Synthesis and characterization of Mg-hydroxyapatite and its cellulose hybridized structure as enhanced bio-carrier of oxaliplatin drug; equilibrium and release kinetics.

An advanced form of magnesium-doped hydroxyapatite (Mg HAP) was synthesized and hybridized with cellulose fibers, producing a safe biocomposite (CF/Mg HAP) as an enhanced delivery structure of traditional oxaliplatin (OXPN) chemotherapy drug during the treatment stages of colorectal cancer. The qualifications of CF/Mg HAP as a carrier for OXPN were followed based on loading, release, and cytotoxicity as compared to Mg HAP. The CF/Mg HAP composite exhibits a notably higher OXPN encapsulation capacity (256.2 mg g-1) than the Mg HAP phase (148.9 mg g-1). The OXPN encapsulation process into CF/Mg HAP displays the isotherm behavior of the Langmuir model (R2 = 0.99) and the kinetic assumptions of pseudo-first-order kinetics (R2 > 0.95). The steric studies reflect a strong increment in the quantities of the free sites after the cellulose hybridization steps (Nm = 178.58 mg g-1) as compared to pure Mg HAP (Nm = 69.39 mg g-1). Also, the capacity of each site was enhanced to be loaded by 2 OXPN molecules (n = 1.43) in a vertical orientation. The OXPN encapsulation energy into CF/Mg HAP (<40 kJ mol-1) reflects physical encapsulation reactions involving van der Waals forces and hydrogen bonding. The OXPN release profiles of CF/Mg HAP exhibit slow and controlled properties for about 100 h, either at pH 5.5 or pH 7.4. The release kinetics and diffusion exponent (>0.45) signify non-Fickian transport and a complex erosion/diffusion release mechanism. The free CF/Mg HAP particles display a considerable cytotoxic effect on the HCT-116 cancer cells (21.82% cell viability), and their OXPN-loaded product shows a strong cytotoxic effect (1.85% cell viability).

Designing Efficient Metal-Free Dye-Sensitized Solar Cells: A Detailed Computational Study.

The modulation of molecular characteristics in metal-free organic dyes holds significant importance in dye-sensitized solar cells (DSSCs). The D-π-A molecular design, based on the furan moiety (π) in the conjugated spacer between the arylamine (D) and the 2-cyanoacrylic acid (A), was developed and theoretically evaluated for its potential application in DSSCs. Utilizing linear response time-dependent density functional theory (TDDFT) with the CAM-B3LYP functional, different donor and acceptor groups were characterized in terms of the electronic absorption properties of these dyes. All the studied dye sensitizers demonstrate the ability to inject electrons into the semiconductor's conduction band (TiO2) and undergo regeneration through the redox potential triiodide/iodide (I3-/I-) electrode. TDDFT results indicate that the dyes with CSSH anchoring groups exhibit improved optoelectronic properties compared to other dyes. Further, the photophysical properties of all dyes absorbed on a Ti(OH)4 model were explored and reported. The observed results indicate that bidentate chemisorption occurs between dyes and TiO4H5. Furthermore, the HOMO-LUMO energy gaps for almost all dye complexes are significantly smaller than those of the free dyes. This decrease of the HOMO-LUMO energy gaps in the dye complexes facilitates electron excitation, and thus more photons can be adsorbed, guaranteeing larger values of efficiency and short-circuit current density.

Efficient D-π-π-A-Type Dye Sensitizer Based on a Benzothiadiazole Moiety: A Computational Study.

The design of highly efficient sensitizers is one of the most significant areas in dye-sensitized solar cell (DSSC) research. We studied a series of benzothiadiazole-based D-π-π-A organic dyes, putting emphasis on the influence of the donor moiety on the DSSC's efficiency. Using (linear-response time-dependent) density functional theory ((TD)DFT)) with the CAM-B3LYP functional, different donor groups were characterized in terms of electronic absorption spectra and key photovoltaic parameters. As a reference, a dye was considered that had a benzothiadiazole fragment linked via thiophene rings to a diphenylamine donor and a cyanoacrylic-acid acceptor. The different systems were first studied in terms of individual performance parameters, which eventually aggregated into power conversion efficiency. Only the amino-substituted species showed a modest increase, whereas the dimethylamino case showed a decrease.

