Triazole‐based ligands functionalized silica: Effects of ligand denticity and donors on catalytic oxidation activity of Pd nanoparticles

Triazole‐based ligands, tris (triazolyl)methanol (Htbtm), bis (triazolyl)‐phenylmethanol (Hbtm), and phenyl (pyridin‐2‐yl)(triazolyl)methanol (Hpytm), with differences in ligand denticity (i.e., bidentate and tridentate) and type of N donors (i.e., triazole and pyridine) were functionalized onto a silica support to produce the corresponding SiO₂‐ L ( L  = tbtm, btm, pytm). Subsequent reactions with Pd (CH₃COO)₂ in CH₂Cl₂ yielded Pd/SiO₂‐ L . ICP‐MS reveals that Pd loadings are higher with increased N loadings, resulting in the following trend: Pd/SiO₂‐tbtm (0.83 mmol Pd g^?1) > Pd/SiO₂‐btm (0.65 mmol Pd g^?1) ~ Pd/SiO₂‐pytm (0.63 mmol Pd g^?1). Meanwhile, TEM images of the used Pd/SiO₂‐ L catalysts after the first catalytic cycle show that the mean size of Pd NPs is highest with Pd/SiO₂‐pytm (8.5 ± 1.5 nm), followed by Pd/SiO₂‐tbtm (6.4 ± 1.6 nm) and Pd/SiO₂‐btm (4.8 ± 1.3 nm). Based on TONs, catalytic studies toward aerobic oxidation of benzyl alcohol to benzaldehyde at 60 °C in EtOH showed that Pd/SiO₂‐pytm possessed the most active surface Pd(0) atoms, most likely as a result of more labile properties of the pyridine–triazole ligand compared to tris‐ and bis (triazolyl) analogs. ICP‐MS and TEM analysis of Pd/SiO₂‐btm indicate minimal Pd leaching and similar average Pd NPs sizes after 1^st and 5^th catalytic runs, respectively, confirming that SiO₂‐btm is an efficient Pd NPs stabilizer. The Pd/SiO₂‐btm catalyst was also active toward aerobic oxidation of various benzyl alcohol derivatives in EtOH and could be reused for at least 7 reaction cycles without a significant activity loss.     

Preparation of a novel Mixed-Ligand divalent metal complexes from solvent free Synthesized Schiff base derived from 2,6-Diaminopyridine with cinnamaldehyde and 2,2′‐Bipyridine: Characterization and antibacterial activities

The solvent-free conditions were employed to synthesise symmetrical Schiff base ligand from 2,6-diaminopyridine with cinnamaldehyde in (1 min) with a fair yield utilizing formic acid as a catalyst. Through coordination chemistry, new heteroleptic complexes of Cu(II), Co(II), Ni(II), Pt(II), Pd(II) and Zn(II) were achieved from Schiff base as a primary chelator (L¹) and 2,2′‐bipyridine (2,2′-bipy) as a secondary chelator (L²). The prepared compounds have been characterized by elemental analysis, molar conductivity, magnetic susceptibility, FTIR, ¹H NMR, UV–visible, mass spectrometry, and thermal gravimetric analysis, and screened in vitro for their potential as antibacterial activity by the agar well diffusion method. The metal complexes were formulated as [M (L¹) (L²) (X)] Y⋅nH₂O, L¹ = Schiff base, L² = 2,2′-bipy, (M = Cu(II), Co(II), Zn(II), Y = 2NO₃, n = 1), (M = Ni(II), X = 2H₂O, Y = 2NO_3, n = 0) and (M = Pd(II) Pt(II), Y = 2Cl, n = 0). Both L¹ and L² act as a neutral bidentate ligand and coordinates via nitrogen atoms of imine and 2,2′-bipy to metal ions. The metal complexes were found to be electrolytic, with square-planar heteroleptic Cu(II), Co(II), Pt(II), and Pd(II) chelates and octahedral Ni(II) complex. As well as tetrahedral geometry, has been proposed for the complex of Zn(II). Furthermore, the biological activity study revealed that some metal chelates have excellent activity than Schiff base when tested against Gram-negative and Gram-positive strains of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Finally, it was found that the Zn(II) and Pd(II) complexes were more effective against both types of bacteria tested than the imine and other metal complexes.     

