1T-Phase Dirac Semimetal PdTe2 Nanoparticles for Efficient Photothermal Therapy in the NIR-II Biowindow.

1T-phase transition-metal dichalcogenides (TMDs) nanomaterials are one type of emerging and promising near-infrared II (NIR-II) photothermal agents (PTAs) derived from their distinct metallic electronic structure, but it is still challenging to synthesize these nanomaterials. Herein, PdTe2 nanoparticles (PTNs) with a 1T crystal symmetry and around 50 nm in size are prepared by an electrochemical exfoliation method, and the corresponding photothermal performances irradiated under a NIR-II laser have been explored. The encapsulation of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-poly(ethylene glycol) (DSPE-PEG) endows PTNs with water solubility, enhanced photothermal stability, and high biocompatibility. Notably, PTN/DSPE-PEG displays a potent absorbance through the NIR-II zone and considerable photothermal conversion efficiency, which is up to 68% when irradiated with a 1060 nm laser. With these unique photothermal properties, excellent in vitro and in vivo tumor inhibition effects of PTN/DSPE-PEG have been achieved under the irradiation of a NIR-II (1060 nm) laser without visible toxicity to normal tissues, suggesting that it is an efficient NIR-II photothermal nanoagent.

A photoelectrochemical enzyme biosensor based on functionalized hematite microcubes for rutin determination by square-wave voltammetry.

A photoelectrochemical biosensing strategy for the highly sensitive detection of the flavonoid rutin was developed by synergizing the photoelectrocatalytic properties of hematite (α-Fe2O3) decorated with palladium nanoparticles (PdNPs) and the biocatalysis towards laccase-based reactions. The integration of α-Fe2O3.PdNPs with a polyphenol oxidase as a biorecognition element yields a novel biosensing platform. Under visible light irradiation, the photoactive biocomposite can generate a stable photocurrent, which was found to be directly dependent upon the concentration of rutin. Under the optimal experimental conditions, the cathodic photocurrent, measured at 0.33 V vs. Ag/AgCl, from the square-wave voltammograms presented a linear dependence on the rutin concentration within the range of 0.008-30.0 × 10-8 mol L-1 (sensitivity: 1.7 µA·(× 10-8 M-1)·cm-2), with an experimental detection limit (S/N = 3) of 8.4 × 10-11 mol L-1. The proposed biosensor device presented good selectivity towards rutin in the presence of various organic compounds and inorganic ions, demonstrating the potential application of this biosensing platform in complex matrices. This bioanalytical device also exhibited excellent operational and analytical properties, such as intra-day (standard deviation, SD = 0.21%) and inter-day (SD = 1.30%) repeatability, and long storage stability (SD = 2.80% over 30 days).Graphical abstract.

Dual palladium-photoredox catalyzed chemoselective C-H arylation of phenylureas.

A highly chemoselective C-H arylation of phenylureas has been accomplished using dual palladium-photoredox catalysis at room temperature without any additives, base or external oxidants. Regioselective C-H arylation of N,N'-diaryl substituted unsymmetrical phenylureas has also been accomplished by a careful choice of aryl groups.

Degradable Holey Palladium Nanosheets with Highly Active 1D Nanoholes for Synergetic Phototherapy of Hypoxic Tumors.

Pd nanosheets (Pd NSs) have attracted extensive attention due to their promising application in photothermal therapy. However, their photodynamic properties have rarely been reported. Herein, holey Pd NSs (H-Pd NSs) with intrinsic photodynamic and hypoxia-resistant capacities are fabricated for the first time using an anisotropic oxidative etching strategy, which introduces one-dimensional nanoholes with active (100) facets on the hole walls. Gradual degradation of H-Pd NSs is observed in simulated physiological media due to the oxidative etching. In vitro and in vivo studies indicate that the single-component H-Pd NSs can act as a photothermal/photodynamic agent for imaging-guided hypoxic tumor therapy, with a high tumor inhibition rate of 99.7%. This work provides ideas for introducing active facets in metallic pore walls, broadening the application of Pd NSs and the design of biodegradable noble metal nanotheranostic agents for cancer therapy.

M/g-C3N4 (M=Ag, Au, and Pd) composite: synthesis via sunlight photodeposition and application towards the degradation of bisphenol A.

