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1.
J Environ Sci (China) ; 145: 128-138, 2024 Nov.
Article in English | MEDLINE | ID: mdl-38844313

ABSTRACT

Zeolites are a promising support for Pd catalysts in lean methane (CH4) combustion. Herein, three types of zeolites (H-MOR, H-ZSM-5 and H-Y) were selected to estimate their structural effects and deactivation mechanisms in CH4 combustion. We show that variations in zeolite structure and surface acidity led to distinct changes in Pd states. Pd/H-MOR with external high-dispersing Pd nanoparticles exhibited the best apparent activity, with activation energy (Ea) at 73 kJ/mol, while Pd/H-ZSM-5 displayed the highest turnover frequency (TOF) at 19.6 × 10-3 sec-1, presumably owing to its large particles with more step sites providing active sites in one particle for CH4 activation. Pd/H-Y with dispersed PdO within pore channels and/or Pd2+ ions on ion-exchange sites yielded the lowest apparent activity and TOF. Furthermore, Pd/H-MOR and Pd/H-ZSM-5 were both stable under a dry condition, but introducing 3 vol.% H2O caused the CH4 conversion rate on Pd/H-MOR drop from 100% to 63% and that on Pd/H-ZSM-5 decreased remarkably from 82% to 36%. The former was shown to originate from zeolite structural dealumination, and the latter principally owed to Pd aggregation and the loss of active PdO.


Subject(s)
Methane , Palladium , Zeolites , Zeolites/chemistry , Methane/chemistry , Catalysis , Palladium/chemistry , Models, Chemical
2.
Environ Geochem Health ; 46(6): 200, 2024 May 02.
Article in English | MEDLINE | ID: mdl-38696110

ABSTRACT

Plant extracts are a great alternative to synthesizing nanoparticles of different metals and metal oxides. This green synthesis method has opened up numerous possibilities in various scientific domains. In present study, Leaf extract from Vitex negundo is a non-deciduous, long-lasting shrub from the Verbenaceae family is used as capping and reducing agents for the synthesis of silver and palladium nanoparticles. The characterization study UV-vis spectrophotometer analysis showed absorbance value around 320 nm which confirming that Ag-Pd nanoparticles have been successfully obtained. Further, SEM is used to investigate the morphology of Ag-Pd NPs, which revealing their spherical and rod-like configuration, aggregation, and the size of the particles are obtained between 50 and 100 nm. The successful synthesis of Ag-Pd NPs was further confirmed by the EDAX chart, which displayed the peak of Ag and Pd at bending energies between 0.5 and 1.5 keV. According to the quantitative study, Ag and Pd ions found about 5.24 and 13.28%, respectively. In addition, surface studies with TEM confirming that synthesized Ag-Pd NPs are predominates with spheres structure morphologies, with sizes averaging 11.20 nm and ranging from 10 to 20 nm. Further, Ag-Pd nanoparticles was applied as potential photocatalyst materials to degrade methylene blue dye and found about 85% of the degradation efficiency within 150 min of the sunlight exposure thus could be used as catalyst to removal of hazardous organic dye molecules.


Subject(s)
Coloring Agents , Metal Nanoparticles , Palladium , Silver , Vitex , Vitex/chemistry , Palladium/chemistry , Silver/chemistry , Metal Nanoparticles/chemistry , Catalysis , Coloring Agents/chemistry , Plant Extracts/chemistry , Plant Leaves/chemistry , Green Chemistry Technology , Photolysis , Microscopy, Electron, Transmission
3.
Mikrochim Acta ; 191(6): 298, 2024 05 06.
Article in English | MEDLINE | ID: mdl-38709403

ABSTRACT

As a real-time fluid biopsy method, the detection of circulating tumor cells (CTCs) provides important information for the early diagnosis, precise treatment, and prognosis of cancer. However, the low density of CTCs in the peripheral blood hampers their capture and detection with high sensitivity and selectivity using currently available methods. Hence, we designed a sandwich-type electrochemical aptasensor that utilizes holothurian-shaped AuPd nanoparticles (AuPd HSs), tetrahedral DNA nanostructures (TDNs), and CuPdPt nanowire networks (NWs) interwoven with a graphdiyne (GDY) sheet for ultrasensitive non-destructive detection of MCF-7 breast cancer cells. CuPdPt NW-GDY effectively enhanced the electron transfer rate and coupled with the loaded TDNs. The TDNs could capture MCF-7 cells with precision and firmness, and the resulting composite complex was combined with AuPd HSs to form a sandwich-type structure. This novel aptasensor showed a linear range between 10 and 106 cells mL-1 and an ultralow detection limit of 7 cells mL-1. The specificity, stability, and repeatability of the measurements were successfully verified. Moreover, we used benzonase nuclease to achieve non-destructive recovery of cells for further clinical studies. According to the results, our aptasensor was more sensitive measuring the number of CTCs than other approaches because of the employment of TDNs, CuPdPt NW-GDY, and AuPd HSs. We designed a reliable sensor system for the detection of CTCs in the peripheral blood, which could serve as a new approach for cancer diagnosis at an early stage.


Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , DNA , Electrochemical Techniques , Gold , Limit of Detection , Metal Nanoparticles , Neoplastic Cells, Circulating , Palladium , Neoplastic Cells, Circulating/pathology , Humans , MCF-7 Cells , Metal Nanoparticles/chemistry , Electrochemical Techniques/methods , Aptamers, Nucleotide/chemistry , Gold/chemistry , DNA/chemistry , Biosensing Techniques/methods , Palladium/chemistry
4.
Luminescence ; 39(5): e4773, 2024 May.
Article in English | MEDLINE | ID: mdl-38757733

ABSTRACT

Two Schiff base probes (S1 and S2) were prepared and synthesized by incorporating thienopyrimidine into salicylaldehyde or 3-ethoxysalicylaldehyde individually, with the aim of detecting Ga3+ and Pd2+ sequentially. Upon chelation with Ga3+, S1 and S2 exhibited fluorescence enhancement in DMSO/H2O buffer. Both S1-Ga3+ and S2-Ga3+ were quenched by Pd2+. The limit of detection for S1 in response to Ga3+ and Pd2+ was 2.86 × 10-7 and 4.4 × 10-9 M, respectively. For S2, the limit of detection for Ga3+ and Pd2+ was 4.15 × 10-8 and 3.0 × 10-9 M, respectively. Furthermore, the complexation ratios of both S1 and S2 with Ga3+ and Pd2+ were determined to be 1:2 through Job's plots, ESI-MS analysis, and theoretical calculations. Two molecular logic gates were constructed, leveraging the response behaviors of S1 and S2. Moreover, the potential utility of S1 and S2 for monitoring Ga3+ and Pd2+ in domestic water was verified.


Subject(s)
Fluorescent Dyes , Gallium , Palladium , Pyrimidines , Schiff Bases , Schiff Bases/chemistry , Palladium/chemistry , Pyrimidines/chemistry , Pyrimidines/analysis , Gallium/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Spectrometry, Fluorescence , Molecular Structure
5.
Anal Chim Acta ; 1309: 342698, 2024 Jun 22.
Article in English | MEDLINE | ID: mdl-38772661

ABSTRACT

BACKGROUND: The lateral flow immunoassay (LFIA) is widely employed as a point-of-care testing (POCT) technique. However, its limited sensitivity hinders its application in detecting biomarkers with low abundance. Recently, the utilization of nanozymes has been implemented to enhance the sensitivity of LFIA by catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). The catalytic performance of nanozymes plays a crucial role in influencing the sensitivity of LFIA. RESULTS: The Cornus officinalis Sieb. et Zucc-Pd@Pt (CO-Pd@Pt) nanozyme with good peroxidase-like activity was synthesized herein through a facile one-pot method employing Cornus officinalis Sieb. et Zucc extract as a reducing agent. The morphology and composition of the CO-Pd@Pt nanozyme were characterized using TEM, SEM, XRD, and XPS. As a proof of concept, the as-synthesized CO-Pd@Pt nanozyme was utilized in LFIA (CO-Pd@Pt-LFIA) for the detection of human chorionic gonadotropin (hCG). Compared to conventional gold nanoparticles-based LFIA (AuNPs-LFIA), CO-Pd@Pt-LFIA demonstrated a significant enhancement in the limit of detection (LOD, 0.08 mIU/mL), which is approximately 160 times lower than that of AuNPs-LFIA. Furthermore, experiments evaluating accuracy, precision, selectivity, interference, and stability have confirmed the practical applicability of CO-Pd@Pt-LFIA for hCG content determination. SIGNIFICANCE: The present study presents a novel approach for the synthesis of bimetallic nanozymes through environmentally friendly methods, utilizing plant extracts as both protective and reducing agents. Additionally, an easily implementable technique is proposed to enhance signal detection in lateral flow immunoassays.


