Ag2Mo2O7: an oxide solid-state Ag+ electrolyte

Ag₂Mo₂O₇ powders and micro-crystals were prepared at 400 °C for 24 h and 500 °C for 6 h using solid-state reactions. The Ag₂Mo₂O₇ samples crystalized in a triclinic P$\bar{1}$ space group with the cell parameters a = 6.0972(1) Å, b = 7.5073(1) Å, c = 7.6779(2) Å, α = 110.43(1)°, β = 93.17(1)°, γ = 113.51(1)°, and V = 294.17(1) ų from Rietveld refinements. Ag₂Mo₂O₇ powder is homogeneous with size of 2–8 μm and the ceramic pellets are in good sintering conditions with a relative density ∼93%. The indirect band gaps E_g(i) of Ag₂Mo₂O₇ from reflectance measurements and DFT calculations are 2.63(1) and 1.80 eV. The vibrational modes of Ag₂Mo₂O₇ were investigated by first-principles (DFT) calculations and Raman spectrum measurements with 24 of 33 predicted Raman modes recorded. According to DOS analyses, the valence bands (VB) of Ag₂Mo₂O₇ are mainly constituted of O-2p and Ag-4d orbitals, while the conduction bands (CB) are mainly composed of Mo-4d and the O-2p orbitals. Regarding the impedance analysis, Ag₂Mo₂O₇ is a silver oxide ion electrolyte with a conductivity of ∼5 × 10⁻⁴ S cm⁻¹ at 450 °C. The carrier activation energy of Ag₂Mo₂O₇ is 0.88(3) eV from the temperature dependent conductivity measurements.

Ag₂Mo₂O₇ is an oxide solid-state Ag⁺ electrolyte with the conductivity ∼5 × 10⁻⁴ S cm⁻¹ at 450 °C and carrier activation energy 0.88(3) eV.     

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.     

Donor moieties with D–π–a framing modulated electronic and nonlinear optical properties for non-fullerene-based chromophores

Herein, a series of non-fullerene-based substantial chromophores (FHD1–FHD6) with a D–π–A framework was designed from a synthesized non-fullerene compound (FH) via structural tailoring with various donor moieties. The FH and its designed derivatives were optimized with frequency analysis at the M06/6-311G (d,p) level to confirm their true minima on potential energy surfaces. These optimized geometries were utilized to perform further analyses, such as absorption, natural bonding orbital (NBO), frontier molecular orbital (FMO), and nonlinear orbital (NLO) analyses at the aforesaid level. Quantum chemical study revealed that all the designed chromophores exhibited a lower band gap than that of the parent molecule with the exception of FHD3. Furthermore, density of states (DOS) analysis supported the findings from the FMO study, and this agreement revealed that the efficient charge was transferred from the HOMO to the LUMO. The NBO investigations disclosed that all the compounds comprised donor moieties with positive charges and acceptors having negative charges. Interestingly, π-conjugated linkers were also found with positive charges, showing an effective donating property. These NBO findings explicated that FHD1–FHD6 exhibited an efficient push–pull mechanism. The λ_max values of the designed chromophores were observed to be greater than the reference compound. The average polarizability 〈α〉, first hyperpolarizability (β_tot), and second hyperpolarizability 〈γ〉 values of FHD2 were found to be 2.170 × 10⁻²², 3.150 × 10⁻²⁷, and 4.275 × 10⁻³² esu, respectively, while all the other derivatives had been reported in the relevant range. Efficient NLO data revealed that FH-based derivatives may contribute significantly toward NLO technology.

Herein, a series of non-fullerene-based substantial chromophores (FHD1–FHD6) with a D–π–A framework was designed from a synthesized non-fullerene compound (FH) via structural tailoring with various donor moieties.     

