acid; DTNB). Au-DTNB@Ag NPs were modified with the OTA aptamer (aptamer-GSNPs) and used as Raman signal probes. The SERS peak of DTNB at 1331 cm^?1 was used for quantitative analysis. MGNPs modified with cDNA (cDNA-MGNPs) were used as capture probes and reinforced substrates. When the Au-DTNB@Ag-Fe₃O₄@Au complexes are formed through oligonucleotide hybridization, the Raman signal intensity of the Raman probe is significantly enhanced. If the OTA concentration in samples increases, more Raman signal probes (aptamer-GSNPs) will dissociate from the cDNA-MGNPs because more OTA aptamer is bound by OTA. This leads to a lower Raman signal after magnetic separation. Under the optimal conditions, the detection limit for OTA is 0.48 pg·mL^?1 based on 3σ criterion. This is attributed to the multiple Raman signal enhancement and the good performance of the OTA aptamer. The good recovery and accuracy of the assay was confirmed by evaluating spiked samples of wine and coffee.

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Graphical abstract Schematic of an aptamer based SERS assay for OTA by integrating Fe₃O₄@AuNPs (MGNPs) with Au-DTNB@Ag NPs with multiple signal enhancement. Aptamer modified Au-DTNB@Ag NPs are used as Raman probes, and MGNPs modified with cDNA are used as capture probes and reinforced substrates.

     

MnO<Subscript>2</Subscript> Nanoparticles and Carbon Nanofibers Nanocomposites with High Sensing Performance Toward Glucose

By combining the advantages of manganese dioxide nanoparticles (MnO₂ NPs) and carbon nanofibers (CNFs), a biosensing electrode surface as a high-performance enzyme biosensor is designed in this work. MnO₂ NPs and CNFs nanocomposites (MnO₂–CNFs) were prepared by using a simple hydrothermal method and then were characterized by scanning electron microscopy, powder X-ray diffraction, fourier transform infrared spectroscopy, energy dispersive spectrometry and electrochemisty. The results showed that MnO₂ NPs are uniformly attached to the surface of CNFs. Meanwhile, the MnO₂–CNFs nanocomposites as a supporting matrix can provide an efficient and advantageous platform for electrochemical sensing applications. On the basis of the improved sensitivity of MnO₂–CNFs modified electrode toward H₂O₂ at low overpotential, a MnO₂–CNFs based glucose biosensor was fabricated by monitoring H₂O₂ produced by an enzymatic reaction between glucose oxidase and glucose. The constructed biosensor exhibited a linear calibration graph for glucose in a concentration range of 0.08–4.6 mM and a low detection limit of 0.015 mM. In addition, the biosensor showed other excellent characteristics, such as high sensitivity and selectivity, short response time, and the relative low apparent Michaelis–Menten constant. Analysis of human urine spiked with glucose at different concentration levels yielded recoveries between 101.0 and 104.8%.     

Synthesis of novel magnetic sulfur-doped Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles for efficient removal of Pb(II)

In this work, we report the synthesis of magnetic sulfur-doped Fe₃O₄ nanoparticles (Fe₃O₄:S NPs) with a novel simple strategy, which includes low temperature multicomponent mixing and high temperature sintering. The prepared Fe₃O₄:S NPs exhibit a much better adsorption performance towards Pb(II) than bare Fe₃O₄ nanoparticles. FTIR, XPS, and XRD analyses suggested that the removal mechanisms of Pb(II) by Fe₃O₄:S NPs were associated with the process of precipitation (formation of PbS), hydrolysis, and surface adsorption. The kinetic studies showed that the adsorption data were described well by a pseudo second-order kinetic model, and the adsorption isotherms could be presented by Freundlich isotherm model. Moreover, the adsorption was not significantly affected by the coexisting ions, and the adsorbent could be easily separated from water by an external magnetic field after Pb(II) adsorption. Thus, Fe₃O₄:S NPs are supposed to be a good adsorbents for Pb(II) ions in environmental remediation.     

Flower-like Au/Ag/TiO<Subscript>2</Subscript> nanocomposites with enhanced photocatalytic efficiency under visible light irradiation

Uniform flower-like TiO₂ coated Au nanostars and core-shell Au@Ag nanostars with different amounts of Ag coating were prepared through a facile method by hydrolysis of TiF₄ under an acidic environment. The photocatalytic capability of these flower-like nanocomposites under visible light irradiation was found to be enhanced by up to 4.7-fold compared to commercial P25 TiO₂ nanoparticles. The enhanced photocatalytic activity was ascribed to improved light absorption and hot electron injection from the photo-excited Au@Ag core to the TiO₂ shell.     

