Sr2MnO2Na1.6Se2: A Metamagnetic Layered Oxychalcogenide Synthesized by Reductive Na Intercalation to Break [Se2]2- Perselenide Dimer Units.

Recent advances in anion-redox topochemistry have enabled the synthesis of metastable mixed-anion solids. Synthesis of the new transition metal oxychalcogenide Sr2MnO2Na1.6Se2 by topochemical Na intercalation into Sr2MnO2Se2 is reported here. Na intercalation is enabled by the redox activity of [Se2]2- perselenide dimers, where the Se-Se bonds are cleaved and a [Na2-x Se2](2+x)- antifluorite layer is formed. Freshly prepared samples have 16(1) % Na-site vacancies corresponding to a formal oxidation state of Mn of +2.32, a mixed-valence between Mn2+ (d5) and Mn3+ (d4). Samples are highly prone to deintercalation of Na, and over two years, even in an argon glovebox environment, the Na content decreased by 4(1) %, leading to slight oxidation of Mn and a significantly increased long-range ordered moment on the Mn site as measured using neutron powder diffraction. The magnetic structure derived from neutron powder diffraction at 5 K reveals that the compound orders magnetically with ferromagnetic MnO2 sheets coupled antiferromagnetically. The aged sample shows a metamagnetic transition from bulk antiferromagnetic to ferromagnetic behavior in an applied magnetic field of 2 T, in contrast to the Cu analogue, Sr2MnO2Cu1.55Se2, where there is only a hint that such a transition may occur at fields exceeding 7 T. This is presumably due to the higher ionic character of [Na2-x Se2](2+x)- layers compared to [Cu2-x Se2](2+x)- layers, reducing the strength of the antiferromagnetic interactions between MnO2 sheets. Electrochemical Na intercalation into Sr2MnO2Se2 leads to the formation of multiphase sodiated products. The work shows the potential of anion redox to yield novel compounds with intriguing physical properties.

Ultrasound assisted phytochemical extraction of red cabbage by using deep eutectic solvent: Modelling using ANFIS and optimization by genetic algorithms.

The present investigation studied the effect of process parameters on the extraction of phytochemicals from red cabbage by the application of ultrasonication and temperature. The solvent selected for the study was deep eutectic solvent (DES) prepared by choline chloride and citric acid. The ultrasound assisted extraction process was modeled using adaptive neuro-fuzzy inference system (ANFIS) algorithm and integrated with the genetic algorithm for optimization purposes. The independent variables that influenced the responses (total phenolic content, antioxidant activity, total anthocyanin activity, and total flavonoid content) were ultrasonication power, temperature, molar ratio of DES, and water content of DES. Each ANFIS model was formed by the training of three Gaussian-type membership functions (MF) for each input, trained by a hybrid algorithm with 500 epochs and linear type MF for output MF. The ANFIS model predicted each response close to the experimental data which is evident by the statistical parameters (R2>0.953 and RMSE <1.165). The integrated hybrid ANFIS-GA algorithm predicted the optimized condition for the process parameters of ultrasound assisted extraction of phytochemicals from red cabbage was found to be 252.114 W for ultrasonication power, 52.715 °C of temperature, 2.0677:1 of molar ratio of DES and 25.947 % of water content in DES solvent with maximum extraction content of responses, with fitness value 3.352. The relative deviation between the experimental and ANFIS predicted values for total phenolic content, antioxidant activity, total anthocyanin activity, and total flavonoid content was found to be 1.849 %, 3.495 %, 2.801 %, and 4.661 % respectively.

Ultrasound assisted phytochemical extraction of persimmon fruit peel: Integrating ANN modeling and genetic algorithm optimization.

In the present study, ultrasound assisted extraction (UAE) of phytochemicals from persimmon fruit peel (PFP) was modeled using an artificial neural network (ANN) and optimized by integrating with genetic algorithm (GA). The range of process parameters selected for conducting the experiments was ultrasonication power (XU) 150---350 W, extraction temperatures (XT) 30---70 °C, solid to solvent ratio (XS) 1:15---1:35 g/ml, and ethanol concentration (XC) 40---80 %. The range of responses total phenolic content (YP), antioxidant activity (YA), total beta carotenoid (YB) and total flavonoid content (YF) at various independent variables combinations were found to be 7.72---24.62 mg GAE/g d.w., 51.44---85.58 %DPPH inhibition, 24.78---56.56 µg/g d.w. and 0.29---1.97 mg QE/g d.w. respectively. The modelling utilised an ANN architecture with a configuration of 4-12-4. The training process employed the Levenberg-Marquardt method, whereas the activation function chosen for the layers was the log sigmoid. The optimum condition predicted by the hybrid ANN-GA model for the independent variables, XU, XT, XS and XC was found to be 230.18 W, 50.66 °C, 28.27 g/ml, and 62.75 % respectively. The extraction process was carried out for 25 min, with 5-minute intervals, at various temperatures between 30 and 60 °C, to investigate the kinetic and thermodynamic characteristics of the process, under the optimal conditions of XU, XS and XC. The UAE of phytochemicals from persimmon peel followed pseudo second order kinetic model and the extraction process was endothermic in nature.

Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures.

Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr2MnO2Cu1.5Ch2 (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu1.5Ch2]2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr2MnO2Ch2 slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.