A magnetic MIP for the selective extraction of buprenorphine (BUP) from real plasma and urine samples and tablets based on computational design as a novel procedure has been developed.

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We show that the time-correlation function formalism can be applied to calculate nonadiabatic electronic population dynamics on the two vibronically coupled diabatic displaced-distorted harmonic potential energy surfaces through conical intersection. We present general formulas for the time-evolved electronic populations at finite temperature with initial sampling from both initial thermal equilibrium and nonequilibrium nuclear distributions. The validity of our formalism is verified through comparison with previous work in a certain limit of our results for case of displaced harmonic oscillator. Finally for illustration, the derived expressions have been applied to determine the electronic population dynamics at conical intersections for SO2 and trans-1,3,5-hexatriene molecules.

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Topological analyses of the electron density using the quantum theory of atoms in molecules (QTAIM) have been carried out at the B3PW91/6-31g (d) theoretical level, on bis(pyrazol-1-yl)methanes derivatives 9-(4-(di (1H-pyrazol-1-yl)-methyl)phenyl)-9H-carbazole (L) and its zinc(II) complexes: ZnLCl2 (1), ZnLBr2 (2) and ZnLI2 (3). The topological parameters derived from Bader theory were also analyzed; these are characteristics of Zn-bond critical points and also of ring critical points. The calculated structural parameters are the frontier molecular orbital energies highest occupied molecular orbital energy (EHOMO), lowest unoccupied molecular orbital energy (ELUMO), hardness (?), softness (S), the absolute electronegativity (?), the electrophilicity index (?) and the fractions of electrons transferred (?N) from ZnLX2 complexes to L. The numerous correlations and dependencies between energy terms of the Symmetry Adapted Perturbation Theory approach (SAPT), geometrical, topological and energetic parameters were detected and described.

Buprenorphine is widely used to aid the cessation of opioids in addicted patients. To the best of our knowledge, there is no selective extraction method for buprenorphine from biological fluids. Here, we describe the synthesis of a molecularly imprinted polymer with the aid of computational design and its application for selective extraction of buprenorphine from plasma and urine. Computational design was used to study intermolecular interactions in the pre-polymerization mixture by the comparison of the binding energy between buprenorphine (template) and functional monomers. The largest interaction energy of template-monomers was obtained at ratio of 1:5 buprenorphine/acrylic acid monomers. Afterwards, the molecularly imprinted polymer was synthesized through precipitation polymerization technique and was employed for selective extraction of buprenorphine. Optimization of various parameters of the molecularly imprinted polymer solid-phase extraction of buprenorphine was carried out by a design of experiment approach using a central composite design and the analyte was determined by employing high-performance liquid chromatography with UV detection. Equilibrium isotherms were studied, and results revealed that the sorption process was in adoption with Langmuir model. Maximum enrichment capacity and Langmuir constant were calculated as 18.2 mg/g and 0.797 L/mg, respectively. Kinetic studies indicated the sorption process followed a pseudo-second-order model.

Four ternary deep eutectic solvents were computationally designed and synthesized, being used as candidate functional monomers in metronidazole molecular imprinting polymer synthesis, allowing selective extraction and determination by ultra high performance liquid chromatography with diode array detection. In terms of metronidazole selective extraction, the best results were obtained by (deep eutectic solvent)2:(ethylene glycol dimethacrylate)11, in which deep eutectic solvent is the functional monomer constructed by combining three components in 6:6:2 ratios of choline chloride:ethylene glycol:methacrylic acid. The effects of different parameters on molecular imprinted solid‐phase extraction of metronidazole were thoroughly explored through screening design and response surface methodology. The adsorption mechanism findings show that the adsorption data are primarily fitted on the Freundlich model based on higher correlation coefficient. Kinetic experiments have shown that the mechanism of adsorption fits the pseudo‐second‐order model. The best extraction recovery (96.5%) was obtained in 25‐min elution time, desorption temperature of 40°C, and 1.0 mL ACN as eluent. Metronidazole was measured by a validated ultra high performance liquid chromatography with diode array detection method. The calibration of the method was linear in the range of 0.1–10 μg/mL with limits of detection and quantification of 0.03 and 0.1 μg/mL, respectively. The method was successfully applied for the determination of metronidazole in human plasma.

MIP-APTES-MNP was designed and characterized to selectively extract OPPs from plasma samples.