GSH-doped GQDs using citric acid rich-lime oil extract for highly selective and sensitive determination and discrimination of Fe3+ and Fe2+ in the presence of H2O2 by a fluorescence “turn-off” sensor

Synthesis and characterization of graphene quantum dots (GQDs) simultaneously doped with 1% glutathione (GSH-GQDs) by pyrolysis using citric acid rich-lime oil extract as a starting material. The excitation wavelength (λ_max = 337 nm) of the obtained GSH-GQD solution is blue shifted from that of bare GQDs (λ_max = 345 nm), with the same emission wavelength (λ_max = 430 nm) indicating differences in the desired N and S matrices decorating the carbon based nanoparticles, without any background effect of both ionic strength and masking agent. For highly Fe³⁺-sensitive detection under optimum conditions, acetate buffer at pH 4.0 in the presence of 50 μM H₂O₂, the linearity range was 1.0–150 μM (R² = 0.9984), giving its calibration curve: y = 34.934x + 169.61. The LOD and LOQ were found to be 0.10 and 0.34 μM, respectively. The method’s precisions expressed in terms of RSDs for repeatability (n = 3 × 3 for intra-day analysis) were 2.03 and 3.17% and for reproducibility (n = 5 × 3 for inter-day analysis) were 3.11 and 4.55% for Fe²⁺ and Fe³⁺, respectively. The recoveries of the method expressed as the mean percentage (n = 3) were found in the ranges of 100.1–104.1 and 98.08–102.7% for Fe²⁺ and Fe³⁺, respectively. The proposed method was then implemented satisfactorily for trace determination of iron speciation in drinking water.

Synthesis and characterization of graphene quantum dots (GQDs) simultaneously doped with 1% glutathione (GSH-GQDs) by pyrolysis using citric acid rich-lime oil extract as a starting material.     

Inhibitory Effect of Colicin E2 on Transport Systems of Escherichia coli in the Presence of the rex Gene of λ Prophage

Purified colicin E₂ was found to cause marked inhibition of the permeation rate of o-nitrophenyl-galactoside (ONPG) in several λ-lysogenic strains of Escherichia coli in the presence of chloramphenicol to prevent prophage induction. The inhibitory effect of colicin E₂ on transport systems was analyzed with cells of E. coli CP78(λ). The dose of colicin E₂ for the half-maximum inhibition of the ONPG-permeation rate was about 9 molecules of the colicin per bacterium under the aerobic condition, which corresponded to about 1 killing unit per bacterium. Kinetics of the transport of [¹⁴C]methylthiogalactoside suggested that colicin E₂ began to inhibit the influx rate of β-galactosides within a few minutes after the colicin addition, and the maximum inhibition reached more than 80%. Extensive leakage of intracellular potassium ion and inhibition of l-proline transport also occurred at the same time. Acid solubilization of cellular deoxyribonucleic acid by the colicin was apparently delayed to the initiation of the transport inhibition. The extents of the inhibition of β-galactoside transport and leakage of potassium ion by the colicin were extensive in cells lysogenic for wild λ phage or λind⁻, whereas the extents were slight in the nonlysogenic cells or cells carrying λrex⁻ prophage. It was concluded that the sensitization of membrane transport systems of E. coli cells to colicin E₂ was achieved by the presence of the rex gene product of λ phage.     

Development of rapid and selective epoxidation of α-pinene using single-step addition of H2O2 in an organic solvent-free process

This study reports substantial improvement in the process for oxidising α-pinene, using environmentally friendly H₂O₂ at high atom economy (∼93%) and selectivity to α-pinene oxide (100%). The epoxidation of α-pinene with H₂O₂ was catalysed by tungsten-based polyoxometalates without any solvent. The variables in the screening parameters were temperatures (30–70 °C), oxidant amount (100–200 mol%), acid concentrations (0.02–0.09 M) and solvent types (i.e., 1,2-dichloroethane, toluene, p-cymene and acetonitrile). Screening the process parameters revealed that almost 100% selective epoxidation of α-pinene to α-pinene oxide was possible with negligible side product formation within a short reaction time (∼20 min), using process conditions of a 50 °C temperature in the absence of solvent and α-pinene/H₂O₂/catalyst molar ratio of 5 : 1 : 0.01. A kinetic investigation showed that the reaction was first-order for α-pinene and catalyst concentration, and a fractional order (∼0.5) for H₂O₂ concentration. The activation energy (E_a) for the epoxidation of α-pinene was ∼35 kJ mol⁻¹. The advantages of the epoxidation reported here are that the reaction could be performed isothermally in an organic solvent-free environment to enhance the reaction rate, achieving nearly 100% selectivity to α-pinene oxide.