Subject(s)
Palladium , Platinum , Palladium/chemistry , Platinum/chemistry , Immunoassay/methods , Humans , Metal Nanoparticles/chemistry , Limit of Detection , Peroxidase/chemistry , Peroxidase/metabolism , Benzidines/chemistry , Catalysis , Oxidation-Reduction
6.
ACS Sens ; 9(5): 2395-2401, 2024 May 24.
Article in English | MEDLINE | ID: mdl-38722860

ABSTRACT

PdNi alloy thin films demonstrate exceptional hydrogen sensing performance and exhibit significant potential for application in surface acoustic wave (SAW) hydrogen sensors. However, the long-term stability of SAW H2 sensors utilizing PdNi films as catalysts experiences a substantial decrease during operation. In this paper, X-ray photoelectron spectroscopy (XPS) is employed to investigate the failure mechanisms of PdNi thin films under operational conditions. The XPS analysis reveals that the formation of PdO species on PdNi thin films plays a crucial role in the failure of hydrogen sensing. Additionally, density functional theory (DFT) calculations indicate that hydrogen atoms encounter a diffusion energy barrier during the penetration process from the PdNiOx surface to the subsurface region. The identification of PdNi film failure mechanisms through XPS and DFT offers valuable insights into the development of gas sensors with enhanced long-term stability. Guided by these mechanisms, we propose a method to restore the hydrogen sensing response time and magnitude to a certain extent by reducing the partially oxidized surface of the PdNi alloy under a hydrogen atmosphere at 70 °C, thereby restoring Pd to its metallic state with zero valence.


Subject(s)
Hydrogen , Nickel , Oxidation-Reduction , Palladium , Sound , Hydrogen/chemistry , Palladium/chemistry , Nickel/chemistry , Surface Properties , Density Functional Theory , Photoelectron Spectroscopy , Alloys/chemistry
7.
ACS Sens ; 9(5): 2529-2539, 2024 May 24.
Article in English | MEDLINE | ID: mdl-38723609

ABSTRACT

Hydrogen (H2) is crucial in the future global energy landscape due to its eco-friendly properties, but its flammability requires precise monitoring. This study introduces an innovative thermocatalytic H2 sensor utilizing ultrathin mica sheets as substrates, coated on both sides with Pd nanocluster (NC) films. The ultrathin mica substrate ensures robustness and flexibility, enabling the sensor to withstand high temperatures and mechanical deformation. Additionally, it simplifies the fabrication process by eliminating the need for complex microelectro-mechanical systems (MEMS) technology. Constructed through cluster beam deposition, the sensor exhibits exceptional characteristics, including a wide concentration range (from 500 ppm to 4%), rapid response and recovery times (3.1 and 2.4 s for 1% H2), good selectivity, high stability, and repeatability. The operating temperature can be as low as 40 °C, achieving remarkably low power consumption. The study explores the impact of double-sided versus single-sided catalytic layers, revealing significantly higher sensitivity and response with the double-sided configuration due to the increased catalytic surface area. Additionally, the research investigates the relationship between the deposition amount of Pd NCs and the sensor's sensitivity, identifying an optimal value that maximizes performance without excessive use of Pd. The sensor's innovative design and excellent performance position it as a promising candidate for meeting the demands of a hydrogen-based energy economy.


Subject(s)
Aluminum Silicates , Hydrogen , Metal Nanoparticles , Palladium , Palladium/chemistry , Hydrogen/chemistry , Catalysis , Metal Nanoparticles/chemistry , Aluminum Silicates/chemistry , Temperature , Surface Properties
8.
Bioelectrochemistry ; 158: 108728, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38733721

ABSTRACT

Herein, an aptasensor based on a signal amplification strategy was developed for the sensitive detection of procymidone (PCM). AgPd nanoparticles/Polenimine Graphite oxide (AgPdNPs/PEI-GO) was weaned as electrode modification material to facilitate electron transport and increase the active sites on the electrode surface. Besides, Pt@Ni-Co nanoboxes (Pt@Ni-CoHNBs) were utilized to be carriers for signaling tags, after hollowing ZIF-67 and growing Pt, the resulting Pt@Ni-CoHNBs has a tremendous amounts of folds occurred on the surface, enables it to carry a larger quantity of thionine, thus amplify the detectable electrochemical signal. In the presence of PCM, the binding of PCM to the signal probe would trigger a change in electrical signal. The aptasensor was demonstrated with excellent sensitivity and a low detection limit of 0.98 pg·mL-1, along with a wide linear range of 1 µg·mL-1 to 1 pg·mL-1. Meanwhile, the specificity, stability and reproducibility of the constructed aptasensor were proved to be satisfactory.


Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , Electrochemical Techniques , Graphite , Limit of Detection , Metal Nanoparticles , Palladium , Platinum , Silver , Graphite/chemistry , Aptamers, Nucleotide/chemistry , Electrochemical Techniques/methods , Platinum/chemistry , Biosensing Techniques/methods , Metal Nanoparticles/chemistry , Palladium/chemistry , Silver/chemistry , Nickel/chemistry , Polyethyleneimine/chemistry , Cobalt/chemistry , Reproducibility of Results
9.
Mikrochim Acta ; 191(6): 352, 2024 05 28.
Article in English | MEDLINE | ID: mdl-38806756

ABSTRACT

Developing convenient and reliable methods for Hg2+ monitoring is highly important. Some precious metal nanomaterials with intriguing peroxidase-like activity have been used for highly sensitive Hg2+ detection. However, H2O2 must be added during these detections, which impedes practical applications of Hg2+ sensors due to its susceptible decomposition by environmental factors. Herein, we discovered that the combination of Hg2+ and palladium metal-organic framework@graphene (Pd-MOF@GNs) exhibits oxidase-like activity (OXD). In the absence of H2O2, this activity not only catalyzes the oxidation of chromogenic substrates such as 3,3',5,5'-tetramethylbenzidine (TMB) or o-phenylenediamine (OPD) to produce a color change but also enhances the electrical signals during OPD oxidation. Based on these properties, an effective and convenient dual-mode colorimetric and electrochemical sensor for Hg2+ has been developed. The colorimetric and amperometric linear relationships for Hg2+ were 0.045 µM-0.25 mM and 0.020 µM-2.0 mM, respectively. The proposed strategy shows good recovery in real sample tests, indicating promising prospects for multiple environmental sample detection of Hg2+ without relying on H2O2. The colorimetric and electrochemical dual-mode Hg2+ sensor is expected to hold great potentials in applications such as environmental monitoring, rapid field detection, and integration into smartphone detection of Hg2+.


Subject(s)
Colorimetry , Electrochemical Techniques , Graphite , Limit of Detection , Mercury , Metal-Organic Frameworks , Palladium , Graphite/chemistry , Colorimetry/methods , Mercury/analysis , Mercury/chemistry , Metal-Organic Frameworks/chemistry , Palladium/chemistry , Electrochemical Techniques/methods , Benzidines/chemistry , Oxidation-Reduction , Water Pollutants, Chemical/analysis , Hydrogen Peroxide/chemistry , Hydrogen Peroxide/analysis , Oxidoreductases/chemistry , Oxidoreductases/metabolism , Phenylenediamines/chemistry
10.
Int J Mol Sci ; 25(10)2024 May 13.
Article in English | MEDLINE | ID: mdl-38791348

ABSTRACT

Hybrid nanomaterials have attracted considerable interest in biomedicine because of their fascinating characteristics and wide range of applications in targeted drug delivery, antibacterial activity, and cancer treatment. This study developed a gelatin-coated Titanium oxide/palladium (TiO2/Pd) hybrid nanomaterial to enhance the antibacterial and anticancer capabilities. Morphological and structural analyses were conducted to characterize the synthesized hybrid nanomaterial. The surface texture of the hybrid nanomaterials was examined by high-resolution transmission electron microscopy (HR-TEM) and field-emission scanning electron microscopy (FE-SEM). The FE-SEM image revealed the bulk of the spherically shaped particles and the aggregated tiny granules. Energy dispersive X-ray spectroscopy (EDS) revealed Ti, Pd, C, and O. X-ray diffraction (XRD) revealed the gelatin-coated TiO2/Pd to be in the anatase form. Fourier transform infrared spectroscopy examined the interactions among the gelatin-coated TiO2/Pd nanoparticles. The gelatin-coated TiO2/Pd nanomaterials exhibited high antibacterial activity against Escherichia coli (22 mm) and Bacillus subtilis (17 mm) compared to individual nanoparticles, confirming the synergistic effect. More importantly, the gelatin-coated TiO2/Pd hybrid nanomaterial exhibited remarkable cytotoxic effects on A549 lung cancer cells which shows a linear increase with the concentration of the nanomaterial. The hybrid nanomaterials displayed higher toxicity to cancer cells than the nanoparticles alone. Furthermore, the cytotoxic activity against human cancer cells was verified by the generation of reactive oxygen species and nuclear damage. Therefore, gelatin-coated TiO2/Pd nanomaterials have potential uses in treating cancer and bacterial infections.


