Critical behavior near room temperature in La0.75Ca0.05Na0.20MnO3 sample

The critical behavior of La_0.75Ca_0.05Na_0.20MnO₃ was studied at around room temperature via magnetization measurements. From the relative slope, we deduced that the Tricritical Mean-Field model was the most suitable model. The estimated critical exponents were found to be β = 0.24 ± 0.004, γ = 0.98 ± 0.065 and δ = 5.08 at T_C = 300 K. These critical exponents satisfied the Widom scaling relation δ = 1 + γ/β, implying the reliability of our values. Based on the critical exponents, the magnetization–field–temperature (M–μ₀H–T) data around T_C collapsed into two curves, obeying the single scaling equation with ε = (T − T_C)/T_C being the reduced temperature. These results suggest short-range interaction in our sample.

A set of typical M²vs. μ₀H/M for La_0.75Ca_0.05Na_0.20MnO₃ sample.     

Analysis based on scaling relations of critical behaviour at PM–FM phase transition and universal curve of magnetocaloric effect in selected Ag-doped manganites

The critical behaviour of Pr_0.5Sr_0.5−xAg_xMnO₃ (0 ≤ x ≤ 0.2) samples around the paramagnetic–ferromagnetic phase transition is studied based on isothermal magnetization measurements. The assessments based on Banerjee''s criteria reveal the samples undergoing a second-order magnetic phase transition. Various techniques such as modified Arrott plot, Kouvel–Fisher method, and critical isotherm analysis were used to determine the values of the ferromagnetic transition temperature T_C, as well as the critical exponents of β, γ and δ. The values of critical exponents, derived from the magnetization data using the Kouvel–Fisher method, are found to be (β = 0.43 ± 0.002, 0.363 ± 0.068 and 0.328 ± 0.012), (γ = 1.296 ± 0.007, 1.33 ± 0.0054 and 1.236 ± 0.012) for x = 0.0, 0.1 and 0.2, respectively. This implies that the Pr_0.5Sr_0.5−xAg_xMnO₃ with 0 ≤ x ≤ 0.2 systems does not belong to a single universality class and indicates that the presence of magnetic disorder in the system must be taken into account to fully describe the microscopic interaction of these manganites. With these values, magnetic-field dependences of magnetization at temperatures around T_C can be well described following a single equation of state for our samples. From magnetic entropy change (ΔS_M), it was possible to evaluate the critical exponents of the magnetic phase transitions. Their values are in good agreement with those obtained from the critical exponents using a modified Arrott plot (MAP). We used the scaling hypotheses to scale the magnetic entropy change and heat capacity changes to a universal curve respectively for Pr_0.5Sr_0.5−xAg_xMnO₃ samples.

The universal curves of magnetic entropy changes and heat capacity changes for Pr_0.5Sr_0.5−xAg_xMnO₃ (0 ≤ x ≤ 0.2) are obtained by using the critical exponents.     

Intracellular time course, pharmacokinetics, and biodistribution of isoniazid and rifabutin following pulmonary delivery of inhalable microparticles to mice

Intracellular concentrations of isoniazid and rifabutin resulting from administration of inhalable microparticles of these drugs to phorbol-differentiated THP-1 cells and the pharmacokinetics and biodistribution of these drugs upon inhalation of microparticles or intravenous administration of free drugs to mice were investigated. In cultured cells, both microparticles and dissolved drugs established peak concentrations of isoniazid (~1.4 and 1.1 μg/10⁶ cells) and rifabutin (~2 μg/ml and ~1.4 μg/10⁶ cells) within 10 min. Microparticles maintained the intracellular concentration of isoniazid for 24 h and rifabutin for 96 h, whereas dissolved drugs did not. The following pharmacokinetic parameters were calculated using WinNonlin from samples obtained after inhalation using an in-house apparatus (figures in parentheses refer to parameters obtained after intravenous administration of an equivalent amount, i.e., 100 μg of either drug, to parallel groups): isoniazid, serum half-life (t_1/2) = 18.63 ± 5.89 h (3.91 ± 1.06 h), maximum concentration in serum (C_max) = 2.37 ± 0.23 μg·ml⁻¹ (3.24 ± 0.57 μg·ml⁻¹), area under the concentration-time curve from 0 to 24 h (AUC_0-24) = 55.34 ± 13.72 μg/ml⁻¹ h⁻¹ (16.64 ± 1.80 μg/ml⁻¹ h⁻¹), and clearance (CL) = 63.90 ± 13.32 ml·h⁻¹ (4.43 ± 1.85 ml·h⁻¹); rifabutin, t_1/2 = 119.49 ± 29.62 h (20.18 ± 4.02 h), C_max = 1.59 ± 0.01 μg·ml⁻¹ (3.47 ± 0.33 μg·ml⁻¹), AUC_0-96 = 109.35 ± 14.78 μg/ml⁻¹ h⁻¹ (90.82 ± 7.46 μg/ml⁻¹ h⁻¹), and CL = 11.68 ± 7.00 ml·h⁻¹ (1.03 ± 0.11 ml·h⁻¹). Drug targeting to the lungs in general and alveolar macrophages in particular was observed. It was concluded that inhaled microparticles can reduce dose frequency and improve the pharmacologic index of the drug combination.     