Products obtained from the oxidation of α-pinene with hydrogen peroxide (H₂O₂) in the presence of tungsten-based polyoxometalates (α-pinene 1, α-pinene oxide 2, pinanediol 3, campholenic aldehyde 4, sobrerol 5, verbenol 6 and verbenone 7).     

Bain and Nishiyama–Wassermann transition path separation in the martensitic transitions of Fe

The importance of martensitic transformations has led to tremendous efforts to explore the microscopic martensitic transition paths. There are five possible transformation paths (for γ → α transition) known for Fe at present, and at an arbitrary activation energy, any of the five paths might be followed. It then becomes considerably difficult to monitor the microscopic phase transition mechanism in experiments. Therefore, it is helpful to realize only one of the paths in a physical process. Based on first-principles calculations, we show that at suitable activation energies the Nishiyama–Wassermann (N–W) transformation path can be realized without the involvement of the Bain path, since the condition E_NW(θ) < E < E_Bain can be satisfied by pure Fe. E is the activation energy of the system, and E_NW(θ) and E_Bain are the energy barriers for the N–W and Bain transformations, respectively. In particular, the potential energy surface (PES) for the N–W transformation has been calculated as being four-dimensional, i.e., E = E(a,b,c,θ), where (a, b, c) are the lattice constants and θ is the shear angle involved in the shear distortion of the N–W path.

The importance of martensitic transformations has led to tremendous efforts to explore the microscopic martensitic transition paths.     

The role of the donor group and electron-accepting substitutions inserted in π-linkers in tuning the optoelectronic properties of D–π–A dye-sensitized solar cells: a DFT/TDDFT study

The design of low-cost and high-efficiency sensitizers is one of the most important factors in the expansion of dye-sensitized solar cells (DSSCs). To obtain effective sensitizer dyes for applications in dye-sensitized solar cells, a series of metal-free organic dyes with the D–π–A–A arrangement and with different donor and acceptor groups have been designed by using computational methodologies based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT). We have designed JK-POZ(1–3) and JK-PTZ(1–3) D–π–A–A organic dyes by modifying the donor and π-linker units of the JK-201 reference dye. Computational calculations of the structural, photochemical properties and electrochemical properties, as well as the key parameters related to the short-circuit current density and open-circuit voltage, including light-harvesting efficiency (LHE), singlet excited state lifetime (τ), reorganization energies (λ_total), electronic injection-free energy (ΔG^inject) and regeneration driving forces (ΔG^reg) of dyes were calculated and analyzed. Moreover, charge transfer parameters, such as the amount of charge transfer (q^CT), the charge transfer distance (D^CT), and dipole moment changes (μ^CT), were investigated. The results show that ΔG^reg, λ_max, λ_total and τ of JK-POZ-3 and JK-PTZ-3 dyes are superior to those of JK-201, indicating that novel JK-POZ-3 and JK-PTZ-3 dyes could be promising candidates for improving the efficiency of the DSSCs devices.

A series of metal-free organic dyes with the D–π–A–A arrangement and with different donor and acceptor groups have been designed theoretically.     

Preparation of Ag3PO4/α-Fe2O3 hybrid powders and their visible light catalytic performances

The inefficiency of conventional photocatalytic treatment for removing rhodamine B is posing potential risks to ecological environments. Here, we construct a highly efficient photocatalyst consisting of Ag₃PO₄ and α-Fe₂O₃ hybrid powders for the treatment of rhodamine B. Ag₃PO₄ nanoparticles (nanoparticles, about 50 nm) are uniformly dispersed on the surface of α-Fe₂O₃ microcrystals (hexagonal sheet, about 1.5 μm). The Ag₃PO₄-deposited uniformity on the α-Fe₂O₃ surface first increased, then decreased on increasing the hybrid ratio of Ag₃PO₄ to α-Fe₂O₃. When the hybrid ratio of Ag₃PO₄ to α-Fe₂O₃ is 1 : 2, the distribution of Ag₃PO₄ particles on the sheet α-Fe₂O₃ is more uniform with excellent Ag₃PO₄/α-Fe₂O₃ interface performance. The catalytic degradation efficiency of hybrids with the introduction of Ag₃PO₄ nanoparticles on the α-Fe₂O₃ surface reached 95%. More importantly, the hybrid material exhibits superior photocatalytic stability. Ag₃PO₄/α-Fe₂O₃ hybrids have good reusability, and the photocatalytic efficiency could still reach 72% after four reuses. The excellent photocatalytic activity of the as-prepared hybrids can be attributed to the heterostructure between Ag₃PO₄ and α-Fe₂O_3, which can effectively inhibit the photoelectron–hole recombination and broaden the visible light response range.