Synthesis and Characterization of Iron-Rich Glauconite Nanorods by a Facile Sonochemical Method for Instantaneous and Eco-friendly Elimination of Malachite Green Dye from Aquatic Environments.

Novel glauconite nanorods (GNRs) were synthesized by the sonication-induced chemical expansion and scrolling process of natural glauconite. The synthetic nanostructure was characterized by different analytical techniques as a superior adsorbent for the malachite green dye (MG). The synthetic GNRs were detected as porous nanorods with an average length of 150 nm to 5 µm, an average diameter of 25 to 200 nm, and a specific surface area of 123.7 m2/g. As an adsorbent for MG, the synthetic GNRs showed superior uptake capacity up to 1265.6 mg/g at the saturation stage, which is higher than most of the recently developed highly adsorbent dyes. The adsorption behavior and mechanistic properties were depicted by using modern and traditional equilibrium modeling. The kinetic assumption of the pseudo-first-order model (R2 > 0.94) and the classic isotherm of the Langmuir equilibrium model (R2 > 0.97) were used to describe the adsorption reactions. The steric investigation demonstrates that each active site on the surface of GNRs can adsorb up to three MG molecules (n = 2.19-2.48) in vertical orientation involving multimolecular mechanisms. Also, the determined active site density (577.89 mg/g) demonstrates the enrichment of the surface of GNRs with numerous adsorption receptors with strong affinity for the MG dye. The energetic study, including Gaussian energy (6.27-7.97 kJ/mol) and adsorption energy (9.45-10.43 kJ/mol), revealed that GNRs had physically adsorbed the dye, which might involve electrostatic attraction, hydrogen bonding, van der Waals forces, and dipole forces. The internal energy, enthalpy, and entropy determined the exothermic and spontaneous uptake of MG.

Experimental and Molecular Modeling Studies on the Complexation of Chromium(III) with the Angiotensin-Converting Enzyme Inhibitor Captopril.

Captopril (CPT) is an inhibitor of angiotensin I converting enzyme, used as a medication for the treatment of people with high blood pressure, renal insufficiency, and cardiovascular diseases. It inhibits the angiogenesis process, vasoconstriction, and tumor metastasis. Some metal-captopril complexes exhibit antimicrobial activities. In the current work, the formation of the CrIII-CPT complex was studied spectrophotometrically and potentiometrically in aqueous solution. Kinetics of CrIII-CPT complex formation was spectrophotometrically studied over the pH range 3.20-4.20, at an ionic strength of 0.3 M at 30-50 °C. CrIII-CPT complex formation was potentiometrically studied at 25 °C, where ligand protonation constants and complexes' overall stability constants were calculated. UV-vis absorption spectra were executed to confirm the complex formation. Density functional theory and molecular dynamics simulation were performed to search the geometries of the CrIII-CPT complex. Atoms in molecules and interaction region indicator calculations are used to investigate intermolecular interactions for the formation of CrIII-CPT complex. The antimicrobial activity of the CPT ligand and CrIII-CPT complex on the prevention and control of environmental pathogenic bacteria, as tested on both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative bacteria Escherichia coli (E. coli) via agar disc diffusion method, assess the ability to use as an antimicrobial agent. CPT had shown good antimicrobial activity against both types of bacteria, which had increased slightly the zone of inhibition in Cr-CPT that indicates the increased efficacy due to Cr(III) antimicrobial activity via its oxidative damage to the bacterial cell wall. No previous study tested the CPT antimicrobial activity against Gram-positive ones such as S. aureus.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate.

BACKGROUND: In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. RESULTS: The results have shown that the reaction is first order with respect to both [IO4(-)] and the complex concentration, and the rate increases over the pH range 2.62 - 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 x 10(-3) s(-1)), is greater than the value of k1 (1.22 x 10(-3) s(-1)) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0 degrees C and I = 0.20 mol dm(-3). It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4(-) to chromium(III). CONCLUSION: The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between DeltaH* and DeltaS* values for these reactions.