Long-range ferromagnetic order in perovskite manganite La0.67Ba0.25Ca0.08Mn(1−x)TixO3 (x = 0.00, 0.05 and 0.10)

In this study, we report the effects of Ti on the critical behavior of La_0.67Ba_0.25Ca_0.08MnO₃ samples prepared by the flux method. Moreover, the critical exponents β, γ and δ are estimated through numerous techniques such as the modified Arrott plot, the Kouvel–Fisher method and critical isotherm analysis of the magnetic measurements on record near the Curie temperature. Compared to standard models, the estimated critical exponents are close to the theoretical values of the mean-field model for these samples. In order to estimate the spontaneous magnetization at a given temperature, we used a process based on the analysis, in the mean-field theory, of the magnetic entropy change (−ΔS_M) vs. magnetization (M). An excellent agreement was found between the spontaneous magnetization determined from −ΔS_Mvs. M² and the classical extrapolation from the Arrott curves (μ₀H/M vs. M²), thus confirming that −ΔS_M is a valid approach to estimate the spontaneous magnetization in this system. The accuracy of the critical exponent values was confirmed with the scaling hypothesis. The magnetization curves fall onto one of two sides, below and above T_C.

In this study, we report the effects of Ti on the critical behavior of La_0.67Ba_0.25Ca_0.08MnO₃ samples prepared by the flux method.     

Impact of synthesis route on structural,magnetic, magnetocaloric and critical behavior of Nd0.6Sr0.4MnO3 manganite

Nd_0.6Sr_0.4MnO₃ polycrystalline manganite was synthesized by two different methods: the auto-combustion reaction (NSMO-AC) and the sol–gel method (NSMO-SG). The structural, magnetic, magnetocaloric and critical behavior of the samples were examined. Rietveld refinements of the XRD patterns revealed that both compounds are pure single phase indexed to the orthorhombic system adopting the Pnma space group. The nanometric size estimated using the Williamson–Hall method was confirmed by TEM micrographs. Magnetic measurements as a function of temperature indicated that both samples underwent a second order ferromagnetic (FM)–paramagnetic (PM) phase transition at Curie temperature (T_C). The relative cooling power was observed to be around 95.271 J kg⁻¹ for NSMO-AC and 202.054 J kg⁻¹ for NSMO-SG at μ₀H = 5 T, indicating that these materials are potential candidates for magnetic refrigeration application close to room temperature. The critical behavior was estimated using diverse techniques based on the isothermal magnetization data recorded around the critical temperature T_C. The calculated values are fully satisfactory to the requirements of the scaling theory, implying their reliability. The estimated critical exponents matched well with the values anticipated for the mean-field model and the 3D Ising model for NSMO-AC and NSMO-SG, respectively, showing that the magnetic interactions depended on the process of elaboration.

The relative cooling power is around 95.271 J kg⁻¹ for NSMO-AC and 202.054 J kg⁻¹ for NSMO-SG at μ₀H = 5 T, making these materials potential candidates for magnetic refrigeration application near room temperature.     

Large magnetic entropy change and prediction of magnetoresistance using a magnetic field in La0.5Sm0.1Sr0.4Mn0.975In0.025O3

A detailed study of the structural, magnetic, magnetocaloric and electrical effect properties in polycrystalline manganite La_0.5Sm_0.1Sr_0.4Mn_0.975In_0.025O₃ is presented. The X-ray diffraction pattern is consistent with a rhombohedral structure with R$\bar{3}$c space group. Experimental results revealed that our compound prepared via a sol–gel method exhibits a continuous (second-order) ferromagnetic (FM) to paramagnetic (PM) phase transition around the Curie temperature (T_C = 300 K). In addition, the magnetic entropy change was found to reach 5.25 J kg⁻¹ K⁻¹ under an applied magnetic field of 5 T, corresponding to a relative cooling power (RCP) of 236 J kg⁻¹. We have fitted the experimental data of resistivity using a typical numerical method (Gauss function). The simulation values such as maximum resistivity (ρ_max) and metal–semiconductor transition temperature (T_M–Sc), calculated from this function, showed a perfect agreement with the experimental data. The shifts of these parameters as a function of magnetic field for our sample have been interpreted. The obtained values of β and γ, determined by analyzing the Arrott plots, are found to be T_C = 298.66 ± 0.64 K, β = 0.325 ± 0.001 and γ = 1.25 ± 0.01. The critical isotherm M (T_C, μ₀H) gives δ = 4.81 ± 0.01. These critical exponent values are found to be consistent and comparable to those predicted by the three-dimensional Ising model with short-range interaction. Thus, the Widom scaling law is fulfilled.