Study on spectroscopic characterization of Pd porphyrin and its interaction with ctDNA

The fluorescence and solid substrate room temperature phosphorescence (SS-RTP) properties of Pd(II) meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin (Pd(II)TMPyP) were studied. The factors influencing the SS-RTP emission, such as filter type, inorganic salt sort, drying temperature, pre-drying time and drying time were investigated in detail. Strong SS-RTP signal can be induced on the slow speed filter paper in the presence of the external inorganic salt, Ca(NO₃)₂, with the maximum excitation and emission wavelengths at 421 nm and 675 nm, respectively. The interaction between calf thymus DNA (ctDNA) and Pd(II)TMPyP was investigated at pH 7.2 using SS-RTP, fluorescence and UV-vis spectroscopy. The SS-RTP intensity of Pd(II)TMPyP was enhanced efficiently with the increasing amount of ctDNA. This phenomenon demonstrates that the intercalated porphyrin is shielded by ctDNA to avoid collision quenching. This result was supported by SS-RTP lifetime measurement, SS-RTP anion quenching experiment and fluorescence polarization measurement. Furthermore, with the addition of ctDNA, the UV-vis spectra of Pd(II)TMPyP shows apparent hypochromicity (40%) at the Soret maximum of 417 nm and a red shift of Δλ = 15 nm, also indicating that Pd(II)TMPyP intercalates into ctDNA bases. The binding constant of Pd(II)TMPyP to ctDNA was calculated to be 4.41 × 10⁵ L/mol based on the derivative McGhee-von Hippel plots.     

CoFe2O4@Methylcellulose/AC as a New,Green, and Eco-friendly Nano-magnetic adsorbent for removal of Reactive Red 198 from aqueous solution

Methylcellulose (MC) is the most common commercial cellulose ether and the most attractive biopolymer due to its cheap cost of biodegradability, biocompatibility, hydrophilicity, and lack of toxicity. In this study, CoFe₂O₄@MC/activated carbon (AC) was synthesized as a unique magnetic nano-adsorbent in the presence of MC biopolymer for Reactive Red 198 (RR198) dye removal. The nano-magnetic adsorbent was characterized by FESEM (Field emission scanning electron microscopy), EDS (Energy-dispersive X-ray spectroscopy), Mapping, Linescan, BET (Brunauer–Emmett–Teller), FTIR (Fourier Transform Infrared Spectroscopy), XRD (X-Ray Diffraction), and VSM (Vibrating-Sample magnetometer). For simple separation by external magnetic fields, the Ms value was 57.91 emu/g. According to XRD analysis, the nano-adsorbent maintains its crystal structure, with an average crystal size of 11 nm. The maximum removal efficiencies of RR198 for synthetic and real wastewater samples under optimal conditions (an initial concentration of 10 mg/L, pH 3, contact time of 10 min, nanocomposite dose of 1.5 g/L, and a temperature of 25 °C) were 92.2% and 78%, respectively. The adsorption experiments were fitted well with the Freundlich isotherm (R² = 0.989) and pseudo-second-order kinetic (R² = 0.995). The values of entropy changes (ΔS = 35.087 kJ/mol.k), enthalpy changes (ΔH = -9.862 kJ/mol), and negative Gibbs free energy changes (ΔG) showed that the adsorption process was exothermic. Finally, the reusability findings showed that after six recovery cycles, the efficiency decreased slightly (90.1%). In the end, it can be concluded that the prepared CoFe₂O₄@Methylcellulose/AC can be used as an efficient adsorbent for the removal of RR198 from an aqueous solution.     

