Effect of Nb and Cr incorporation on the structural and magnetic properties of rapidly quenched FeCoSiB microwires

Rapidly quenched microwires with a nominal composition of Fe₃₉Co₃₉Si₈B₁₄ (#A_O), Fe₃₇Co₃₇Nb₄Si₈B₁₄ (#A_N) and Fe₃₆Co₃₆Nb₄Cr₂Si₈B₁₄ (#A_NC) have been investigated. Devitrification of as-quenched microwires showed that crystallization temperatures increased with simultaneous incorporation of Nb and Cr as in #A_NC alloy. Addition of these elements also contributed to an increase in activation energy in #A_N and #A_NC alloys. Nb addition reduced the particle size, which became much finer in the case of the Cr-containing alloy. Although Nb addition did not have much effect on lowering the Curie temperature T_C of the amorphous phase, Cr substitution lowered T_C to 698 K from high values of 785 K and 787 K observed in the #A_O and #A_NC alloys, respectively. However, the Cr addition revealed a better Giant magneto-impedance (GMI) response compared to the other alloys. Such improved GMI properties in the Cr-containing alloy are attributed to lower values of the coercivity and magnetostriction in the alloy containing both Nb and Cr.     

Application of a Multilayer Perceptron Artificial Neural Network for the Prediction and Optimization of the Andrographolide Content in Andrographis paniculata

Andrographolide, the principal secondary metabolite of Andrographis paniculata, displays a wide spectrum of medicinal activities. The content of andrographolide varies significantly in the species collected from different geographical regions. Therefore, this study aims at investigating the role of different abiotic factors and selecting suitable sites for the cultivation of A. paniculata with high andrographolide content using a multilayer perceptron artificial neural network (MLP-ANN) approach. A total of 150 accessions of A. paniculata collected from different regions of Odisha and West Bengal in eastern India showed a variation in andrographolide content in the range of 0.28–5.45% on a dry weight basis. The MLP-ANN was trained using climatic factors and soil nutrients as the input layer and the andrographolide content as the output layer. The best topological ANN architecture, consisting of 14 input neurons, 12 hidden neurons, and 1 output neuron, could predict the andrographolide content with 90% accuracy. The developed ANN model showed good predictive performance with a correlation coefficient (R²) of 0.9716 and a root-mean-square error (RMSE) of 0.18. The global sensitivity analysis revealed nitrogen followed by phosphorus and potassium as the predominant input variables influencing the andrographolide content. The andrographolide content could be increased from 3.38% to 4.90% by optimizing these sensitive factors. The result showed that the ANN approach is reliable for the prediction of suitable sites for the optimum andrographolide yield in A. paniculata.     

Polymeric Nanoformulation of Zoledronic Acid Rescues Osteoblasts from the Harmful Effect of its Native Form: An In Vitro Investigation of Cytotoxic Potential on Osteoblasts and Osteosarcoma Cells

Osteosarcoma (OS) is a malignant tumor, fatal for pediatric patients who do not respond to chemotherapy, alternative therapies and drugs can provide better outcomes. Zoledronic acid (Zol) belonging to the class of bisphosphonates (BPs) has a direct antitumor ability to prevent Ras GTPases modification and stimulate apoptosis. Despite advances in maintaining balance in skeletal events and direct anticancer properties, Zol causes cytotoxicity to normal healthy pre-osteoblast cells, hampering mineralization and differentiation. The study reports the preparation and evaluation of a nanoformulation that can diminish the existing drawbacks of native Zol. The cytotoxic effect is evaluated on bone cancer cells and healthy bone cells with three different cell lines namely, K7M2 (mouse OS cell line), SaOS2 (human OS cell line), and MC3T3E1 (healthy cell counterpart). It is observed that Zol nanoformulation is uptaken more (95%) in K7M2 whereas in MC3T3E1, the percent population internalizing nanoparticles (NPs) is 45%. Zol has a sustained release of 15% after 96 h from the NP which leads to a rescuing effect on the normal pre-osteoblast cells. In conclusion, it can be stated that Zol nanoformulation can be used as a good platform for a sustained release system with minimum side effects to normal bone cells.     