Rietveld refinement for the sample LSSMIO. Experimental data (the point symbols), calculated data (the solid lines), difference between them is shown at the bottom of the diagram and Bragg positions are marked by vertical bars.     

Synthesis,solid state self-assembly driven by antiparallel π⋯π stacking and {⋯H–C–C–F}2 dimer synthons,and in vitro acetyl cholinesterase inhibition activity of phenoxy pendant isatins

A series of novel phenoxy pendant isatins PI1–12 have been synthesized in excellent yields by a simple nucleophilic substitution reaction involving isatins and 1-(2-bromoethoxy)-4-substituted benzenes, and characterized by their FT-IR, ¹H NMR, ¹³C NMR and GC-MS data, and in the case of PI4 by its single crystal X-ray analysis. The solid-state structure of PI4 showed an intriguing and unique 1D-supramolecular chain-based self-assembled structure, the driving force of which is mainly the strong antiparallel π⋯π stacking and {⋯H–C–C–F}₂ dimer synthons. This compound not only highlights the potential of the isatin moiety in forming strong antiparallel π⋯π stacking interactions but also provides a platform to have considerable insight into the nature, strength and directionality of much debated π–π and C–H⋯F–C interactions. The in vitro biological studies revealed that three phenoxy pendant isatins PI1, PI2 and PI4 are highly potent inhibitors of acetylcholinesterase enzyme with IC₅₀ values of 0.52 ± 0.073 μg ml⁻¹, 0.72 ± 0.012 μg ml⁻¹ and 0.68 ± 0.011 μg ml⁻¹, respectively, showing comparable activity to the standard drug, donepezil (IC₅₀ = 0.73 ± 0.015 μg ml⁻¹). A simple and efficient synthesis of phenoxy pendant isatins PI1–12 from inexpensive and commercially available starting materials, and their high potential of acetyl cholinesterase inhibition provide an attractive opportunity to find more effective medication for Alzheimer''s disease (AD).

The phenoxy pendant isatins were observed to be highly potent inhibitors of acetylcholinesterase. In addition, the solid-state structure of a phenoxy pendant isatin showed an intriguing 1D-supramolecular self-assembled structure.     

Evaluation of Nd0.8−xSr0.2CaxCoO3−δ(x = 0, 0.05, 0.1, 0.15, 0.2) as a cathode material for intermediate-temperature solid oxide fuel cells

A series of Nd_0.8−xSr_0.2Ca_xCoO_3−δ(x = 0, 0.05, 0.1, 0.15, 0.2) cathode materials was synthesized by sol–gel method. The effect of Ca doping amount on the structure was examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), thermal expansion, and X-ray photoelectron spectroscopy (XPS). Electrochemical properties were evaluated for possible application in solid oxide fuel cell (SOFC) cathodes. Results showed that second phase NdCaCoO_4+δ is generated when the Ca doping amount is higher than 0.1. The increase in Ca limits the electronic compensation capacity of the material, resulting in a decrease in thermal expansion coefficient (TEC). With the increase of Ca content, the conductivity increases at first and then decreases, and the highest value of 443 S cm⁻¹ is at x = 0.1 and T = 800 °C. Nd_0.7Sr_0.2Ca_0.1CoO_3−δ exhibits the lowest area specific resistance of 0.0976 Ω cm² at 800 °C. The maximum power density of Nd_0.7Sr_0.2Ca_0.1CoO_3−δ at 800 °C is 409.31 mW cm⁻². The Ca-doped material maintains good electrochemical properties under the coefficient of thermal expansion (CTE) reduction and thus can be used as an intermediate-temperature SOFC (IT-SOFC) cathode.

The increase in Ca for Nd_0.8−xSr_0.2Ca_xCoO_3−δ limits the electronic compensation capacity, resulting in a decrease in CTE. The Ca-doped material maintains good electrochemical properties under CTE reduction and thus can be used as an IT-SOFC cathode.     

Influence of Ni content on structural,magnetocaloric and electrical properties in manganite La0.6Ba0.2Sr0.2Mn1−xNixO3 (0 ≤ x ≤ 0.1) type perovskites