Spectroscopic,biological activity studies,and DFT calculations,of Pd(II) and Pt(II) complexes of 4-Methylene-3-phenyl-3,4-dihydroquinazoline-2(1H)-thione

Four palladium (II) and platinum(II) complexes with the formula [MCl₂(HPhqS)₂] and [M(PhqS)₂] (M^II = Pd and Pt), were synthesized by treating Na₂PdCl₄ or K₂PtCl₄ with 2 mol of 4-Methylene-3-phenyl-3,4-dihydroquinazoline-2(1H)-thione (HPhqS) with or without the present base. The geometry around the Pd(II) and Pt(II) ions was a square planner and the HPhqS ligand was bonded as monodentate through the sulfur atom in complexes (1) and (2), while as bidentate chelating ligand through the nitrogen and sulfur atoms in complexes (3) and (4) as revealed by the data collection from spectroscopic studies. The prepared compounds were fully characterized by different physicochemical and spectroscopic methods. Furthermore, the free HPhqS ligand and its complexes were evaluated in vitro in regard to their antimicrobial activity against five bacteria species (Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, staphylococcus epidermidis and staphylococcus aureus). Moreover, the cytotoxic activity of the compounds was examined against breast (MCF-7) and lung (A549) cancer cell lines, and the [PdCl₂(LH)₂] (1) and [PtCl₂(LH)₂] (2) appeared a highest inhibitory effect against MCF-7 cell lines with IC₅₀ = 4.291 ± 0.181 μM and 3.479 ± 0.162 μM, respectively, in comparison to the standard control and other complexes. The prepared ligand accompanied by the synthesized complexes were optimized using B3LYP method and 6–311++G(d,p) biases sets for the ligand and SDD basis set for the central metal. Different quantum parameters including electron affinity, ionization energy, dipole moment, hardness and vibrational frequencies were calculated for the ligand and its complexes. The total energy calculated for the two tautomeric structures of the ligand HPhqS showed a slightly higher value of the thione form over the thiol form. In addition, the trans-[PdCl₂(HPhqS)₂] complex possessed the highest dipole moment values while the cis-[PtCl₂(HPhqS)₂] showed non. In general, the obtained theoretical results showed a good match to the experimental findings.     

Synthesis,characterization and evaluation of biological properties of selenium nanoparticles from Solanum lycopersicum

Synthesis of nanoparticles by green synthesis has a large number of biomedical applications worldwide. In this study, Selenium Nanoparticles (SeNPs) were synthesized by using sodium salt of selenium and Solanum lycopersicum (tomato) fruit juice and seeds extract. The plant extracts were used as a reducing agent in ratio 1:4 i.e. sodium selenite salt (Na₂SeO₃). SeNPs were characterized by UV–visible spectrophotometry, FTIR and Zeta Sizer analysis. The UV-graphs indicated the highest peak of absorbance at 350 nm. Whereas, FTIR analysis of SeNPs indicated absorbance bands at 3262.35–1633.72 cm^?1. Zeta sizer analysis showed the average size of SeNPs for Fruit juice extract as 1020 d.nm. with PDI 0.432. In case of seeds extract, average size was 1155 d.nm. with PDI 0.761; and the PDI value for both extracts showed polyderse nature of these NPs. SeNPs possessed significant antimicrobial activity against selected strains of E. coli, S. aureus, M. luteus, S. enterica, B. subtilis, K. pneumoniae and P. aureginosa. The α-amylase inhibitory assay of these SeNPs indicated that they had antidiabetic role with IC₅₀ value 24.4642 µg/mL. The DPPH assay showed that SeNPs of Solanum lycopersicum have antioxidant activity with IC₅₀ value of 20.7398 µg/mL.     

Highly selective solid-phase extraction of trace Pd(II) by murexide functionalized halloysite nanotubes

The originality on the high efficiency of murexide modified halloysite nanotubes as a new adsorbent of solid phase extraction has been reported to preconcentrate and separate Pd(II) in solution samples. The new adsorbent was confirmed by Fourier transformed infrared spectra, X-ray diffraction, scanning electron microscope, transmission electron microscope and N₂ adsorption–desorption isotherms. Effective preconcentration conditions of analyte were examined using column procedures prior to detection by inductively coupled plasma-optical emission spectrometry (ICP-OES). The effects of pH, the amount of adsorbent, the sample flow rate and volume, the elution condition and the interfering ions were optimized in detail. Under the optimized conditions, Pd(II) could be retained on the column at pH 1.0 and quantitatively eluted by 2.5 mL of 0.01 mol L^?1 HCl–3% thiourea solution at a flow rate of 2.0 mL min^?1. The analysis time was 5 min. An enrichment factor of 120 was accomplished. Common interfering ions did not interfere in both separation and determination. The maximum adsorption capacity of the adsorbent at optimum conditions was found to be 42.86 mg g^?1 for Pd(II).The detection limit (3σ) of the method was 0.29 ng mL^?1, and the relative standard deviation (RSD) was 3.1% (n = 11). The method was validated using certified reference material, and has been applied for the determination of trace Pd(II) in actual samples with satisfactory results.     