We construct a highly efficient photocatalyst consisting of Ag₃PO₄ and α-Fe₂O₃ hybrid powders for the treatment of rhodamine B. The catalytic degradation efficiency reached 95% after 10 min.     

Unspecified verticality of Franck–Condon transitions,absorption and emission spectra of cyanine dyes,and a classically inspired approximation

The computed vertical energy, E_v,a/f, from the equilibrium geometry of the initial electronic state is frequently considered as representative of the experimental excitation/emission energy, E_abs/fl = hc/λ_max. Application of the quantum mechanical version of the Franck–Condon principle does not involve precise specification of nuclear positions before, after, or during an electronic transition. Moreover, the duration of an electronic transition is not experimentally accessible in spectra with resolved vibrational structure. It is shown that computed vibronic spectra based on TDDFT methods and application of quantum mechanical FC analysis predict E_abs = hc/λ_max with a 10-fold improvement in accuracy compared to E_v,a for nine cyanine dyes. It is argued that part of the reason for accuracy when this FC analysis is compared to experiment as opposed to E_v,a/f is the unspecified verticality of transitions in the context of the quantum version of the FC principle. Classical FC transitions that preserve nuclear kinetic energy before and after an electronic transition were previously found to occur at a weighted average of final and initial electronic state molecular geometries known as the r-centroid. Inspired by this approach a qualitative method using computed vertical and adiabatic energies and the harmonic approximation is developed and applied yielding a 5-fold improvement in accuracy compared to E_v,a. This improvement results from the dominance of low frequency vibronic transitions in the cyanine dye major band. The model gives insight into the nature of the redshift when qPCR dye EvaGreen is complexed to λDNA and is applicable to the low frequency band of similar non cyanine dyes such as curcumin. It is found that the computed vibronic cyanine dye spectra from time-dependent FC analysis at 0 K and 298 K show decreased intensity at higher temperature suggestive of increased intensity with restricted motion shown when cyanine dyes are used in biomedical imaging. A 2-layer ONIOM model of the DNA minor groove indicates restricted motion of the TC-1 dye excited state in this setting indicative of enhanced fluorescence.

Insight into cyanine dye λ_max from quantum and classical FC principle; high accuracy with classically inspired approach.     

Mechanofluorochromism of (D–π–)2A-type azine-based fluorescent dyes

Bathochromic or hypsochromic shift-type mechanofluorochromism (b-MFC or h-MFC) was found for (D–π–)₂A-type azine-based fluorescent dyes OUY-2, OUK-2, and OUJ-2 possessing intramolecular charge-transfer (ICT) characteristics from two (diphenylamino)carbazole–thiophene units as D (electron-donating group)–π (π-conjugated bridge) moieties to a pyridine, pyrazine, or triazine ring as A (electron-withdrawing group): grinding of the recrystallized dyes induced red or blue shifts of the fluorescent colors, that is, bathochromic or hypsochromic shifts of the fluorescence maximum wavelengths (λ^fl-solid_max). The degrees of MFC evaluated by the absolute value of differences (Δλ^fl-solid_max) in λ^fl-solid_max before and after grinding of the recrystallized dyes increased in the order of OUY-2 (+7 nm) < OUK-2 (−17 nm) < OUJ-2 (+45 nm), so that OUJ-2 exhibits obvious b-MFC, but OUK-2 exhibits h-MFC. X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) demonstrated that the recrystallized dyes were in the crystalline state but the ground dyes were in the amorphous state. When the ground solids were heated above their crystallization temperatures (T_c), the colors and fluorescent colors recovered to the original ones before grinding or converted to other ones, that is, heating the ground solids in the amorphous state induced the recrystallization to recover the original microcrystals or to form other microcrystals due to polymorph transformation. However, (D–π–)₂Ph-type fluorescent dye OTK-2 having a phenyl group as a substitute for the azine rings exhibited non-obvious MFC. Molecular orbital (MO) calculations indicated that the values of the dipole moments (μ_g) in the ground state were 4.0 debye, 1.4 debye, 3.2 debye, and 2.9 debye for OTK-2, OUY-2, OUK-2, and OUJ-2, respectively. Consequently, on the basis of experimental results and MO calculations, we have demonstrated that the MFC of the (D–π–)₂A-type azine-based fluorescent dyes is attributed to reversible switching between the crystalline state of the recrystallized dyes and the amorphous state of the ground dyes with changes in the intermolecular dipole–dipole and π–π interactions before and after grinding. Moreover, this work reveals that (D–π–)₂A fluorescent dyes possessing dipole moments of ca. 3 debye as well as moderate or intense ICT characteristics make it possible to activate the MFC.