Subject(s)
Anti-Bacterial Agents , Antineoplastic Agents , Escherichia coli , Gelatin , Nanostructures , Palladium , Titanium , Titanium/chemistry , Titanium/pharmacology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Humans , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Gelatin/chemistry , Palladium/chemistry , Palladium/pharmacology , Escherichia coli/drug effects , Nanostructures/chemistry , A549 Cells , Bacillus subtilis/drug effects , Microbial Sensitivity Tests , X-Ray Diffraction , Metal Nanoparticles/chemistry
11.
Chemistry ; 30(28): e202401199, 2024 May 17.
Article in English | MEDLINE | ID: mdl-38695718

ABSTRACT

Invited for the cover of this issue are Tatiyana Serebryanskaya, Mikhail Kinzhalov and co-workers at St. Petersburg State University, the Research Institute for Physical Chemical Problems, Belarusian State University, Togliatti State University and Blokhin National Medical Research Center of Oncology. The image depicts the shield of Pallas Athena with the structure of a palladium carbene complex that protects against triple-negative breast cancer. Read the full text of the article at 10.1002/chem.202400101.


Subject(s)
Antineoplastic Agents , Cell Proliferation , Coordination Complexes , Triple Negative Breast Neoplasms , Triple Negative Breast Neoplasms/drug therapy , Triple Negative Breast Neoplasms/pathology , Humans , Coordination Complexes/chemistry , Coordination Complexes/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Proliferation/drug effects , Female , Cell Line, Tumor , Palladium/chemistry , Methane/analogs & derivatives , Methane/chemistry , Methane/pharmacology
12.
Int J Mol Sci ; 25(9)2024 Apr 26.
Article in English | MEDLINE | ID: mdl-38731956

ABSTRACT

X-ray fluorescence imaging (XFI) can localize diagnostic or theranostic entities utilizing nanoparticle (NP)-based probes at high resolution in vivo, in vitro, and ex vivo. However, small-animal benchtop XFI systems demonstrating high spatial resolution (variable from sub-millimeter to millimeter range) in vivo are still limited to lighter elements (i.e., atomic number Z≤45). This study investigates the feasibility of focusing hard X-rays from solid-target tubes using ellipsoidal lens systems composed of mosaic graphite crystals with the aim of enabling high-resolution in vivo XFI applications with mid-Z (42≤Z≤64) elements. Monte Carlo simulations are performed to characterize the proposed focusing-optics concept and provide quantitative predictions of the XFI sensitivity, in silico tumor-bearing mice models loaded with palladium (Pd) and barium (Ba) NPs. Based on simulation results, the minimum detectable total mass of PdNPs per scan position is expected to be on the order of a few hundred nanograms under in vivo conform conditions. PdNP masses as low as 150 ng to 50 ng could be detectable with a resolution of 600 µm when imaging abdominal tumor lesions across a range of low-dose (0.8 µGy) to high-dose (8 µGy) exposure scenarios. The proposed focusing-optics concept presents a potential step toward realizing XFI with conventional X-ray tubes for high-resolution applications involving interesting NP formulations.


Subject(s)
Graphite , Graphite/chemistry , Animals , Mice , Optical Imaging/methods , Monte Carlo Method , Nanoparticles/chemistry , Palladium/chemistry , Computer Simulation , Spectrometry, X-Ray Emission/methods
13.
Chemosphere ; 358: 142198, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38697566

ABSTRACT

In the electrical industry, there are many hazardous gases that pollute the environment and even jeopardize human health, so timely detection and effective control of these hazardous gases is of great significance. In this work, the gas-sensitive properties of Pd-modified g-C3N4 interface for each hazardous gas molecule were investigated from a microscopic viewpoint, taking the hazardous gases (CO, NOx) that may be generated in the power industry as the detection target. Then, the performance of Pd-modifiedg-C3N4 was evaluated for practical applications as a gas sensor material. Novelly, an unconventional means was designed to briefly predict the effect of humidity on the adsorption properties of this sensor material. The final results found that Pd-modified g-C3N4 is most suitable as a potential gas-sensitizing material for NO2 gas sensors, followed by CO. Interestingly, Pd-modified g-C3N4 is less suitable as a potential gas-sensitizing material for NO gas sensors, but has the potential to be used as a NO cleaner (adsorbent). Unconventional simulation explorations of humidity effects show that in practical applications Pd-modified g-C3N4 remains a promising material for gas sensing in specific humidity environments. This work reveals the origin of the excellent properties of Pd-modified g-C3N4 as a gas sensor material and provides new ideas for the detection and treatment of these three hazardous gases.