Mineralization of TiO<Subscript>2</Subscript> nanoparticles for the determination of titanium in rat tissues

In order to draw appropriate conclusions about the possible adverse biological effects of titanium dioxide nanoparticles (TiO₂—NPs), the so-called “dose?effect” relationship must be explored. This requires proper quantification of titanium in complex matrices such as animal organs for future toxicological studies. This study presents the method development for mineralizing TiO₂—NPs for analysis of biological tissues. We compared the recovery and quantification limits of the four most commonly used mineralization methods for metal oxides. Microwave-assisted dissolution in an HNO3–HF mixture followed by H₂O₂ treatment produced the best results for a TiO₂—NPs suspension, with 96 ± 8% recovery and a limit of quantification as low as 0.9 µg/L. This method was then used for the determination of titanium levels in tissue samples taken from rats. However, our tests revealed that even this method is not sensitive enough for quantifying titanium levels in single olfactory bulbs or hippocampus in control animals.     

Catalytic Systems for the H<Subscript>2</Subscript>S Wet Oxidation at room Temperature

The catalytic wet oxidation process is the most attractive process for small-scale hydrogen sulfide (H₂S) removal from natural gas. The catalytic wet oxidation process is anticipated to be cost effective and simple so that it can be used for treating sour gases containing small amounts of H₂S and can be easily operated even in isolated sites. The development of effective catalyst is the key technology in the wet catalytic oxidation of H₂S. The scale of operation for the process has to be flexible so its use will not be limited by the flow rates of the gas to be treated. The heterogeneous catalytic wet oxidation of H₂S has been attempted on activated carbons, but the H₂S removal capacity still shows the low removal efficiency. The catalytic wet oxidation of H₂S was studied over Fe/MgO for an effective removal of H₂S. In order to develop a sulfur removal technology, one has to know what surface species of catalyst are the most active. This article discusses the following systematic studies: (i) the catalytic preparation to disperse Fe metal well on MgO support for enhancing H₂S removal capacity, (ii) the effect of the catalytic morphology on the activity of Fe/MgO for the H₂S wet oxidation, (iii) the influence of precursor and support on the activity of Fe/MgO for catalytic wet oxidation of H₂S to sulfur.     

Transition metal salts of H<Subscript>4</Subscript>PMo<Subscript>11</Subscript>VO<Subscript>40</Subscript> for efficient H<Subscript>2</Subscript>S removal in the liquid redox process

Several transition metal (Cu²⁺, Fe³⁺, Zn²⁺, Mn⁴⁺, and Cr⁶⁺) salts of H₄PMo₁₁VO₄₀ were prepared and their solutions were used initially for H₂S removal in the liquid redox process. H₂S removal tests were performed by dynamic absorption experiments. Among these polyoxometalates, that with the Cu²⁺ cation was found to have pronounced H₂S removal performance with the removal efficiency of up to 98%. The relevant oxidative desulfurization mechanism and the role of Cu²⁺ were studied.     

Magnetic carbon nitride nanocomposites as enhanced peroxidase mimetics for use in colorimetric bioassays,and their application to the determination of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose

Graphite-like carbon nitride ? Fe₃O₄ magnetic nanocomposites were synthesized by a chemical co-precipitation method. The nanocomposites were characterized by transmission electron microscopy, X-ray diffraction, FTIR spectroscopy, X-ray photoelectron spectroscopy and magnetization hysteresis loops. The nanocomposites exhibit enhanced peroxidase-like activity (compared to that of graphite-like carbon nitride or Fe₃O₄ NPs). More specifically, they are capable of catalyzing the oxidation of different peroxidase substrates (such as TMB, ABTS or OPD) by H₂O₂ to produce the typical color reactions (blue, green or orange). The nanocomposites retain their magnetic properties and can be separated by an external magnet. On the basis of these findings, a highly sensitive and selective method was applied to the determination of H₂O₂ and glucose (by using glucose oxidase). It was successfully applied to the determination of glucose in (spiked) human serum. Compared to other nanomaterial-based peroxidase mimetics, the one described here provides distinctly higher sensitivity for both H₂O₂ and glucose, with detection limits as low as 0.3 μM and 0.25 μM, respectively.

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Graphical abstract The magnetic carbon nitride nanocomposite exhibits enhanced peroxidase-like activity that is much larger than that of graphite-like carbon nitride or Fe₃O₄ NPs alone. This finding was applied to design a highly sensitive and selective colorimetric assay for H₂O₂ and glucose.

     

Ag2S nanoparticles as an emerging single-component theranostic agent

Last two decades, with the rapid changes and development of nanotechnology and biological materials, diverse multi-functional nanomaterials emerging, which offers a novel way to treat and diagnose diseases, and therefore spawned the new biomedical technology of theranostics, which integrates the treatment and diagnosis or monitoring of diseases into one. Ag₂S as a bio-nanomaterial with low biotoxicity has attracted more and more attention due to its good photoluminescence properties and fluorescence imaging of small animals in the second near-infrared region (NIR-II). Meanwhile, Ag₂S has the ability to absorb near-infrared light strongly because of its local surface plasma resonance (LSPR) effect and had become a kind of photothermal converters with good photothermal conversion efficiency. More interestingly, both photothermal effect and fluorescence characteristics of Ag₂S nanoparticles (NPs) are closely related to their particle sizes. However, the relationship between photothermal effect and fluorescence characteristics of Ag₂S NPs and their sizes has not been reviewed so far. Herein, the synthesis methods and influencing factors of synthesize Ag₂S NPs with different sizes were compared firstly, and then the photothermal effect and fluorescence characteristics of Ag₂S NPs with different sizes were summarized. Finally, the possibilities and challenges of using Ag₂S NPs to construct theranostic agent were discussed in the end.     