Bathochromic or hypsochromic shift-type mechanofluorochromism (b-MFC of h-MFC) was found for (D–π–)₂A-type azine-based fluorescent dyes: grinding of the recrystallized dyes induced bathochromic or hypsochromic shifts of the fluorescence bands.     

Designing triazatruxene-based donor materials with promising photovoltaic parameters for organic solar cells

To address the increasing demand of efficient photovoltaic compounds for modern hi-tech applications, efforts have been made herein to design and explore triazatruxene-based novel donor materials with greater efficiencies. Five new molecules, namely M1–M5, were designed by structural modification of acceptor moiety (rhodanine-3-acetic acid) of well known experimentally synthesized JY05 dye (reference R), and their optoelectronic properties are evaluated to be used as donor molecules in organic solar cells. In these molecules M1–M5, triazatruxene acts as a donor unit and benzene spaced different end-capped moieties including 2-(4-(dicyanomethylene)-2-thioxothiazolidin-3-yl)acetic acid (A1), (E)-2-(4-(1-cyano-2-methoxy-2-oxoethylidene)-2-thioxothiazolidin-3-yl)acetic acid (A2), (Z)-2-(3′-ethyl-4′-oxo-2,2′-dithioxo-3′,4′-dihydro-2′H,5H-[4,5′-bithiazolylidene]-3(2H)-yl)acetic acid (A3), (Z)-2-(4′-(dicyano-methylene)-3′-ethyl-2,2′-dithioxo-3′,4′-dihydro-2′H,5H-[4,5′-bithiazol-ylidene]-3(2H)-yl)acetic acid (A4) and 2-((4Z,4′E)-4′-(1-cyano-2-methoxy-2-oxoethylidene)-3′-ethyl-2,2′-dithioxo-3′,4′-dihydro-2′H,5H-[4,5′-bithiazolylidene]-3(2H)-yl)acetic acid (A5) respectively, as acceptor units. The electronic, photophysical and photovoltaic properties of the designed molecules M1–M5 have been compared with reference molecule R. All designed molecules exhibit reduced energy gap in the region of 1.464–2.008 eV as compared to reference molecule (2.509 eV). Frontier molecular orbital (FMO) surfaces confirm the transfer of charge from donor to acceptor units. All designed molecules M1–M5 exhibited an absorption spectrum in the visible region and they were broader as compared to that of reference R. Especially, M5 with highest λ_max value 649.26 nm and lowest transition energy value 1.90 eV was accredited to the strong electron withdrawing end-capped acceptor moiety A5. The highest value of open circuit voltage (V_oc) 1.02 eV with respect to HOMO_donor–LUMO_BTP-4Cl was shown by M5 among all investigated molecules which was 0.15 V larger than reference molecule R. The designed molecule M5 is proven to be the best candidate for both electron and hole transport mobilities due to its smallest λ_e (0.0212 eV) and λ_h (0.0062 eV) values among all studied molecules.

Five new molecules (M1–M5) were designed by structural modification of acceptor moiety (rhodanine-3-acetic acid) of well-known synthesized dye JY05, and their optoelectronic properties are evaluated to be used as donor molecules in organic solar cells.     