Metal framework as a novel approach for the fabrication of electric double layer capacitor device with high energy density using plasticized Poly(vinyl alcohol): Ammonium thiocyanate based polymer electrolyte

High performance electric double-layer capacitors (EDLCs) based on poly (vinyl alcohol) (PVA): ammonium thiocyanate (NH₄SCN):Cu(II)-complex plasticized with glycerol (GLY) have been fabricated. The maximum DC ionic conductivity (σ_DC) of 2.25 × 10^-3 S cm⁻¹ is achieved at ambient temperature. The X-ray diffraction (XRD) patterns confirmed that the addition of both Cu(II)–complex and GLY enhanced the amorphous region within the samples. Through the Fourier transform infrared (FTIR) the interactions between the host polymer and other components of the prepared electrolyte are observed. The FESEM images reveal that the surface morphology of the samples showed a uniform smooth surface at high GLY concentration. This is in good agreement with the XRD and FTIR results. Transference numbers of ion (t_ion) and electron (t_el) for the highest conducting composite polymer electrolyte (CPE) are recognized to be 0.971 and 0.029, respectively. The linear sweep voltammetry (LSV) revealed that the electrochemical stability window for the CPE is 2.15 V. These high values of t_ion and potential stability established the suitability of the synthesized systems for EDLC application. Cyclic voltammetry (CV) offered nearly rectangular shape with the lack of Faradaic peak. The specific capacitance and energy density of the EDLC are nearly constant within 1000 cycles at a current density of 0.5 mA/cm² with average of 155.322F/g and 17.473 Wh/Kg, respectively. The energy density of the EDLC in the current work is in the range of battery specific energy. The EDLC performance was found to be stable over 1000 cycles. The low value of equivalent series resistance reveals that the EDLC has good electrolyte-electrode contact. The EDLC exhibited the initial high power density of 4.960 × 10³ W/Kg.     

Novel nano-structured Pd+yttrium doped ZrO2 cathodes for intermediate temperature solid oxide fuel cells

Novel nano-structured Pd+yttrium doped ZrO₂ (YSZ) electrodes have been developed as cathodes of intermediate temperature solid oxide fuel cells (IT-SOFCs). Nano-sized Pd particles were introduced into the rigid and porous YSZ structure by PdCl₂ solution impregnation. The results show that Pd nanoparticles (20–80 nm) were uniformly distributed in the porous YSZ structure; and such nano-structured composite cathodes were highly active for the O₂ reduction reaction, with polarization resistances (R_E) of 0.11 and 0.22 Ω cm² at 750 and 700 °C and activation energy of 105 kJ mol⁻¹ that is significantly lower than those for the conventional perovskite-based cathodes (130–201 kJ mol⁻¹).     

Synthesis, characterization, antibacterial and cytotoxic activity of new palladium(II) complexes with dithiocarbamate ligands: X-ray structure of bis(dibenzyl-1-S:S′-dithiocarbamato)Pd(II)

Six palladium(II) dithiocarbamates of general formula Pd(AmDTC)₂, where HAmDTC = aminedithiocarbamic acid, [Pd(II) piperidinedithiocarbamate (1), Pd(II) 4-methylpiperidinedithiocarbamate (2), Pd(II) N-methylbenzyldithiocarbamate (3), Pd(II) dibenzyldithiocarbamate (4), Pd(II) dicyclohexyldithiocarbamate (5), Pd(II) N-cyclohexyl-N-methyldithiocarbamate (6)] have been synthesized and characterized by elemental analyses, FT-IR, ¹H and ¹³C NMR. The X-ray structure of Pd(II), compounds 3 and 4, showed that the ligands are chelated by both sulfur atoms with bond angles S1-Pd-S4 = 179.24(2)° and S2-Pd-S3 = 179.09(5)°, with a distorted square planar geometry around Pd. All these complexes were screened for cytotoxic and antibacterial effects and showed significant antibacterial activity and no substantial in vitro cytotoxicity indicating specificity of the compounds.     