Effect of active impurities on the condensation of nanoparticles from supersaturated carbon vapor in the combined laser photolysis of C<Subscript>3</Subscript>O<Subscript>2</Subscript> and H<Subscript>2</Subscript>S

The effect of active H₂S, HS^·, and atomic hydrogen impurities on the condensation of highly supersaturated carbon vapor obtained in the combined laser photolysis of a mixture of C₃O₂ and H₂S diluted with argon was studied. The concentrations of carbon vapor, HS^·, and atomic hydrogen obtained in the laser photolysis of the mixture were determined using the absorption cross sections of C₃O₂ and H₂S molecules measured in this work and the measured amount of absorbed laser radiation. The time profiles of the sizes of growing nanoparticles synthesized in C₃O₂ + Ar and C₃O₂ + H₂S + Ar mixtures were measured using the laser-induced incandescence (LII) method. An improved LII model was developed, which simultaneously took into account the heating and cooling of nanoparticles and the temperature dependence of the thermophysical properties of nanoparticles, as well as the cooling of nanoparticles by evaporation and thermal emission. The size distributions of carbon nanoparticles formed in the presence and absence of active impurities were determined with the use of a transmission electron microscope. The final average size of carbon nanoparticles was found to decrease from 12 to 9 nm upon the addition of H₂S to the system, whereas the rate of nanoparticle growth decreased by a factor of 3, and the properties of nanoparticles changed. In particular, the translational energy accommodation coefficient for Ar molecules at the surface of carbon nanoparticles was found to decrease from 0.44 to 0.30. A comparison of the calculated total carbon balance at the early stage of nanoparticle formation with experimental data demonstrated that the reaction C + H₂S → HCS^· + H, which removes a portion of carbon vapor from the condensation process, has a determining effect on the carbon balance in the system. It was found that HS^· and atomic hydrogen affect the carbon balance in the system only slightly. Thus, the experimentally observed decrease in the rate of nanoparticle growth and in the sizes of nanoparticles can be explained by a decrease in the concentration of free carbon upon the addition of H₂S molecules to the system.     

A review on nanomaterial-based electrochemical sensors for H<Subscript>2</Subscript>O<Subscript>2</Subscript>, H<Subscript>2</Subscript>S and NO inside cells or released by cells

The incorporation of nanomaterials into electrochemical sensors is an attractive approach towards the improvement of the sensitivity of amperometry and also can provide improved sensor selectivity and stability. This review (with 137 references) details the current state of the art and new trends in nanomaterial-based electrochemical sensing of hydrogen peroxide (H₂O₂), hydrogen sulfide (H₂S) and nitric oxide (NO) in cells or released by cells. The article starts with a discussion of the significance of the three analytes, and this is followed by three sections that summarize the electrochemical detection schemes for H₂O₂, H₂S and NO. Each section first summarizes the respective physiological roles, and then reviews electrochemical sensors based on the use of carbon nanomaterials, noble metal nanomaterials, metal oxide nanomaterials, and layered doubled hydroxides. The materials are compiled in three tables along with figures of merit for the various sensors.

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Graphical abstract Nanomaterial-based electrochemical sensors for Reactive oxygen species (H₂O₂), Reactive nitrogen species (NO) and Reactive hydrogen sulfide species (H₂S) inside cells or released by cells.

     

Synthesis and characterization of η<Superscript>3</Superscript>-allyl palladium(II) complexes with Ph<Subscript>2</Subscript>P(S)CHP(S)Ph<Subscript>2</Subscript> and OC(CF<Subscript>3</Subscript>)CHCO(C<Subscript>4</Subscript>H<Subscript>3</Subscript>S) co-ligands

The new complexes [(η³-Me₂CCMeCH₂)Pd{η²-Ph₂P(S)CHP(S)Ph₂] (1), [(η³-Me₂CCMeCH₂)Pd{η²-OC(CF₃) CHCO(C₄H₃S)}] (2) and [(η³-CH₂CMeCH₂)Pd{η²-OC(CF₃)CHCO(C₄H₃S)}] (3) have been synthesized by reacting [(η³-allyl)Pd(μ-Cl)]₂ with Ph₂P(S)CH₂P(S)Ph₂ and OC(CF₃)CH₂CO(C₄H₃S) in the presence of base. All have been characterized by elemental analysis, FT-IR, ¹H-n.m.r and FAB-mass spectroscopy. Spectroscopic studies suggest that both ligands are bidentate, forming six-membered Pd-S-P-C-P-S and Pd-O-C-C-C-O palladacycles, the η³-allyl group completing the coordination sphere.