Microstructure–mechanical properties of Ag0/Au0 doped K–Mg–Al–Si–O–F glass-ceramics

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied. The thermal parameters viz., glass transition temperature (T_g) and crystallization temperature (T_c) were extensively changed by varying NPs (in situ or ex situ). Tc was found to be increased (T_c = 870–875 °C) by 90–110 °C when ex situ NPs were present in the glass system. Under controlled heat-treatment at 950 ± 10 °C, the glasses were converted into glass-ceramics with the predominant presence of crystalline phase (XRD) fluorophlogopite mica, [KMg₃(AlSi₃O₁₀)F₂]. Along with the secondary phase enstatite (MgSiO₃), the presence of Ag and Au particles (FCC system) were identified by XRD. A microstructure containing spherical crystallite precipitates (∼50–400 nm) has been observed through FESEM in in situ doped GCs. An ex situ Ag doped GC matrix composed of rock-like and plate-like crystallites mostly of size 1–3 μm ensured its superior machinability. Vicker''s and Knoop microhardness of in situ doped GCs were estimated within the range 4.45–4.61 GPa which is reduced to 4.21–4.34 GPa in the ex situ Ag system. Machinability of GCs was found to be in the order, ex situ Ag > ex situ Au ∼ in situ Ag > in situ Au. Thus, the ex situ Ag/Au doped SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ GC has potential for use as a machinable glass-ceramic.

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied.     

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.     

Mn-based catalysts supported on γ-Al2O3, TiO2 and MCM-41: a comparison for low-temperature NO oxidation with low ratio of O3/NO

Mn-Based catalysts supported on γ-Al₂O₃, TiO₂ and MCM-41 synthesized by an impregnation method were compared to evaluate their NO catalytic oxidation performance with low ratio O₃/NO at low temperature (80–200 °C). Activity tests showed that the participation of O₃ remarkably promoted the NO oxidation. The catalytic oxidation performance of the three catalysts decreased in the following order: Mn/γ-Al₂O₃ > Mn/TiO₂ > Mn/MCM-41, indicating that Mn/γ-Al₂O₃ exhibited the best catalytic activity. In addition, there was a clear synergistic effect between Mn/γ-Al₂O₃ and O₃, followed by Mn/TiO₂ and O₃. The characterization results of XRD, EDS mapping, BET, H₂-TPR, XPS and TG showed that Mn/γ-Al₂O₃ had good manganese dispersion, excellent redox properties, appropriate amounts of coexisting Mn³⁺ and Mn⁴⁺ and abundant chemically adsorbed oxygen, which ensured its good performance. In situ DRIFTS demonstrated the NO adsorption performance on the catalyst surface. As revealed by in situ DRIFTS experiments, the chemically adsorbed oxygen, mainly from the decomposition of O₃, greatly promoted the NO adsorption and the formation of nitrates. The Mn-based catalysts showed stronger adsorption strength than the corresponding pure supports. Due to the abundant adsorption sites provided by pure γ-Al₂O₃, under the interaction of Mn and γ-Al₂O₃, the Mn/γ-Al₂O₃ catalyst exhibited the strongest NO adsorption performance among the three catalysts and produced lots of monodentate nitrates (–O–NO₂) and bidentate nitrates (–O₂NO), which were the vital intermediate species for NO₂ formation. Moreover, the NO–TPD studies also demonstrated that Mn/γ-Al₂O₃ showed the best NO desorption performance among the three catalysts. The good NO adsorption and desorption characteristics of Mn/γ-Al₂O₃ improved its high catalytic activity. In addition, the activity test results also suggested that Mn/γ-Al₂O₃ exhibited good SO₂ tolerance.

The Mn/γ-Al₂O₃ catalyst exhibited excellent performance for NO conversion in the presence of a low ratio of O₃/NO, which was due to the coexistence of Mn³⁺ and Mn⁴⁺ and abundant chemically adsorbed oxygen.     

