Photocatalytic degradation of antibiotic sulfamethizole by visible light activated perovskite LaZnO3.

In this work, the perovskite LaZnO3 was synthesized via sol-gel method and applied for photocatalytic treatment of sulfamethizole (SMZ) antibiotics under visible light activation. SMZ was almost completely degraded (99.2% ± 0.3%) within 4 hr by photocatalyst LaZnO3 at the optimal dosage of 1.1 g/L, with a mineralization proportion of 58.7% ± 0.4%. The efficient performance of LaZnO3 can be attributed to its wide-range light absorption and the appropriate energy band edge levels, which facilitate the formation of active agents such as ·O2-, h+, and ·OH. The integration of RP-HPLC/Q-TOF-MS and DFT-based computational techniques revealed three degradation pathways of SMZ, which were initiated by the deamination reaction at the aniline ring, the breakdown of the sulfonamide moieties, and a process known as Smile-type rearrangement and SO2 intrusion. Corresponding toxicity of SMZ and the intermediates were analyzed by quantitative structure activity relationship (QSAR), indicating the effectiveness of LaZnO3-based photocatalysis in preventing secondary pollution of the intermediates to the ecosystem during the degradation process. The visible-light-activated photocatalyst LaZnO3 exhibited efficient performance in the occurrence of inorganic anions and maintained high durability across multiple recycling tests, making it a promising candidate for practical antibiotic treatment.

Boron Silicon B2Si3q and B3Si2p Clusters: The Smallest Aromatic Ribbons.

The small binary boron silicon clusters B2Si3q with q going from -2 to +2 and B3Si2p with p varying from -3 to +1 were reinvestigated using quantum chemical methods. The thermodynamic stability of these smallest ribbon structures is governed by both Hückel and ribbon models for aromaticity. The more negative the cluster charge, the more ribbon character is shown. In contrast, the more positive the charge state, the more pronounced the Hückel character becomes. The ribbon aromaticity character can also be classified into ribbon aromatic, semiaromatic, antiaromatic, and triplet aromatic when the electron configuration of a ribbon structure is described as [...π2(n+1)σ2n], [...π2n+1σ2n], [...π2nσ2n], and [...π2n+1σ2n-1], respectively. Geometry optimizations of the B2Si3 lowest-energy structure by some density functional theory (DFT) functionals result in a nonplanar shape because it possesses an antiaromatic ribbon character. However, its π aromaticity assigned by the Hückel rule is stronger in such a way that several other DFT and coupled-cluster theory CCSD(T) calculations show that B2Si3 is indeed stable in a planar form (Cs). A new global equilibrium structure for the anion B2Si32-, which is a ribbon semiaromatic species, was identified. Some benchmark tests were also carried out to evaluate the performance of popular methods for the treatment of binary B-Si clusters. At odds with some previous studies, we found that with reference to the high accuracy CCSD(T)/CBS method, the hybrid TPSSh functional is reliable for a structure search, whereas the hybrid B3LYP functional is more suitable for simulations of some experimental spectroscopic results.

Experimental and theoretical studies on the synthesis of 1,4,5-trisubstituted pyrrolidine-2,3-diones.

Substituted 4-acetyl-3-hydroxy-3-pyrroline-2-ones have been prepared via three-component reactions and the tautomerism of these 3-pyrroline-2-ones is due to the slight difference of energy, and the significantly large rate constant of transformation between two tautomers. 1,4,5-Trisubstituted pyrrolidine-2,3-dione derivatives were prepared from the above mentioned 2-pyrrolidinone derivatives and aliphatic amines, which exist in enamine form and are stabilized by an intramolecular hydrogen bond. A possible reaction mechanism between 3-pyrroline-2-one and aliphatic amine (CH3NH2) was proposed based on computational results and the main product is formed favorably following the PES via the lowest ΔG # pathway in both the gas-phase and an ethanol solvent model. DFT calculations showed that kinetic selectivity is more significant than thermodynamic selectivity for forming main products.

SERS Chemical Enhancement of 2,4,5-Trichlorophenoxyacetic Acid Adsorbed on Silver Substrate.