Subject(s)
Air Pollutants , Palladium , Air Pollutants/analysis , Palladium/chemistry , Adsorption , Water/chemistry , Environmental Monitoring/methods , Gases/analysis , Humidity , Carbon Monoxide/analysis , Nitriles/chemistry , Nitriles/analysis
14.
ACS Appl Mater Interfaces ; 16(21): 27511-27522, 2024 May 29.
Article in English | MEDLINE | ID: mdl-38752668

ABSTRACT

Electron transfer is considered to be a typical parameter that affects the catalytic activity of nanozymes. However, there is still controversy regarding whether higher or lower electron transfer numbers are beneficial for improving the catalytic activity of nanozymes. To address this issue, we propose the introduction of Pd doping as an important electron regulation strategy to tune electron transfer between Pt and ZIF-8 carriers (PtxPd1@ZIF-8). We observe a volcano-shaped relationship between the electron transfer number and catalytic activity, reaching its peak at Pt4Pd1@ZIF-8. Mechanism studies indicate that as the electron transfer number from Pt to ZIF-8 carriers increases, the d-band center of the active site Pt increases, reducing the occupancy of antibonding states and enhancing the adsorption capacity of the key intermediate (*O). However, a further increase in the adsorption of *O energy makes it difficult to desorb and participate in the next reaction, thus exhibiting volcanic activity. The optimized Pt4Pd1@ZIF-8 nanozyme is applied to develop an immunoassay for the detection of zearalenone, achieving a detection limit of 0.01 µg/L, which is 6 times higher than that of the traditional enzyme-linked immunosorbent assay. This work not only reveals the potential regulatory mechanism of electron transfer on the catalytic activity of nanozymes but also improves the performance of nanozyme-based biosensors.


Subject(s)
Metal-Organic Frameworks , Palladium , Platinum , Catalysis , Platinum/chemistry , Palladium/chemistry , Metal-Organic Frameworks/chemistry , Electron Transport , Immunoassay/methods
15.
Spectrochim Acta A Mol Biomol Spectrosc ; 317: 124408, 2024 Sep 05.
Article in English | MEDLINE | ID: mdl-38723464

ABSTRACT

To investigate the structure and bioactivity relationship, six Pd(II)/Pt(II) complexes with N-isobutylglycine (L1) and cyclohexylglycine (L2) as N^O amino acid bidentate ligands, 1,10'-phenanthroline (phen) and 2,2'-bipyridine (bipy) as N^N donor ligands, and [Pd(L1)(bipy)]NO3 (1), [Pd(L2)(bipy)]NO3 (2), [Pd(L1)(phen)]NO3 (3), [Pd(L2)(phen)]NO3·2H2O (4), [Pt(L1)(phen)]NO3 (5), along with [Pt(L2)(phen)]NO3 (6) were prepared and then characterized. The geometry of each compound was validated by doing a DFT calculation. Furthermore, tests were conducted on the complexes' water solubilities and lipophilicity. All bipy complexes had superior aqueous solubility and less lipophilicity in comparison with phen complexes, as well as complexes containing cyclohexyl-glycine compared to isobutyl-glycine complexes, probably because of the steric effects and polarity of cyclohexylglycine. The in-vitro anticancer activities of these compounds were examined against HCT116, A549, and MCF7 cancerous cell lines. Data revealed that all Pd/Pt complexes demonstrate higher anticancer activity than carboplatin, and complexes 3 and 4 are more cytotoxic than cisplatin against the HCT116 cell line, particularly against MCF7 cancerous cells. In addition, among all compounds, complex 4 has more anticancer ability than oxaliplatin. Due to different solubility and lipophilicity behavior, the accumulation of Pt complexes and clinical Pt drugs in each cancerous cell was investigated. The binding capabilities of these complexes to DNA, as the main target in chemotherapy, occur through minor grooves and intercalate into DNA, which was done using absorption, fluorescence, and circular dichroism spectroscopy. Finally, the docking simulation study showed the mode of DNA bindings is in good agreement with the spectral binding data.