Copper–cobalt catalysts supported on mechanically mixed HZSM-5 and γ-Al2O3 for higher alcohols synthesis via carbon monoxide hydrogenation

Mechanically mixed γ-Al₂O₃ and HZSM-5 (Si/Al = 50) with different mass ratio were utilized as support for Cu–Co higher alcohol synthesis catalysts prepared through incipient wetness impregnation. The textural and structural properties were studied using Ar low temperature adsorption and desorption, H₂-temperature programmed reduction (H₂-TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) and catalytic performance measurements. The results indicated that the mechanically mixed HZSM-5 and γ-Al₂O₃ supported copper–cobalt catalysts were superior to either γ-Al₂O₃ or HZSM-5 supported ones with the same metal loading. The results revealed that using HZSM-5 and γ-Al₂O₃ mechanically mixed benefited the dispersion of metallic phases and stronger synergetic functions between smaller nanoparticles containing copper and/or cobalt, which is essential for HAS from CO hydrogenation. Under working conditions of P = 5.0 MPa, T = 300 °C, V(H₂) : V(CO) : V(N₂) = 4 : 2 : 1 and GHSV = 7200 mL g⁻¹ h⁻¹, mechanically mixed HZSM-5 and γ-Al₂O₃ supported catalysts showed higher catalytic activity than those over single support. For CuCo catalysts upon support containing 50.0 wt% HZSM-5 and 50.0 wt% γ-Al₂O₃, the CO conversion was 21.3% and the C₂₊ alcohol selectivity was 41.8%.

CuCo bimetallic catalysts over the mixed supports showed smaller average particle size, better dispersion of cobalt and copper species, and good activity for higher alcohols synthesis.     

Ag8SnS6: a new IR solar absorber material with a near optimal bandgap

We report the synthesis and photovoltaic properties of a new ternary solar absorber – Ag₈SnS₆ nanocrystals prepared by successive ionic layer adsorption reaction (SILAR) technique. The synthesized Ag₈SnS₆ nanocrystals have a bandgap E_g of 1.24–1.41 eV as revealed from UV-Vis and external quantum efficiency (EQE) measurements. Its photovoltaic properties were characterized by assembling a liquid-junction Ag₈SnS₆ sensitized solar cell for the first time. The best cell yielded a J_sc of 9.29 mA cm⁻², a V_oc of 0.23 V, an FF of 31.3% and a power conversion efficiency (PCE) of 0.64% under 100% incident light illumination using polysulfide electrolyte and Au counter electrode. The efficiency improved to 1.43% at a reduced light intensity of 10% sun. When the polysulfide was replaced by a cobalt electrolyte with a lower redox level, the V_oc increased to 0.54 V and PCE increased to 2.29% under 0.1 sun, a respectable efficiency for a new solar material. The EQE spectrum covers the spectral range of 300–1000 nm with a maximum EQE of 77% at λ = 600 nm. The near optimal E_g and the respectable photovoltaic performance suggest that Ag₈SnS₆ nanocrystals have potential to be an efficient IR solar absorber.

We report the synthesis and photovoltaic properties of a new ternary solar absorber – Ag₈SnS₆ nanocrystals prepared by successive ionic layer adsorption reaction (SILAR) technique.     

Microstructural analysis,magnetic properties,magnetocaloric effect,and critical behaviors of Ni0.6Cd0.2Cu0.2Fe2O4 ferrites prepared using the sol–gel method under different sintering temperatures

This work focuses on the microstructural analysis, magnetic properties, magnetocaloric effect, and critical exponents of Ni_0.6Cd_0.2Cu_0.2Fe₂O₄ ferrites. These samples, denoted as S1000 and S1200, were prepared using the sol–gel method and sintered separately at 1000 °C and 1200 °C, respectively. XRD patterns confirmed the formation of cubic spinel structures and the Rietveld method was used to estimate the different structural parameters. The higher sintering temperature led to an increased lattice constant (a), crystallite size (D), magnetization (M), Curie temperature (T_C), and magnetic entropy change (−ΔS_M) for samples that exhibited second-order ferromagnetic–paramagnetic (FM–PM) phase transitions. The magnetic entropy changed at an applied magnetic field (μ₀H) of 5 T, reaching maximum values of about 1.57–2.12 J kg⁻¹ K⁻¹, corresponding to relative cooling powers (RCPs) of 115 and 125 J kg⁻¹ for S1000 and S1200, respectively. Critical exponents (β, γ, and δ) for samples around their T_C values were studied by analyzing the M(μ₀H, T) isothermal magnetizations using different techniques and checked by analyzing the −ΔS_Mvs. μ₀H curves. The estimated values of β and γ exponents (using the Kouvel–Fisher method) and δ exponent (from M(T_C, μ₀H) critical isotherms) were β = 0.443 ± 0.003, γ = 1.032 ± 0.001, and δ = 3.311 ± 0.006 for S1000, and β = 0.403 ± 0.008, γ = 1.073 ± 0.016, and δ = 3.650 ± 0.005 for S1200. Obviously, these critical exponents were affected by an increased sintering temperature and their values were different to those predicted by standard theoretical models.