In this work, natural sunlight successfully induced the deposition of gold (Au), silver (Ag), and palladium (Pd) nanoparticles (NPs) with 17.10, 9.07, and 12.70 wt% onto the surface of graphitic carbon nitride (g-C3N4). The photocatalytic evaluation was carried out by adopting Bisphenol A (BPA) as a pollutant under natural sunlight irradiation. The presence of noble metals was confirmed by EDX, HRTEM, and XPS analysis. The deposition of Ag NPs (7.9 nm) resulted in the degradation rate which was 2.15-fold higher than pure g-C3N4 due to its relatively small particle size, contributing to superior charge separation efficiency. Au/g-C3N4 unveiled inferior photoactivity because the LSPR phenomenon provided two pathways for electron transfer between Au NPs and g-C3N4 further diminished the performance. The improved degradation lies crucially on the particle size and Schottky barrier formation at the interface of M/g-C3N4 (M=Au, Ag, and Pd) but not the visible light harvesting properties. The mechanism insight revealed the holes (h+) and superoxide radical (•O2-) radical actively involved in photocatalytic reaction for all composites.

General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols.

A general, efficient, and site-selective visible light-induced Pd-catalyzed remote desaturation of aliphatic alcohols into valuable allylic, homoallylic, and bis-homoallylic alcohols has been developed. This transformation operates via a hybrid Pd-radical mechanism, which synergistically combines the favorable features of radical approaches, such as a facile remote C-H HAT step, with that of transition-metal-catalyzed chemistry (selective ß-hydrogen elimination step). This allows achieving superior degrees of regioselectivity and yields in the desaturation of alcohols compared to those obtained by the state-of-the-art desaturation methods. The HAT at unactivated C(sp3)-H sites is enabled by the easily installable/removable Si-auxiliaries. Formation of the key hybrid alkyl Pd-radical intermediates is efficiently induced by visible light from alkyl iodides and Pd(0) complexes. Notably, this method requires no exogenous photosensitizers or external oxidants.

Facile Synthesis of r-GO@Pd/TiO2 Nanocomposites and Its Photocatalytic Activity Under Visible Light.

Reduced Graphene Oxide Wrapped Pd/TiO2 (r-GO@Pd/TiO2) which exhibited high photocatalytic activity under visible light was synthesized from commercial chemicals. The classic sol-gel method and the Ar gas bubbling composition was used in the preparation of the catalyst. Furthermore, the best Pd-doping concentration in crystals, the wrapping concentration of r-GO over nanoparticles, and the optimal calcination temperature were investigated to enhance the photocatalytic activity of the hybrid catalyst. The experimental results showed that the catalytic efficiency of r-GO@Pd/TiO2 reached maximum value at the optimum synthesis conditions: 0.7 wt% Pd-doped TiO2 by sol-gel process, calcination temperature of 550 °C, 1 mg of GO for 100 .gram wrapped Pd/TiO2. X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM) techniques were conducted to determine the nanostructure of the catalysts. The average crystallite size of nanoparticles was 14 nm with perfect dispersion of Pd dots and wraps of r-GO membrane. Methyl Blue was used as an organic dye model to test the ability in wastewater treatment of the catalysts. A comparison between different catalysts' characteristics was also studied. The r-GO@Pd/TiO2 showed a higher photocatalytic activity compared to Pd/TiO2 and commercial P25. Additionally, the complete dye reduction under visible light excitation indicated that wrapping r-GO round Pd/TiO2 improved the photocatalytic activity of catalysts. The determination of the stability of r-GO@Pd/TiO2 showed that its photocatalysis was persistent over several times of recycling examination. Therefore, r-GO@ Pd/TiO2 in wastewater treatment.

Effect of heating palladium-silver alloys on ceramic bond strength.

STATEMENT OF PROBLEM: The effects of different heat treatments on the internal oxidation and metal-ceramic bond in Pd-Ag alloys with different trace elements require further documentation. PURPOSE: The purpose of this in vitro study was to determine whether heat treatment affects the metal-ceramic bond strength of 2 Pd-Ag alloys containing different trace elements. MATERIAL AND METHODS: Thirteen cast specimens (25×3×0.5 mm) from each of 2 Pd-Ag alloy groups (W-1 and Argelite 61+3) were allocated to heat treatments before porcelain application: heating under reduced atmospheric pressure of 0.0014 MPa and 0.0026 MPa and heating under normal atmospheric pressure. Bond strengths were evaluated using a 3-point bending test according to ISO9693. Results were analyzed using 2-way ANOVA and Tukey HSD test (α=.05). Visual observation was used to determine the failure types of the fractured specimens. Scanning electron microscopy and energy dispersive spectroscopy were used to study morphologies, elemental compositions, and distributions in the specimens. RESULTS: The W-1 group had a mean bond strength significantly higher than that of Argelite 61+3 (P<.001). Heating under reduced atmospheric pressures of 0.0014 MPa and 0.0026 MPa resulted in similar bond strengths (P=.331), and both pressures had significantly higher bond strengths than that of heating under normal atmospheric pressure (P=.002, P<.001). Heating under different air pressures resulted in Pd-Ag alloys that contained either Sn or In and Ga, with various degrees of internal oxidation and different quantities of metallic nodules. CONCLUSIONS: Heating under reduced atmospheric pressure effectively improved the bond strength of the ceramic-to-Pd-Ag alloys.