We present a detailed study on the physical properties of La_0.6Ba_0.2Sr_0.2Mn_1−xNi_xO₃ samples (x = 0.00, 0.05 and 0.1). The ceramics were fabricated using the sol–gel route. Structural refinement, employing the Rietveld method, disclosed a rhombohedral R$\bar{3}$c phase. The magnetization vs. temperature plots show a paramagnetic–ferromagnetic (PM–FM) transition phase at the T_C (Curie temperature), which decreases from 354 K to 301 K. From the Arrott diagrams M²vs. μ₀H/M, we can conclude the phase transition is of the second order. Based on measurements of the isothermal magnetization around T_C, the magnetocaloric effects (MCEs) have been calculated. The entropy maximum change (−ΔS_M) values are 7.40 J kg⁻¹ K⁻¹, 5.6 J kg⁻¹ K⁻¹ and 4.48 J kg⁻¹ K⁻¹, whereas the relative cooling power (RCP) values are 232 J kg⁻¹, 230 J kg⁻¹ and 156 J kg⁻¹ for x = 0.00, 0.05 and 0.10, respectively, under an external field (μ₀H) of 5 T. Through these results, the La_0.6Ba_0.2Sr_0.2Mn_1−xNi_xO₃ (0 ≤ x ≤ 0.1) samples can be suggested for use in magnetic refrigeration technology above room temperature. The electrical resistivity (ρ) vs. temperature plots exhibit a transition from metallic behavior to semiconductor behavior in the vicinity of T_M–SC. The adiabatic small polaron hopping (ASPH) model is applied in the PM-semiconducting part (T > T_MS). Throughout the temperature range, ρ is adjusted by the percolation model. This model is based on the phase segregation of FM-metal clusters and PM-insulating regions.

We present a detailed study on the physical properties of La_0.6Ba_0.2Sr_0.2Mn_1−xNi_xO₃ samples (x = 0.00, 0.05 and 0.1).     

Formation and dissociation of synthetic hetero-double-helix complex in aqueous solutions: significant effect of water content on dynamics of structural change

A 1 : 1 mixture of the ethynylhelicene pseudoenantiomers (M)-tetramer and (P)-pentamer, which possess hydrophilic terminal tri(ethyleneglycol) (TEG) groups, changes their structures in the water–THF (10 μM) solvent system between dissociated random-coils and an associated hetero-double-helix upon heating and cooling. A small change in water content between 30 and 33% significantly affects the dynamics of structural changes. At 30% water content, heating to 60 °C causes rapid formation of random-coil and cooling to 10 °C causes the rapid formation of hetero-double-helix, accompanied by repeated changes in Δε at 369 nm between 0 and −2000 cm⁻¹ M⁻¹. Heating and cooling experiments at constant rates between 60 and 10 °C resulted in sigmoidal curves in Δε/temperature profiles, which indicate rapid structural changes. Different phenomena occurred at 33% water content. Heating to 60 °C and cooling to 0 °C initially induced changes in Δε between 0 and −2000 cm⁻¹ M⁻¹, and repeated cycles gradually reduced the range between 0 and −500 cm⁻¹ M⁻¹. Heating and cooling experiments at constant rates between 60 and 10 °C caused small changes in Δε, and repeated cycles at 10 °C gradually increased Δε to −500 cm⁻¹ M⁻¹. These phenomena involved rapid changes in molecular structure and slow structural changes in the water–THF solvent system. The sharp switching of the dynamics of structural changes at water content between 30 and 33% indicated discontinuous structural changes in the hydration of TEG and/or in water clusters in the vicinity of oligomer molecules.

Significant structural changes by small change in water content from 30 to 33%.     

Aromatic fluorocopolymers based on α-(difluoromethyl)styrene and styrene: synthesis,characterization, and thermal and surface properties

A study on the α-(difluoromethyl)styrene (DFMST) reactivity under conventional radical copolymerization conditions is presented. Although the homopolymerization of DFMST failed, its radical bulk copolymerization with styrene (ST) led to the synthesis of fluorinated aromatic polymers (FAPs). The resulting novel poly(DFMST-co-ST) copolymers were characterized by ¹H, ¹⁹F and ¹³C NMR spectroscopies that evidenced the successful incorporation of DFMST units into copolymers and enabled the assessment of their respective molar percentages (10.4–48.2 mol%). The molar masses were in the range of 1900–17 200 g mol⁻¹. The bulkier CF₂H group in the α-position induced the lower reactivity of the DFMST comonomer. ST and DFMST monomer reactivity ratios (r_DFMST = 0.0 and r_ST = 0.70 ± 0.05 at 70 °C) were determined based on linear least-square methods. These values indicate that DFMST monomer is less reactive than ST, retards the polymerization rate, and thus reduces the molar masses. Moreover, the thermal properties (T_g, T_d) of the resulting copolymers indicate that the presence of DFMST units incorporated into poly(ST) structure promotes an increase of the T_g values up to 109 °C and a slightly better thermal stability than that of poly(ST). Additionally, the thermal decomposition of poly(DFMST-co-ST) copolymer (10.4/89.6) was assessed by simultaneous thermal analysis coupled with Fourier-transform infrared spectroscopy and thermogravimetric analysis coupled with mass spectrometry showing that H₂O, CO₂, CO and styrene were released. The surface analysis was focused on the effects of the –CF₂H group at the α-position of styrene comonomers on surface free energy of the copolymer films. Water and diiodomethane contact angle (CA) measurements confirmed that these copolymers (M_n = 2300–17 200 g mol⁻¹) are not exactly the same as polystyrenes (M_n = 2100–21 600 g mol⁻¹) in the solid state. The CA hysteresis for poly(ST) (6–8°) and poly(DFMST-co-ST) copolymers (3–5°) reflected these differences even more accurately.