Cu–Ce substituted cobalt nano ferrite - Structural,morphological, and magnetic behavior prepared by sol-gel auto-combustion

Sol-gel auto-combustion synthesized Co_1-xCu_xFe_2-yCe_yO₄ (x = 0.0, 0.25, 0.5 and 0.75; y = 0.0, 0.03, 0.06, and 0.09), Cu–Ce substituted Co ferrite nanopowders. Investigations have been done on how Cu–Ce substitution affects the structural and magnetic characteristics. The Cu–Ce substitution variation effect on structural and magnetic properties is studied with X-ray diffraction (XRD), Field effect scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and Vibrating sample magnetometer (VSM). The XRD was used to identify the crystal phase, and the role of Cu–Ce substituted for Co indicates how it formed. There is no change in the crystal structure, and no additional characteristic peak linked to Cu²⁺ and Ce³⁺ ions substitution was found in the XRD. The powder was sintered at 1100 °C. The crystallite sizes were found in between 33 and 62 nm. Increasing the Cu–Ce content decreases the lattice constant and is found between 8.4044 and 8.3309 Å. The FESEM images were used to analyze the nanostructural properties. The range of 110–128 nm is the value of average grain size. Two vibrational bands can be seen in FTIR spectra at about 600 cm⁻¹ (v₁) and 400 cm⁻¹ (v₂). They are attributed to the spinel lattices A and B sites, respectively. The tetrahedral site has a greater vibrational frequency of 566.09 cm^−1, while the octahedral site has a lower vibrational frequency of 420.09 cm⁻¹. FTIR spectra show the tetrahedral stretching peaks shifting towards lower frequencies with increasing Cu²⁺ and Ce³⁺ ions content. At ambient temperature, the magnetic properties of Cu–Ce substituted cobalt ferrites revealed a strong hysteresis loop. There was a decrease in magnetic saturation and an increase in coercivity.     

Hydrodechlorination of CCl4 over carbon-supported palladium–gold catalysts prepared by the reverse “water-in-oil” microemulsion method

Two series of carbon-supported Pd–Au catalysts were prepared by the reverse “water-in-oil, W/O” method, characterized by various techniques and investigated in the reaction of tetrachloromethane with hydrogen at 423 K. The synthesized nanoparticles were reasonably monodispersed having an average diameter of 4–6 nm (Pd/C and Pd–Au/C) and 9 nm (Au/C). Monometallic palladium catalysts quickly deactivated during the hydrodehalogenation of CCl₄. Palladium–gold catalysts with molar ratio Pd:Au = 90:10 and 85:15 were stable and much more active than the monometallic palladium and Au-richer Pd–Au catalysts. The selectivity toward chlorine-free hydrocarbons (especially for C₂₊ hydrocarbons) was increased upon introducing small amounts of gold to palladium. Simultaneously, for the most active Pd–Au catalysts, the selectivity for undesired dimers C₂H_xCl_y, which are considered as coke precursors, was much lower than for monometallic Pd catalysts. Reasons for synergistic effects are discussed. During CCl₄ hydrodechlorination the Pd/C and Pd–Au/C catalysts were subjected to bulk carbiding.     