Subject(s)
Antineoplastic Agents , Coordination Complexes , Glycine , Palladium , Humans , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Glycine/chemistry , Glycine/analogs & derivatives , Glycine/pharmacology , Palladium/chemistry , Palladium/pharmacology , Ligands , Structure-Activity Relationship , Cell Line, Tumor , Coordination Complexes/pharmacology , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Platinum/chemistry , Platinum/pharmacology , DNA/metabolism , DNA/chemistry , Solubility
16.
Mikrochim Acta ; 191(6): 340, 2024 05 24.
Article in English | MEDLINE | ID: mdl-38787447

ABSTRACT

A new sandwich-type electrochemical biosensing platform was developed by gold @polyphthalenediamine nanohybrids (AuNP@PoPD) as the sensing platform and phosphorus doped reduced graphene oxide-hemin-palladium nanoparticles (PrGO-Hemin-PdNP) as the signal amplifier for phosphatidylinositol proteoglycan 3 (GPC3). AuNP@PoPD, co-electrodeposited into the screen printed electrode with high conductivity and stability, is dedicated to assembling the primary GPC3 aptamer (GPC3Apt). The second GPC3Apt immobilized on the high conductivity and large surface area of PrGO-Hemin-PdNP was utilized as an electrochemical signal reporter by hemin oxidation (PrGO-Hemin-PdNP-GPC3Apt). In the range 0.001-10.0 ng/mL, the hemin oxidation current signal of the electrochemical aptasensor increased log-linearly with the concentration of GPC3, the lowest detection limit was 0.13 pg/mL, and the sensitivity was 2.073 µA/µM/cm2. The aptasensor exhibited good sensing performance in a human serum sample with the relative error of 4.31-8.07%. The sandwich sensor showed good selectivity and stability for detection GPC3 in human serum samples, providing a new efficient and sensitive method for detecting HCC markers.


Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , Electrochemical Techniques , Glypicans , Gold , Graphite , Hemin , Limit of Detection , Metal Nanoparticles , Palladium , Glypicans/blood , Humans , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Aptamers, Nucleotide/chemistry , Hemin/chemistry , Graphite/chemistry , Palladium/chemistry , Gold/chemistry , Biosensing Techniques/methods , Metal Nanoparticles/chemistry , Electrodes
17.
J Org Chem ; 89(11): 8005-8010, 2024 Jun 07.
Article in English | MEDLINE | ID: mdl-38804706

ABSTRACT

Trace palladium in synthetic materials can be rapidly and inexpensively semiquantified by a catalysis-based fluorometric method that converts resorufin allyl ether to resorufin. However, whether sulfur compounds would interfere with this method has not been systematically studied. Herein, we show that although thiourea in solution interferes with quantification, sulfide, thiol, and thiocarbamate do not. The fluorometric method can also detect palladium bound to sulfur-based scavenger resin and outperform inductively coupled plasma mass spectrometry for detecting trace palladium in ibuprofen.


Subject(s)
Fluorometry , Ibuprofen , Palladium , Palladium/chemistry , Ibuprofen/chemistry , Ibuprofen/analysis , Catalysis , Fluorometry/methods , Molecular Structure , Sulfur Compounds/chemistry , Sulfur Compounds/analysis
18.
Org Lett ; 26(22): 4818-4823, 2024 Jun 07.
Article in English | MEDLINE | ID: mdl-38809781

ABSTRACT

We have successfully accomplished a catalytic asymmetric total synthesis of entecavir, a first-line antihepatitis B virus medication. The pivotal aspect of our strategy lies in the utilization of a Pd-catalyzed enyne borylative cyclization reaction, enabling the construction of a highly substituted cyclopentene scaffold with exceptional stereoselectivity. Additionally, we efficiently accessed the crucial 1,3-diol enyne system early in our synthetic route through a diarylprolinol organocatalyzed enantioselective cross-aldol reaction and Re-catalyzed allylic alcohol relocation. By strategically integrating these three catalytic protocols, we established a practical pathway for acquiring valuable densely heteroatom-substituted cyclopentene cores.