A study on the α-(difluoromethyl)styrene (DFMST) reactivity under conventional radical (co)polymerization conditions is presented.     

Development and validation of a sensitive LC-MS/MS method for pioglitazone: application towards pharmacokinetic and tissue distribution study in rats

In the present study, a sensitive LC-MS/MS method was developed and validated to measure pioglitazone (PGZ) concentrations in rat plasma and tissues. The chromatographic separation was achieved by using a YMC Pro C₁₈ column (100 mm × 4.6 mm, 3μ) with a mobile phase consisting of formic acid (0.1% v/v) and acetonitrile (5 : 95) at a flow rate of 0.7 mL min⁻¹ and injection volume of 10 μL (IS: rosiglitazone). Mass spectrometric detection was done using triple quadrupole mass spectrometry using the ESI interface operating in a positive ionization mode. The developed method was validated over a linearity range of 1–500 ng mL⁻¹ with detection and a lower quantification limit of 0.5 ng mL⁻¹ and 1 ng mL⁻¹. The method accuracy ranged from 95.89–98.78% (inter-day) & 93.39–97.68% (intra-day) with a precision range of 6.09–8.12% for inter-day & 7.55–9.87% for intra-day, respectively. The PGZ shows the highest C_max of 495.03 ng mL⁻¹ in plasma and the lowest C_max, 24.50 ± 2.71 ng mL⁻¹ in bone. The maximum T_max of 5.00 ± 0.49 h was observed in bone and a minimum of 1.01 ± 0.05 h in plasma. The AUC_{(0–24 h and 0–∞)} values are highest in plasma (1056.58 ± 65.78 & 1069.38 ± 77.50 ng h⁻¹ mL⁻¹) and lowest in brain (166.93 ± 15.70 &167.12 ± 16.77 ng h⁻¹ mL⁻¹), and the T_1/2 was highest in plasma (5.62 ± 0.74 h) and lowest in kidney (2.78 ± 0.19). The developed method was successfully used to measure the PGZ pharmacokinetic and tissue distribution. Further, the developed method could be utilized for validating target organ (adipose tissue) specific delivery of PGZ (nano-formulations) in addition to conventional dosage forms.

The developed method was investigated for target and off-target distribution of pioglitazone and could be applied to validate the site-specific delivery systems.     

Influence of Al2O3 nanoparticle doping on depolarization temperature,and electrical and energy harvesting properties of lead-free 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

In this research article, the effects of Al₂O₃ nanoparticles (0–1.0 mol%) on the phase formation, microstructure, dielectric, ferroelectric, piezoelectric, electric field-induced strain and energy harvesting properties of the 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (BNT–6BT) ceramic were investigated. All ceramics have been synthesized by a conventional mixed oxide method. The XRD and Raman spectra showed coexisting rhombohedral and tetragonal phases throughout the entire compositional range. An increase of the grain size, T_F–R, T_m, ε_max and δ_A values was noticeable when Al₂O₃ was added. Depolarization temperature (T_d), which was determined by the thermally stimulated depolarization current (TSDC), tended to increase with Al₂O₃ content. The good ferroelectric properties (P_r = 32.64 μC cm⁻², E_c = 30.59 kV cm⁻¹) and large low-field d₃₃ (205 pC N⁻¹) values were observed for the 0.1 mol% Al₂O₃ ceramic. The small Al₂O₃ additive improved the electric field-induced strain (S_max and ). The 1.0 mol% Al₂O₃ ceramic had a large piezoelectric voltage coefficient (g₃₃ = 32.6 × 10⁻³ Vm N⁻¹) and good dielectric properties (ε_r,max = 6542, T_d = 93 °C, T_F–R = 108 °C, T_m = 324 °C and δ_A = 164 K). The highest off-resonance figure of merit (FoM) for energy harvesting of 6.36 pm² N⁻¹ was also observed for the 1.0 mol% Al₂O₃ ceramic, which is suggesting that this ceramic has potential to be one of the promising lead-free piezoelectric candidates for further use in energy harvesting applications.

In this research article, the effects of Al₂O₃ nanoparticles (0–1.0 mol%) on the phase, microstructure, dielectric, ferroelectric, piezoelectric, electric field-induced strain and energy harvesting of the BNT–6BT ceramic were investigated.     