CH3OH electrooxidation by nanosized Pd loaded on porous LaMnO3

Generating the multifunctional influence by adding a promoter or employing a support for electrocatalytic particles is a remarkable approach to advance the efficiency and stability of anode electrode in the non-reforming methanol fuel cell. So, the coprecipitation assisted with ultrasonic is selected to fabricate porous LaMnO₃; and the nanosized Pd is loaded on LaMnO₃ via wetness incorporation. The samples are characterized through scanning electron microscopy, Fourier-transform infrared spectroscopy (FT-IR), vibrating sample magnetometry, Energy-dispersive X-ray spectroscopy (EDX), Transmission electron microscopy (TEM), Brunauer-Emmett-Teller and X-ray diffraction analysis. The electrochemical studies are carried out to identify the behavior and efficiency of electrocatalysts toward CH₃OH electrooxidation. Based on adsorption/desorption of hydrogen, the electrochemical surface area presented an ascending performance as nanosized Pd (76.63 m² g^?1) < Pd/LaMnO₃ (93.35 m² g^?1). The Pd/LaMnO₃ has higher electrocatalytic activity, stability, and CO-tolerance ability for the CH₃OH electrooxidation of as compared with nanosized Pd as non-supported Pd. The functions of current vs. time were determined by fitting and simulating of the experimental data. The transferred charge throughout CH₃OH electrooxidation vs. time was computed using the lower Riemann sum of plots, corresponding to experimental results and the integration of obtained functions. The introduced nanocomposite was used as anodic material in a single CH₃OH fuel cell.     

Dimeric and monomeric palladium(II) parent-amido (NH2) complexes: Synthesis,characterization, and reactivity

The treatment of [PdL₃(NH₃)]OTf (L₃ = (PEt₃)₂(Ph) (1), (2,6-(Cy₂PCH₂)₂C₆H₃) (3)) with NaNH₂ in THF afforded dimeric and monomeric parent-amido palladium(II) complexes with bridging and terminal NH₂, respectively, anti-[Pd(PEt₃)(Ph)(μ-NH₂)]₂ (2) and Pd(2,6-(Cy₂PCH₂)₂C₆H₃)(NH₂) (4). The dimeric complex 2 crystallizes in the space group P2₁/n with a = 13.228(2) Å, b = 18.132(2) Å, c = 24.745(2) Å, β = 101.41(1)°, and Z = 4. It has been found that there are two crystallographically independent molecules with Pd(1)–Pd(2) and Pd(3)–Pd(4) distances of 2.9594 (10) and 2.9401(9) Å, respectively. The monomeric amido complex 4 protonates from trace amounts of water to give the cationic ammine species [Pd(2,6-(Cy₂PCH₂)₂C₆H₃)(NH₃)]⁺. Complex 4 reacts with diphenyliodonium triflate ([Ph₂I]OTf) to give aniline complex [Pd(2,6-(Cy₂PCH₂)₂C₆H₃)(NH₂Ph)]OTf (5). Reaction of 4 with dialkyl acetylenedicarboxylate (DMAD, DEAD) yields diastereospecific palladium(II) vinyl derivative (Z)–(Pd(Cy₂PCH₂)₂C₆H₃)(CR = CR(NH₂)) (R = CO₂Me (6a), CO₂Et (6b)). Reacting complexes 6a and 6b with p-nitrophenol produces (Pd(Cy₂PCH₂)₂C₆H₃)(OC₆H₄–p-NO₂) (8) and cis-CHR = CR(NH₂), exclusively.     

A study of the reactions of methionine- and histidine-containing peptides with palladium(II) complexes: The key role of steric crowding on palladium(II) in the selective cleavage of the peptide bond

¹H NMR spectroscopy was applied to study the reactions of palladium(II) complexes, cis-[Pd(dpa)Cl₂] and cis-[Pd(dpa)(H₂O)₂]²⁺ (dpa is 2,2′-dipyridylamine acting as a bidentate ligand) with the dipeptides methionylglycine (Met-Gly) and histidylglycine (His-Gly), and the N-acetylated derivatives of these dipeptides, MeCOMet-Gly and MeCOHis-Gly. All reactions were carried out in the pH range 2.0–2.5 with equimolar amounts of the palladium(II) complex and the peptide at two different temperatures, 25 and 60 °C. In the reactions of cis-[Pd(dpa)Cl₂] and cis-[Pd(dpa)(H₂O)₂]²⁺ with Met-Gly and His-Gly, no hydrolysis of the peptide bond was observed. The final product in these reactions was the [Pd(dpa)₂]²⁺ complex. The square-planar structure of this complex was confirmed by X-ray analysis. The reaction of the cis-[Pd(dpa)(H₂O)₂]²⁺ complex with the MeCOHis-Gly and MeCOMet-Gly peptides under the previously mentioned experimental conditions was remarkably selective in the cleavage of the amide bond involving the carboxylic group of methionine in the side chain. The modes of coordination of cis-[Pd(dpa)Cl₂] and cis-[Pd(dpa)(H₂O)₂]²⁺ in the reactions with the non-acetylated peptides and the total steric inhibition of the hydrolytic reaction between cis-[Pd(dpa)(H₂O)₂]²⁺ and MeCOHis-Gly can be attributed to the steric bulk of the palladium(II) complex. This finding should be taken into consideration in designing new palladium(II) complexes for the regioselective cleavage of peptides and proteins.     