Subject(s)
Antiviral Agents , Cyclopentanes , Guanine , Hepatitis B virus , Cyclopentanes/chemistry , Cyclopentanes/chemical synthesis , Catalysis , Antiviral Agents/chemistry , Antiviral Agents/chemical synthesis , Stereoisomerism , Molecular Structure , Guanine/chemistry , Guanine/analogs & derivatives , Hepatitis B virus/drug effects , Cyclization , Palladium/chemistry
19.
Nano Lett ; 24(22): 6634-6643, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38742828

ABSTRACT

The effect of strong metal-support interaction (SMSI) has never been systematically studied in the field of nanozyme-based catalysis before. Herein, by coupling two different Pd crystal facets with MnO2, i.e., (100) by Pd cube (Pdc) and (111) by Pd icosahedron (Pdi), we observed the reconstruction of Pd atomic structure within the Pd-MnO2 interface, with the reconstructed Pdc (100) facet more disordered than Pdi (111), verifying the existence of SMSI in such coupled system. The rearranged Pd atoms in the interface resulted in enhanced uricase-like catalytic activity, with Pdc@MnO2 demonstrating the best catalytic performance. Theoretical calculations suggested that a more disordered Pd interface led to stronger interactions with intermediates during the uricolytic process. In vitro cell experiments and in vivo therapy results demonstrated excellent biocompatibility, therapeutic effect, and biosafety for their potential hyperuricemia treatment. Our work provides a brand-new perspective for the design of highly efficient uricase-mimic catalysts.


Subject(s)
Hyperuricemia , Manganese Compounds , Oxides , Urate Oxidase , Hyperuricemia/drug therapy , Urate Oxidase/chemistry , Urate Oxidase/therapeutic use , Urate Oxidase/metabolism , Oxides/chemistry , Manganese Compounds/chemistry , Manganese Compounds/pharmacology , Humans , Palladium/chemistry , Palladium/pharmacology , Animals , Catalysis , Uric Acid/chemistry , Mice
20.
Environ Sci Pollut Res Int ; 31(23): 34661-34674, 2024 May.
Article in English | MEDLINE | ID: mdl-38713350

ABSTRACT

Rapid passivation and aggregation of nanoscale zero-valent iron (nZVI) seriously limit its performance in the remediation of different contaminants from wastewater. To overcome such issues, in the present study, nano-palladium/iron (nPd/Fe) was simultaneously improved by biochar (BC) prepared from discarded peanut shells and green complexing agent sodium citrate (SC). For this purpose, a composite (SC-nPd/Fe@BC) was successfully synthesized to remove 2,4-dichlorophenol (2,4-DCP) from wastewater. In the SC-nPd/Fe@BC, BC acts as a carrier with dispersed nPd/Fe particles to effectively prevent its agglomeration, and increased the specific surface area of the composite, thereby improving the reactivity and stability of nPd/Fe. Characterization results demonstrated that the SC-nPd/Fe@BC composites were well dispersed, and the agglomeration was weakened. The formation of the passivation layer on the surface of the particles was inhibited, and the mechanism of SC and BC improving the reactivity of nPd/Fe was clarified. Different factors were found to influence the reductive dichlorination of 2,4-DCP, including Pd loading, Fe:C, SC addition, temperature, initial pH, and initial pollutant concentration. The dechlorination results revealed that the synergistic effect of the BC and SC made the removal efficiency and dechlorination rate of 2,4-DCP by SC-nPd/Fe@BC reached to 96.0 and 95.6%, respectively, which was better than that of nPd/Fe (removal: 46.2%, dechlorination: 45.3%). Kinetic studies explained that the dechlorination reaction of 2,4-DCP and the data were better represented by the pseudo-first-order kinetic model. The reaction rate constants followed the order of SC-nPd/Fe@BC (0.0264 min-1) > nPd/Fe@BC (0.0089 min-1) > SC-nPd/Fe (0.0081 min-1) > nPd/Fe (0.0043 min-1). Thus, SC-nPd/Fe@BC was capable of efficiently reducing 2,4-DCP and the dechlorination efficiency of BC and SC synergistically assisted composite on 2,4-DCP was much better than that of SC-nPd/Fe, nPd/Fe@BC and nPd/Fe. Findings suggested that SC-nPd/Fe@BC can be promising for efficient treatment of chlorinated pollutants.


Subject(s)
Charcoal , Chlorophenols , Iron , Palladium , Chlorophenols/chemistry , Palladium/chemistry , Iron/chemistry , Charcoal/chemistry , Water Pollutants, Chemical/chemistry , Citric Acid/chemistry , Wastewater/chemistry
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