Facile and rapid synthesis of Pd nanodendrites for electrocatalysis and surface-enhanced Raman scattering applications.

Numerous properties from metal nanostructures can be tuned by controlling both their size and shape. In particular, the latter is extremely important because the type of crystalline surface affects the surface electronic density. This paper describes a simple approach to the synthesis of highly-structured, anisotropic palladium nanostructured dendrites. They were obtained using an eco-friendly biomolecule 5-hydroxytryptophan, which acts as both a reducing and stabilizing agent. The growth mechanism is proposed for the evolution of dendrites morphology. It was found that the concentration of 5-hydroxytryptophan played a vital role on the morphology of the nanostructured Pd dendrites. This nanomaterial shows enhanced electrocatalytic performance towards the oxidation of formic acid, and it exhibits surface-enhanced Raman scattering properties towards the prostate specific antigen. These properties may be explored in fuel cells and biosensors, respectively.

Solar energy assisted starch-stabilized palladium nanoparticles and their application in C-C coupling reactions.

Present work reports a novel one step, greener protocol for the synthesis of starch-stabilized palladium nanoparticles (PdNPs) with an average particle diameter of 30-40 nm. These particles were stable and uniform in size. In present protocol, the concentrated solar energy mediated reduction of palladium chloride was achieved by using citric acid as a reducing agent and starch as a capping agent. UV-Visible spectroscopy, Transmission Electron Microscopy, Field Emission Gun-Scanning Electron Microscopy, Selected Area Electron Diffraction and Electron dispersive X-ray Spectral analysis techniques were used to characterize this starch capped PdNPs. Herein; we are reporting such combination of starch and citric acid in the synthesis of PdNPs for the first time. The catalytic activity of synthesized nanoparticles has been checked for Suzuki and Heck cross coupling reactions. The product yield was confirmed by GC. The products were confirmed using GC-MS analysis and also using GC with the help of authentic standards. Solar energy assisted starch stabilized PdNPs showed excellent activity in the C-C bond formation between aryl halides (I, Br) with phenyl boronic acid and its derivatives. In addition, the catalyst showed good activity in the Heck coupling reaction of C-C bond formation of aryl halides with aromatic alkene. The use of starch, citric acid, water and solar energy makes present protocol greener.

Graded bit patterned magnetic arrays fabricated via angled low-energy He ion irradiation.

A bit patterned magnetic array based on Co/Pd magnetic multilayers with a binary perpendicular magnetic anisotropy distribution was fabricated. The binary anisotropy distribution was attained through angled helium ion irradiation of a bit edge using hydrogen silsesquioxane (HSQ) resist as an ion stopping layer to protect the rest of the bit. The viability of this technique was explored numerically and evaluated through magnetic measurements of the prepared bit patterned magnetic array. The resulting graded bit patterned magnetic array showed a 35% reduction in coercivity and a 9% narrowing of the standard deviation of the switching field.

Radiofrequency heating and magnetically induced displacement of dental magnetic attachments during 3.0 T MRI.

OBJECTIVE: The aim of this study was to estimate the risk of injury from dental magnetic attachments due to their radiofrequency (RF) heating and magnetically induced displacement during 3.0 T MRI. METHODS: To examine the magnetic attachments, we adopted the American Society for Testing and Materials F2182-02a and F2052-06 standards in two MRI systems (Achieva 3.0 T Nova Dual; Philips, Tokyo, Japan, and Signa HDxt 3.0 T; GE Healthcare, Milwaukee, WI). The temperature change was measured in a cylindrical keeper (GIGAUSS D600; GC, Tokyo, Japan) with coping of the casting alloy and a keeper with a dental implant at the maximum specific absorption rate (SAR) for 20 min. To measure the magnetically induced displacement force, three sizes of keepers (GIGAUSS D400, D600 and D1000) were used in deflection angle tests conducted at the point of the maximum magnetic field strength. RESULTS: Temperature elevations of both coping and implant were higher in the Signa system than in the Achieva system. The highest temperature changes in the keeper with implant and keeper with coping were 0.6 °C and 0.8 °C in the Signa system, respectively. The temperature increase did not exceed 1.0 °C at any location. The deflection angle (α) was not measurable because it exceeded 90°. GIGAUSS D400 required an extra 3.0 g load to constrain the deflection angle to less than 45°; GIGAUSS D600 and D1000 required 5.0 and 9.0 g loads, respectively. CONCLUSIONS: Dental magnetic attachments pose no risk due to RF heating and magnetically induced displacement at 3.0 T MRI. However, it is necessary to confirm that these keepers are securely attached to the prosthesis before imaging.