Surface-enhanced Raman spectroscopy (SERS) was employed to gain an understanding of the chemical enhancement mechanism of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), an Agent Orange, adsorbed on a silver substrate surface. Experimental measurements were performed using a micro-Raman spectrophotometer with an excitation wavelength of 532 nm and successfully detected 2,4,5-T at a relatively low concentration of 0.4 nM. Density functional theory (DFT) calculations on the interactions of the 2,4,5-T molecule with some small silver clusters, Agn with n = 4, 8, and 20, as well as with extended Ag surfaces, demonstrate that the most stable adsorption configuration is formed via coordination of Cl9 sites and carbonyl C═O group on the 2,4,5-T ligand to the Ag atoms on surfaces. Analyses of charge transfer mechanism and frontier orbitals distributions show an electron transfer from 2,4,5-T to the cluster in the ground state, and an inversed trend occurs for the excited singlet state process, consequently leading to a chemical enhancement of SERS signals. The obtained results are of importance for subsequent work in guiding the design of mobile sensors specifically used for services of rapid screening and detection of these toxic compounds present in the environment, as well as agricultural and food products. Extensive computations pointed out that small silver clusters, in particular of Ag20 size, can be used as appropriate models for a metal nanoparticle surface.

Characteristics of nonconventional hydrogen bonds and stability of dimers of chalcogenoaldehyde derivatives: a noticeable role of oxygen compared to other chalcogens.

In this work, twenty-four stable dimers of RCHZ with R = H, F, Cl, Br, CH3 or NH2 and Z = O, S, Se or Te were determined. It was found that the stability of most dimers is primarily contributed by the electrostatic force, except for the dominant role of the induction term in those involving a Te atom, which has been rarely observed. Both electron-donating and -withdrawing groups in substituted formaldehyde cause an increase in the strength of nonconventional Csp2-H⋯Z hydrogen bonds, as well as the dimers, in which the electron donating effect plays a more crucial role. The strength of nonconventional hydrogen bonds decreases in the following order: Csp2-H⋯O ≫ Csp2-H⋯S > Csp2-H⋯Se > Csp2-H⋯Te. Remarkably, a highly significant role of the O atom compared to S, Se and Te in increasing the Csp2-H stretching frequency and strength of the nonconventional hydrogen bonds and dimers is found. A Csp2-H stretching frequency red-shift is observed in Csp2-H⋯S/Se/Te, while a blue-shift is obtained in Csp2-H⋯O. When Z changes from O to S to Se and to Te, the Csp2-H blue-shift tends to decrease and eventually turns to a red-shift, in agreement with the increasing order of the proton affinity at Z in the isolated monomer. The magnitude of the Csp2-H stretching frequency red-shift is larger for Csp2-H⋯Te than Csp2-H⋯S/Se, consistent with the rising trend of proton affinity at the Z site and the polarity of the Csp2-H bond in the substituted chalcogenoaldehydes. The Csp2-H blue-shifting of the Csp2-H⋯O hydrogen bonds is observed in all dimers regardless of the electron effect of the substituents. Following complexation, the electron-donating derivatives exhibit a stronger Csp2-H blue-shift compared to the electron-withdrawing ones. Notably, the stronger Csp2-H blue-shift turns out to involve a less polarized Csp2-H bond and a decrease in the occupation at the σ*(Csp2-H) antibonding orbital in the isolated monomer.

Role of O-H⋯O/S conventional hydrogen bonds in considerable Csp2 -H blue-shift in the binary systems of acetaldehyde and thioacetaldehyde with substituted carboxylic and thiocarboxylic acids.

Stable binary complexes of RCZOH⋯CH3CHZ (R = CH3, H, F; Z = O, S) are due to contributions from the O-H⋯O/S and Csp2 -H⋯O/S hydrogen bonds. The strength of Csp2 /O-H⋯O is 1.5 to 2 times greater than that of the Csp2 /O-H⋯S bond. The substitution of H(Csp2 ) of HCZOH by CH3 causes a decrease in complex stability, while the opposite trend occurs for the F atom. A very large red shift of the O-H stretching frequency in O-H⋯O/S bonds was observed. A surprising Csp2 -H blue shift up to 104.5 cm-1 was observed for the first time. It is found that the presence of O-H⋯O/S hydrogen bonds and a decisive role of intramolecular hyperconjugation interactions in the complex cause a significant blue shift of the Csp2 -H covalent bonds. A striking role of O compared to the S atom in determining the blue shift of Csp2 -H stretching vibration and stability of binary complexes is proposed. The obtained results show that the ratio of deprotonation enthalpy and proton affinity could be considered as an index for the classification of the non-conventional hydrogen bond. SAPT2+ results show that the strength of RCSOH⋯CH3CHS complexes is dominated by electrostatic and induction energies, while a larger contribution to the stability of remaining complexes is detected for the electrostatic component.