This work focuses on the microstructural analysis, magnetic properties, magnetocaloric effect, and critical exponents of Ni_0.6Cd_0.2Cu_0.2Fe₂O₄ ferrites.     

Naproxen release aspect from boron-doped carbon nanodots as a bifunctional agent in cancer therapy

In this present study, boron–carbon nanodots were synthesized by the hydrothermal method. Boron–carbon nanodots were prepared by varying the concentration ratios of boronic acid and citric acid: 1 : 25, 2 : 1, and 25 : 1, respectively. The precursors were then poured into a Teflon autoclave and heated at 240° for 4 h. This research aims to synthesise and evaluate the potential of boron–carbon nanodots as a bioimaging agent and naproxen delivery carrier. An X-ray diffractogram showed that the boron–carbon nanodots were amorphous. To analyse the functional groups, FTIR and XPS analysis was carried out. Spectrofluorometric analysis (λ_ex 320 nm) showed that the formulation of boron–carbon nanodots 2 : 1 (BCD 2 : 1) has the most ideal fluorescent properties at λ_em 453 nm, whereas UV-vis analysis showed λ_max at 223 nm, with a quantum yield of 52.29%. A confocal laser scanning micrograph and toxicity test (MTT assays) showed that boron–carbon nanodots delivered naproxen efficiently with loading amount and loading efficiency of naproxen 28% and 65%, respectively. Furthermore, it induced an anticancer effect in HeLa cells. This result indicated that boron–carbon nanodots can be used as a bioimaging agent and naproxen delivery carrier.

In this present study, boron–carbon nanodots were synthesized by the hydrothermal method.     

Antiproliferative activity of new pentacyclic triterpene and a saponin from Gladiolus segetum Ker-Gawl corms supported by molecular docking study

A new triterpenoidal saponin identified as 3-O-[β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 4)-β-d-xylopyranosyl]-2β,3β,16α-trihydroxyolean-12-en-23,28-dioic acid-28-O-α-l-rhamnopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 2)-α-l-arabinopyranoside 1 together with a new oleanane triterpene identified as 2β,3β,13α,22α-tetrahydroxy olean-23,28-dioic acid 2 and 6 known compounds (3–8) have been isolated from Gladiolus segetum Ker-Gawl corms. The structural elucidation of the isolated compounds was confirmed using different chemical and spectroscopic methods, including 1D and 2D NMR experiments as well as HR-ESI-MS. Moreover, the in vitro cytotoxic activity of the fractions and that of the isolated compounds 1–8 were investigated against five human cancer cell lines (PC-3, A-549, HePG-2, MCF-7 and HCT-116) using doxorubicin as a reference drug. The results showed that the saponin fraction exhibited potent in vitro cytotoxic activity against the five human cancer cell lines, whereas the maximum activity was exhibited against the PC-3 and A-549 cell lines with the IC₅₀ values of 1.13 and 1.98 μg mL⁻¹, respectively. In addition, compound 1 exhibited potent activity against A-549 and PC-3 with the IC₅₀ values of 2.41 μg mL⁻¹ and 3.45 μg mL⁻¹, respectively. Interestingly, compound 2 showed the maximum activity against PC-3 with an IC₅₀ of 2.01 μg mL⁻¹. These biological results were in harmony with that of the molecular modeling study, which showed that the cytotoxic activity of compound 2 might occur through the inhibition of the HER-2 enzyme.

A new triterpenoidal saponin 1, a new oleanane triterpene 2, and 6 known compounds (3–8) have been isolated from Gladiolus segetum Ker-Gawl corms.