Binuclear and tetranuclear Zn(ii) complexes with thiosemicarbazones: synthesis,X-ray crystal structures,ATP-sensing,DNA-binding,phosphatase activity and theoretical calculations

Two Zinc(ii) complexes [Zn₄(L¹)₄]·2H₂O (1) and [Zn₂(L²)₂]·2H₂O (2) of pyruvaldehydethiosemicarbazone ligands are reported. The complexes were characterized by elemental analysis, IR, NMR, UV-vis spectroscopy and by single-crystal X-ray crystallography. X-ray crystal structure determinations of the complexes show that though Zn : ligand stoichiometry is 1 : 1 in both the complexes, the molecular unit is tetranuclear for 1 and binuclear for 2. Both the complexes show selective sensing of ATP at pH 7.4 (0.01 M HEPES) in CH₃CN–H₂O (9 : 1) medium in the presence of other anions like AcO⁻, NO₃⁻, F⁻, Cl⁻, H₂PO₄⁻, HPO₄²⁻ and P₂O₇²⁻. The UV-titration experiments of complexes 1 and 2 with ATP results in binding constants of 2.0(±0.07) × 10⁴ M⁻¹ and 7.1(±0.05) × 10³ M⁻¹ respectively. The calculated detection limits of 6.7 μM and 1.7 μM for 1 and 2 respectively suggest that the complexes are sensitive detectors of ATP. High selectivity of the complexes is confirmed by the addition of ATP in presence of an excess of other anions. DFT studies confirm that the ATP complexes are more favorable than those with the other inorganic phosphate anions, in agreement with the experimental results. Phosphatase like activity of both complexes is investigated spectrophotometrically using 4-nitrophenylphosphate (NPP) as a substrate, indicating the complexes possess significant phosphate ester hydrolytic efficiency. The kinetics for the hydrolysis of the substrate NPP was studied by the initial rate method at 25 °C. Michaelis–Menten derived kinetic parameters indicate that rate of hydrolysis of the P–O bond by complex 1 is much greater than that of complex 2, the k_cat values being 212(±5) and 38(±2) h⁻¹ respectively. The DNA binding studies of the complexes were investigated using electronic absorption spectroscopy and fluorescence quenching. The absorption spectral titrations of the complexes with DNA indicate that the CT-DNA binding affinity (K_b) of complex 1 (2.10(±0.07) × 10⁶ M⁻¹) is slightly greater than that of 2 (1.11(±0.04) × 10⁶ M⁻¹). From fluorescence spectra the apparent binding constant (K_app) values were calculated and they are found to be 5.41(±0.01) × 10⁵ M⁻¹ for 1 and 3.93(±0.02) × 10⁵ M⁻¹ for 2. The molecular dynamics simulation demonstrates that the Zn(ii) complex 1 is a good intercalator of DNA.

A binuclear and a tetranuclear zinc(ii) of pyruvaldehyde thiosemicarbazone show selective sensing of ATP at pH 7.4 (0.01 M HEPES) in CH₃CN–H₂O (9 : 1) medium. The DNA binding and phosphatase activities of the complexes are also reported.     

β-Myrcene/isobornyl methacrylate SG1 nitroxide-mediated controlled radical polymerization: synthesis and characterization of gradient,diblock and triblock copolymers

β-Myrcene (My), a natural 1,3-diene, and isobornyl methacrylate (IBOMA), from partially bio-based raw materials sources, were copolymerized by nitroxide-mediated polymerization (NMP) in bulk using the SG1-based BlocBuilder™ alkoxyamine functionalized with an N-succinimidyl ester group, NHS-BlocBuilder, at T = 100 °C with initial IBOMA molar feed compositions f_IBOMA,0 = 0.10–0.90. Copolymer reactivity ratios were r_My = 1.90–2.16 and r_IBOMA = 0.02–0.07 using Fineman–Ross, Kelen–Tudos and non-linear least-squares fitting to the Mayo–Lewis terminal model and indicated the possibility of gradient My/IBOMA copolymers. A linear increase in molecular weight versus conversion and a low dispersity (Đ ≤ 1.41) were exhibited by My/IBOMA copolymerization with f_IBOMA,0 ≤ 0.80. My-rich and IBOMA-rich copolymers were shown to have a high degree of chain-end fidelity by performing subsequent chain-extensions with IBOMA and/or My, and by ³¹P NMR analysis. The preparation by NMP of My/IBOMA thermoplastic elastomers (TPEs), mostly bio-sourced, was then attempted. IBOMA-My-IBOMA triblock copolymers containing a minor fraction of My or styrene (S) units in the outer hard segments (M_n = 51–95 kg mol⁻¹, Đ = 1.91–2.23 and F_IBOMA = 0.28–0.36) were synthesized using SG1-terminated poly(ethylene-stat-butylene) dialkoxyamine. The micro-phase separation was suggested by the detection of two distinct T_gs at about −60 °C and +180 °C and confirmed by atomic force microscopy (AFM). A plastic stress–strain behavior (stress at break σ_B = 3.90 ± 0.22 MPa, elongation at break ε_B = 490 ± 31%) associated to an upper service temperature of about 140 °C were also highlighted for these triblock polymers.

β-Myrcene (My), a natural 1,3-diene, and isobornyl methacrylate (IBOMA), from partially bio-based raw materials sources, were copolymerized by nitroxide-mediated polymerization (NMP) in bulk.     