Expedient Access to Enantioenriched 1-Azaspiro Cyclobutanones Enabled by Modified Heyns Rearrangement

Leveraging the unexplored regions of chemical space, the integration of spirocyclic cyclobutane in a molecular scaffold opens up a new vista in modern drug discovery. Despite recent advancements in achieving the synthesis of such motifs, strategies for their asymmetric construction have not been well-recognized and remain a formidable challenge. Herein, for the first time, we have demonstrated a chiral Brønsted acid-catalyzed enantioselective synthesis of 1-azaspiro cyclobutanone enabled by an unusual reactivity of enamine that explore the potentiality of Heyns rearrangement upon electrophilic modification. This design strategy offers viable access to a wide range of cyclobutanone containing spiroindoline and spiropyrrolidine derivatives in good yields with excellent stereoselectivities (up to >99 % ee, >20 : 1 dr). Furthermore, the practicality of this methodology has been shown by a scale-up synthesis of spirocyclic products and their facile post-synthetic modifications.     

Effect of Fluorine Substitution on Absorption and Emission Properties of Figure-eight-shaped [5]Helicene Dimer: A Computational Study at RI-MP2/RI-ADC(2) Level

Chirality is a very important characteristic of optically active molecules and polyaromatics with helical structures, and plays a vital role in various applications in material science. In the present work, we show the effects of fluorine substitution at various positions in a figure-8-shaped [5]helicene dimer on the ground and excited state g-factors. Calculations for the ground and excited states are performed at the MP2 and ADC(2) levels of theory, respectively. The results reveal that fluorination has a large effect on the excited state structures. The values of the excited state dissymmetry factors for the molecules with fluorinations at both ends of the figure-8 systems are smaller than that of the parent system. On the other hand, fluorinations only in the stacked-phenyl region results in an increase in the value of . The perfluorinated system shows the smallest .     

Post-Synthetic Modification of Zr-based Metal-Organic Frameworks with Imidazole: Variable Optical Behavior and Sensing

UiO-66-NH₂-IM, a fluorescent metal-organic framework (MOF), was synthesized by post-synthetic modification of UiO-66-NH₂ with 2-imidazole carboxaldehyde via a Schiff base reaction. It was examined using various characterization techniques (PXRD, FTIR, NMR, SEM, TGA, UV-Vis DRS, and photoluminescence spectroscopy). The emissive feature of UiO-66-NH₂-IM was utilized to detect volatile organic compounds (VOCs), metal ions, and anions, such as acetone, Fe³⁺, and carbonate (CO₃²⁻). Acetone turns off the high luminescence of UiO-66-NH₂-IM in DMSO, with the limit of detection (LOD) being 3.6 ppm. Similarly, Fe³⁺ in an aqueous medium is detected at LOD=0.67 μM (0.04 ppm) via quenching. On the contrary, CO₃²⁻ in an aqueous medium significantly enhances the luminescence of UiO-66-NH₂-IM, which is detected with extremely high sensitivity (LOD=1.16 μM, i. e., 0.07 ppm). Large Stern-Volmer constant, K_sv, and low LOD values indicate excellent sensitivity of the post-synthetic MOF. Experimental data supported by density functional theory (DFT) calculations discern photo-induced electron transfer (PET), resonance energy transfer (RET), inner filter effect (IFE), or proton abstraction as putative sensing mechanisms. NMR and computational studies propose a proton abstraction mechanism for luminescence enhancement with CO₃²⁻. Moreover, the optical behavior of the post-synthetic material toward analytes is recyclable.     

Catalytic Deactivation and Regeneration of Nickel Microparticles in a Home-Built Microchannel-Coupled Millireactor: Substrate Specificity and Multiphase Flow Dependency

Substrate-assisted product desorption often proposed in heterogeneous catalysis (nanozymes) denounces the catalytic deactivation of these catalysts. On the contrary, the catalytic deactivation of rigid heterogeneous catalyst becomes noticeable in a continuous flow reactor. Surprisingly, it has been addressed inadequately and in an isolated manner. In this study, we have developed a cost-effective non-lithographic method for the fabrication of a PDMS-based microchannel-coupled-millreactor. Immobilized nickel particles are resistant to leaching in the flow process. During continuous operation, millireactors show a strong catalytic activity for reduction of resazurin and p-nitrophenol with a conversion rate of almost 100 %. Catalytic poisoning is ubiquitous and gets gradually prominent whereas complete catalytic deactivation of magnetic Ni-microparticles is found to be an instantaneous process. Relatively large-sized resorufin binds predominantly to the surface and thereby blocks the access of the substrate to the Ni-particles. The dissociations of product molecules - resorufin and p-aminophenol are the rate-limiting steps that caused the abrupt deactivation of Ni-microparticle. The kinetic mechanism of heterogeneous derived from the Langmuir-Hinshelwood mechanism satisfactorily explains the catalytic poisoning and deactivation of nickel microparticles. This study sheds light on the intricacies of catalytic activity and poisoning of magnetic nickel microparticles.