Thermal decomposition of nickel(II), palladium(II), and platinum(II) complexes of <Emphasis Type="Italic">N</Emphasis>-allyl-<Emphasis Type="Italic">N</Emphasis>′-pyrimidin-2ylthiourea

Thermal decomposition of Ni(II), Pd(II), and Pt(II) complexes of N-pyrimidin-2ylthiourea (AllPmTu) have been studied by TG, DTG, and DTA and by electron impact (EI) mass spectra. The complexes have the molecular formulae as [Ni(AllPmTu)Cl₂(H₂O)], [Ni(AllPmTu)₂Cl₂(H₂O)₂], and [M(AllPmTu)Cl₂], where M = Pd^II or Pt^II, and [Pt(AllPmTu)₂]. The TG curves show that Ni(II) complexes decompose in three stages to yield NiO as a residue, while Pd(II) and Pt(II) decompose in two stages to yield MS residues. The initial mass losses correspond to elimination of allylamine for Pd(II) and Pt(II) complexes but, allyisothiocyanate for both Ni(II) complexes revealing that sulfur atom of thiourea part is involved in coordination to Pd(II) and Pt(II) but does not to Ni(II). Kinetic parameters (E ^#, n, ΔH ^#, ΔS ^#, ΔG ^#) of the decomposition stages are determined and correlated with bonding and structural properties of the complexes. The EI mass spectra of the complexes show fragments corresponding to the evolved and intermediate species.     

Adsorption of tetracycline using CuCoFe2O4@Chitosan as a new and green magnetic nanohybrid adsorbent from aqueous solutions: Isotherm,kinetic and thermodynamic study

Utilizing a new microwave-assisted method, CuCoFe₂O₄@Chitosan (Ch) was synthesized as a very strong, magnetically separable nano-adsorbent. The magnetic nanohybrid adsorbent was characterized by FESEM (Field emission scanning electron microscopy), EDS (energy dispersive X-ray), Mapping & Linescan, BET (Brunauer-Emmett-Teller), FTIR (Fourier-transform infrared spectroscopy), XRD (X-ray diffraction analysis), TGA (Thermogravimetric analysis), and VSM (Vibrating Sample Magnetometer) techniques. Then, the adsorption process of Tetracycline (TC) was investigated. The highest percentage of pollutant adsorption on the synthetic and real samples was recorded at an initial concentration of 5 mg/L, pH 3.5, contact time of 20 min, the dose of 0.4 g/L, and temperature of 25 °C, 93.07 %, and 67%, respectively. The TC adsorption process via the synthesized magnetic nanocomposite was consistent with the Freundlich isotherm model (R² = 0.992) and pseudo-second-order kinetic (K₂ = 0.267). The outcomes of thermodynamic analyses, which included entropy changes (ΔS = 10.122 J/mol.k), enthalpy changes (ΔH = ?1.975 kJ/mol), and the Gibbs negative free energy (ΔG = ?4.992 kJ/mol), revealed that the adsorption process was spontaneous, favorable, and exothermic. The good magnetic properties allow easy separation after the adsorption operation. Finally, the efficiency of the nano-adsorbent in the removal process was 82.16% after four adsorption–desorption cycles. Some advantages of this research are a fast and green method for synthesis of adsorbent, fast kinetic, and magnetic properties to easy separation.     