A series of four novel alkaline earth metal–organic frameworks constructed of Ca(ii), Sr(ii), Ba(ii) ions and tetrahedral MTB linker: structural diversity,stability study and low/high-pressure gas adsorption properties

A series of four novel microporous alkaline earth metal–organic frameworks (AE-MOFs) containing methanetetrabenzoate linker (MTB) with composition {[Ca₄(μ₈-MTB)₂]·2DMF·4H₂O}_n (UPJS-6), {[Ca₄(μ₄-O)(μ₈-MTB)_3/2(H₂O)₄]·4DMF·4H₂O}_n (UPJS-7), {[Sr₃(μ₇-MTB)_3/2]·4DMF·7H₂O}_n (UPJS-8) and {[Ba₃(μ₇-MTB)_3/2(H₂O)₆]·2DMF·4H₂O}_n (UPJS-9) (UPJS = University of Pavol Jozef Safarik) have been successfully prepared and characterized. The framework stability and thermal robustness of prepared materials were investigated using thermogravimetric analysis (TGA) and high-energy powder X-ray diffraction (HE-PXRD). MOFs were tested as adsorbents for different gases at various pressures and temperatures. Nitrogen and argon adsorption showed that the activated samples have moderate BET surface areas: 103 m² g⁻¹ (N₂)/126 m² g⁻¹ (Ar) for UPJS-7′′, 320 m² g⁻¹ (N₂)/358 m² g⁻¹ (Ar) for UPJS-9′′ and UPJS-8′′ adsorbs only a limited amount of N₂ and Ar. It should be noted that all prepared compounds adsorb carbon dioxide with storage capacities ranging from 3.9 to 2.4 wt% at 20 °C and 1 atm, and 16.4–13.5 wt% at 30 °C and 20 bar. Methane adsorption isotherms show no adsorption at low pressures and with increasing pressure the storage capacity increases to 4.0–2.9 wt% of CH₄ at 30 °C and 20 bar. Compounds displayed the highest hydrogen uptake of 3.7–1.8 wt% at −196 °C and 800 Torr among MTB containing MOFs.

Four novel microporous alkaline earth metal–organic frameworks (AE-MOFs) containing methanetetrabenzoate linker (MTB): UPJS-6, UPJS-7, UPJS-8 and UPJS-9 have been successfully prepared, characterized and tested as adsorbents for different gases.     

Pt-grown carbon nanofibers for detection of hydrogen peroxide

Removal of left-over catalyst particles from carbon nanomaterials is a significant scientific and technological problem. Here, we present the physical and electrochemical study of application-specific carbon nanofibers grown from Pt-catalyst layers. The use of Pt catalyst removes the requirement for any cleaning procedure as the remaining catalyst particles have a specific role in the end-application. Despite the relatively small amount of Pt in the samples (7.0 ± 0.2%), they show electrochemical features closely resembling those of polycrystalline Pt. In O₂-containing environment, the material shows two separate linear ranges for hydrogen peroxide reduction: 1–100 μM and 100–1000 μM with sensitivities of 0.432 μA μM⁻¹ cm⁻² and 0.257 μA μM⁻¹ cm⁻², respectively, with a 0.21 μM limit of detection. In deaerated solution, there is only one linear range with sensitivity 0.244 μA μM⁻¹ cm⁻² and 0.22 μM limit of detection. We suggest that the high sensitivity between 1 μM and 100 μM in solutions where O₂ is present is due to oxygen reduction reaction occurring on the CNFs producing a small additional cathodic contribution to the measured current. This has important implications when Pt-containing sensors are utilized to detect hydrogen peroxide reduction in biological, O₂-containing environment.

Application specific Pt-grown carbon nanofibers for H₂O₂ detection were characterized and the roles of dissolved oxygen and chloride ions on the electrochemical performance were assessed in detail.     

One-step synthesis,characterization and properties of novel hybrid electromagnetic nanomaterials based on polydiphenylamine and Co–Fe particles in the absence and presence of single-walled carbon nanotubes