Palladium-catalyzed decarboxylative arylation of potassium cyanoacetate: synthesis of α-diaryl nitriles from aryl halides.

A palladium-catalyzed decarboxylative coupling of potassium cyanoacetate with aryl bromides and chlorides is described. The reaction conditions feature the absence of additional strong inorganic bases and provide ester functional group tolerance. With Pd(dba)(2) and XPhos ligand as the catalyst system, α-diaryl nitriles can be obtained in good yields.

Complete oxidation of acetaldehyde and toluene over a Pd/WO(3) photocatalyst under fluorescent- or visible-light irradiation.

Acetaldehyde was completely oxidized to CO(2) over a Pd/WO(3) photocatalyst under fluorescent-light irradiation in a flow-type reactor, and Pd/WO(3) was also used to completely oxidize toluene to CO(2) in a batch reactor under visible-light irradiation.

A possible in vivo generator 103Pd/103mRh--recoil considerations.

The use of Auger emitters as potential radiopharmaceuticals is increasingly investigated. One such radionuclide of interest is (103m)Rh. This can be produced from (103)Ru or from (103)Pd in an in vivo generator. A potential problem with this concept is the recoil of the (103m)Rh out of the carrier molecule and even out of the target cell. In order to determine whether this would happen in the (103)Pd/(103m)Rh case calculations were done to prove that this does not happen. From theoretical considerations it seems that the (103)Pd/(103m)Rh in vivo generator system would be possible.

Highly conducting patterned Pd nanowires by direct-write electron beam lithography.

Palladium hexadecylthiolate is shown to serve as a negative-tone direct-write electron resist to produce nanopatterns down to 30 nm. The written patterns do not deviate much from the precursor in composition, while a post-treatment at 230 degrees C in air produced metallic Pd nanowires with residual carbon less than 10% and resistivity close to the bulk value, a desirable property of interconnects in nanocircuitry. The as-written patterns contain small nanocrystals (<5 nm) in a hydrocarbon matrix, which upon annealing aggregate to form well-connected networks of larger nanocrystals (5-15 nm), thus giving rise to metallic conductivity.

EPR investigations on radiation induced chemical transformations in Pd(ClO4)2/i-PrOH/HClO4 system from 77 to 300 K.

The EPR studies have been carried out on gamma irradiated samples of Pd(ClO4)2 in 9 M/4M HClO4 in the presence and absence of isopropanol [i-PrOH (5%, v/v)], in the temperature range of 77-300 K. The EPR studies revealed the formation of Pd+ complex, Pd3+ complex and several radicals such as H., OH., ClO3., ClO4. and O3- on radiolysis of these systems. Reduction of Pd2+ to Pd clusters could not be observed in the absence of i-PrOH and warming of the irradiated sample finally resulted in recovery of Pd2+ complex. However, in the presence of 5% i-PrOH, strongly oxidizing radicals like OH., ClO3. and ClO4. are suppressed and (CH3)2C.OH radical was produced along with reducing species like H.. EPR spectra in these strongly reducing conditions showed formation of Pd+ complex, which on heating above 230 K, disproportionated into Pd0 and Pd2+ complex and finally lead to formation of Pd metal aggregates. Simultaneously, pulse radiolysis technique has been employed as an alternative method to verify the EPR observations.

Hysteresis effect in FePd magnetic stripes studied by coherent soft X-ray resonant magnetic scattering.

An FePd thin film sample, showing magnetic stripe domains as imaged by magnetic force microscopy, has been measured by soft X-ray resonant magnetic scattering in reflection geometry. Illumination with coherent radiation, produced by inserting a 20 microm pinhole in front of the sample, leads to a magnetic speckle pattern in the scattered intensity that gives access to the domain morphology. Application of an in-plane magnetic field for a few seconds gives a strong change in the observed intensity fluctuations, which indicates a large degree of variation between the two patterns taken before and after field exposure. From the speckle pattern we calculate a degree of coherence of beta = 0.5 for the incident beam.

Separation of 111Ag from neutron irradiated natural palladium using alumina as an adsorbent.

A simple method is presented for the separation of no-carrier-added 111Ag from neutron irradiated natural palladium. The method is based on sorption of 111Ag in 0.01 M HCl on alumina. Palladium is removed by washing with 0.1 M HCl and the 111Ag is eluted with 4 M HCl. The overall yields of 111Ag are better than 85% with < 1 microg/ml palladium as an impurity. The whole procedure from dissolving the target to the final 111Ag solution takes about 2 h.