In vitro assessment of cytotoxicity, anti-inflammatory, antifungal properties and crystal structures of metallacyclic palladium(II) complexes

Metallacyclic palladium(II) complexes [Pd(L)(R₃P)Cl], L = TIQDTC (1,2,3,4-tetrahydroisoquinolinedithiocarbamate), 4MpipDTC (4-methylpipradinedithiocarbamate), MPizDTC (N-methylpiperazinedithiocarbamate), R₃P = Ph₃P, (o-tolyl)₃P, Ph₂ClP, were synthesized in a 1:1 molar metal-ligand ratio. These complexes were characterized by elemental analyses, FT-IR, multinuclear (¹H, ¹³C and ³¹P) NMR. The X-ray crystal structures of [Pd(TIQDTC)(Ph₃P)Cl] and [Pd(TIQDTC)((o-tolyl)₃P)Cl] show a slightly distorted square planar environment around the Pd(II) ion with S-Pd-S and P-Pd-Cl average bond angles of 74.51 and 92.41, respectively. These complexes were screened for cytotoxic, antifungal, anti-inflammatory and antibacterial activity. Some complexes exhibit a significant activity against fungi.     

Visible light photocatalytic activity of BiVO4 particles with different morphologies

Bismuth vanadate (BiVO₄) particles with different morphologies were synthesized by a one-step hydrothermal process and their optical and photocatalytic properties were investigated. Their crystal structure and microstructures were characterized using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). XRD patterns demonstrate that the as-prepared samples are monoclinic cell. FESEM shows that BiVO₄ crystals can be fabricated in different morphologies by simply manipulating the reaction parameters of hydrothermal process. The UV–visible diffuse reflectance spectra (UV–vis DRS) reveal that the band gaps of BiVO₄ photocatalysts are about 2.07–2.21 eV. The as-prepared BiVO₄ photocatalysts exhibit higher photocatalytic activities in the degradation of rhodamine B (Rh B) under visible light irradiation (λ > 420 nm) compared with traditional N-doped TiO₂ (N-TiO₂). Furthermore, wheat like BiVO₄ sample reveals the highest photocatalytic activity. Up to 100% Rh B is decolorized after visible light irradiation for 180 min. The reason for the difference in the photocatalytic activities for BiVO₄ samples obtained at different conditions were systematically studied based on their shape, size and the variation of local structure.     

Phosphino-(α-sulfinylalkyl)phosphonium ylide complexes (Rh,Pd) with a configurationally stable asymmetric ylidic carbon

The synthesis and structure of Rh(I) and Pd(II) complexes of chiral P,C-chelating phosphino-(α-sulfinylalkyl)phosphonium ylide ligands with a trisubstituted asymmetric ylidic center P⁺–C1R(S1(O)p-Tol)–M (R = alkyl group) have been investigated, and compared to those of the analogous disubstituted ylide complexes (R = H). Reaction of the ethyl onium ylide of o-bis(diphenylphosphino)benzene with (?)-menthyl-(S)-p-tolylsulfinate afforded the corresponding racemic erythro phosphino-(α-sulfinylethyl)phosphonium in 90% de (R = Me). The racemization process is interpreted by a Berry-like pseudorotation mechanism driven by the steric repulsion between the α-methyl substituent and the bulky menthyloxy S-substituent or sulfur lone pair in the intermediate ylide-sulfinyl adduct. The ylide of phosphino-(α-sulfinylethyl)phosphonium reacts with [Rh(cod)₂][PF₆] and PdCl₂(MeCN)₂ to afford the corresponding P,C1-chelated threo-Rh(I) and erythro-Pd(II) mononuclear complexes in 70% yield and total diastereoselectivity. These respective complexes act as efficient catalytic precursors for the hydrogenation of (Z)-α-acetamidocinnamic acid and allylic substitution of 3-acetoxy-1,3-diphenyl-1-propene with sodium dimethyl malonate. The bonding features of the erythro-Pd(II) complex exhibiting a sulfinyl O?Pd interaction are studied theoretically at the DFT level using ELF and MESP analyses. The η²-P,C haptomeric form of the ylide ligand is estimated to compete at 19% with the η¹-C haptomeric form dominating at 81%.