A one-step preparation method for hybrid electromagnetic nanomaterials based on polydiphenylamine (PDPA) and bimetallic Co–Fe particles in the absence and presence of single-walled carbon nanotubes (SWCNT) was proposed. During IR heating of PDPA in the presence of Co(ii) and Fe(iii) salts in an inert atmosphere at T = 450–600 °C, the polycondensation of diphenylamine (DPA) oligomers and dehydrogenation of phenyleneamine units of the polymer with the formation of C N bonds and reduction of metals by evolved hydrogen with the formation of bimetallic Co–Fe particles dispersed in a polymer matrix occur simultaneously. When carbon nanotubes are introduced into the reaction system, a nanocomposite material is formed, in which bimetallic Co–Fe particles immobilized on SWCNT are distributed in the matrix of the polymer. According to XRD data, reflection peaks of bimetallic Co–Fe particles at diffraction scattering angles 2θ = 69.04° and 106.5° correspond to a solid solution based on the fcc-Co crystal lattice. According to SEM and TEM data, a mixture of particles with sizes of 8–30 nm and 400–800 nm (Co–Fe/PDPA) and 23–50 nm and 400–1100 nm (Co–Fe/SWCNT/PDPA) is formed in the nanocomposites. The obtained multifunctional Co–Fe/PDPA and Co–Fe/SWCNT/PDPA nanomaterials demonstrate good thermal, electrical and magnetic properties. The saturation magnetization of the nanomaterials is M_S = 14.99–31.32 emu g⁻¹ (Co–Fe/PDPA) and M_S = 29.48–48.84 emu g⁻¹ (Co–Fe/SWCNT/PDPA). The electrical conductivity of the nanomaterials reaches 3.5 × 10⁻³ S cm⁻¹ (Co–Fe/PDPA) and 1.3 S cm⁻¹ (Co–Fe/SWCNT/PDPA). In an inert medium, at 1000 °C the residue is 71–77%.

In a self-organizing system within one stage under IR heating conditions, hybrid nanomaterials are formed with a structure that contains bimetallic Co–Fe particles, free or immobilized on the SWCNT surface, dispersed in the polymer PDPA matrix.     

Structural transformation of methasterone with Cunninghamella blakesleeana and Macrophomina phaseolina

An anabolic-androgenic synthetic steroidal drug, methasterone (1) was transformed by two fungi, Cunninghamella blakesleeana and Macrophimina phaseclina. A total of six transformed products, 6β,7β,17β-trihydroxy-2α,17α-dimethyl-5α-androstane-3-one (2), 6β,7α,17β-trihydroxy-2α,17α-dimethyl-5α-androstane-3-one (3), 6α,17β-dihydroxy-2α,17α-dimethyl-5α-androstane-3,7-dione (4), 3β,6β,17β-trihydroxy-2α,17α-dimethyl-5α-androstane-7-one (5), 7α,17β-dihydroxy-2α,17α-dimethyl-5α-androstane-3-one (6), and 6β,9α,17β-trihydroxy-2α,17α-dimethyl-5α-androstane-3-one (7) were synthesized. Among those, compounds 2–5, and 7 were identified as new transformed products. MS, NMR, and other spectroscopic techniques were performed for the characterization of all compounds. Substrate 1 (IC₅₀ = 23.9 ± 0.2 μg mL⁻¹) showed a remarkable anti-inflammatory activity against nitric oxide (NO) production, in comparison to standard LNMMA (IC₅₀ = 24.2 ± 0.8 μg mL⁻¹). Whereas, its metabolites 2, and 7 showed moderate inhibition with IC₅₀ values of 38.1 ± 0.5 μg mL⁻¹, and 40.2 ± 3.3 μg mL⁻¹, respectively. Moreover, substrate 1 was found to be cytotoxic for the human normal cell line (BJ) with an IC₅₀ of 8.01 ± 0.52 μg mL⁻¹, while metabolites 2–7 were identified as non-cytotoxic. Compounds 1–7 showed no cytotoxicity against MCF-7 (breast cancer), NCI-H460 (lung cancer), and HeLa (cervical cancer) cell lines.

Fungal transformation of methasterone resulted in six products (2–7). 2–5, and 7 were identified as new. Substrate 1 showed remarkable anti-inflammatory activity but was cytotoxic. Products 2 and 7 showed moderate activity but were non-cytotoxic.     

Microporous carbon in the selective electro-oxidation of molecular biomarkers: uric acid,ascorbic acid,and dopamine

Herein, we demonstrate the superior electrocatalytic activities of microporous carbon in the oxidation of three molecular biomarkers, ascorbic acid (AA), dopamine (DA), and uric acid (UA), which are co-present in biological fluids. The voltammetric responses of AA, DA, and UA at the low-cost microporous carbon electrode show significantly better sensitivity and selectivity than other more expensive and commonly used electrode materials such as copper(ii) oxide, copper(i) oxide, and carbon nanotube. Differential pulse voltammetry at the microporous carbon electrode allows the detection of AA, DA, and UA with linear ranges of 100–2000 μM (AA), 10–150 μM (DA), and 10–150 μM (UA), sensitivities of 6.8 ± 0.2 nA μM⁻¹ (AA), 261.4 ± 3.4 nA μM⁻¹ (DA), and 93.5 ± 2.0 nA μM⁻¹ (UA), and detection limits of 23.1 μM (AA), 0.2 μM (DA), and 1.7 μM (UA). The method has been validated with a synthetic urine sample to yield ∼100% recoveries for all three analytes. The developed method has been further applied in the investigation of the peroxide scavenging activity of UA.

Herein, we demonstrate the superior electrocatalytic activities of microporous carbon in the oxidation of three molecular biomarkers, ascorbic acid (AA), dopamine (DA), and uric acid (UA), which are co-present in biological fluids.