Antimicrobial Activity against Fusarium oxysporum f. sp. dianthi of TiO2/ZnO Thin Films under UV Irradiation: Experimental and Theoretical Study.

We deposited bare TiO2 and TiO2/ZnO thin films to study their antimicrobial capacity against Fusarium oxysporum f. sp. dianthi. The deposit of TiO2 was performed by spin coating and the ZnO thin films were deposited onto the TiO2 surface by plasma-assisted reactive evaporation technique. The characterization of the compounds was carried out by scanning electron microscopy (SEM) and powder X-ray diffraction techniques. Furthermore, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were performed to support the observed experimental results. Thus, the removal of methylene blue (MB) by adsorption and posterior photocatalytic degradation was studied. Adsorption kinetic results showed that TiO2/ZnO thin films were more efficient in MB removal than bare TiO2 thin films, and the pseudo-second-order model was suitable to describe the experimental results for TiO2/ZnO (q e = 12.9 mg/g; k 2 = 0.14 g/mg/min) and TiO2 thin films (q e = 12.0 mg/g; k 2 = 0.13 g/mg/min). Photocatalytic results under UV irradiation showed that TiO2 thin films reached 10.9% of MB photodegradation (k = 1.0 × 10-3 min-1), whereas TiO2/ZnO thin films reached 20.6% of MB photodegradation (k = 3.9 × 10-3 min-1). Both thin films reduced the photocatalytic efficiency by less than 3% after 4 photocatalytic tests. DFT study showed that the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap decreases for the mixed nanoparticle system, showing its increased reactivity. Furthermore, the chemical hardness shows a lower value for the mixed system, whereas the electrophilicity index shows the biggest value, supporting the larger reactivity for the mixed nanoparticle system. Finally, the antimicrobial activity against F. oxysporum f. sp. dianthi showed that bare TiO2 reached a growth reduction of 68% while TiO2/ZnO reached a growth reduction of 90% after 250 min of UV irradiation.

Adsorption properties of M-UiO-66 (M = Zr(IV); Hf(IV) or Ce(IV)) with BDC or PDC linker.

The increasing CO2 emissions and their direct impact on climate change due to the greenhouse effect are environmental issues that must be solved as soon as possible. Metal-organic frameworks (MOFs) are one class of crystalline adsorbent materials that are thought to have enormous potential in CO2 capture applications. In this research, the effect of changing the metal center between Zr(IV), Ce(IV), and Hf(IV), and the linker between BDC and PDC has been fully studied. Thus, the six UiO-66 isoreticular derivatives have been synthesized and characterized by FTIR, PXRD, TGA, and N2 adsorption. We also report the BET surface area, CO2 adsorption capacities, kinetics, and the adsorption isosteric heat (Qst) of the UiO-66 derivatives mentioned family. The CO2 adsorption kinetics were evaluated using pseudo-first order, pseudo-second order, Avrami's kinetic models, and the rate-limiting step with Boyd's film diffusion, interparticle diffusion, and intraparticle diffusion models. The isosteric heats of CO2 adsorption using various MOFs are in the range 20-65 kJ mol-1 observing differences in adsorption capacities between 1.15 and 4.72 mmol g-1 at different temperatures due to the electrostatic interactions between CO2 and extra-framework metal ions. The isosteric heat of adsorption calculation in this report, which accounts for the unexpectedly high heat released from Zr-UiO-66-PDC, is finally represented as an increase in the interaction of CO2 with the PDC linker and an increase in Qst with defects.

Tunable optical properties of isoreticular UiO-67 MOFs for photocatalysis: a theoretical study.

A theoretical study of the reported photocatalytic systems based on Zr-based MOF (UiO-67) with biphenyl-4,4'-dicarboxylic acid (bpdc) and 2,2'-bipyridine-5,5'-dicarboxylic acid (bpydc) as linkers was performed. Quantum chemical calculations were carried out to understand the optical properties of the materials and to facilitate the rational design of new UiO-67 derivatives with potentially improved features as photocatalysts under ambient conditions. Hence, the effect of the structural modifications on the optical properties was studied considering different designs based on the nature of the linkers: in 1 only the bpdc linker was considered, or the mixture 1 : 1 between bpdc and bpydc linkers (labeled as 1A). Also, substituents R, -NH2, and -SH, were included in the 1A MOF only over the bpdc linker (labeled as 1A-bpdc-R) and on both bpdc and bpydc linkers (labeled as 1A-R). Thus a family of six isoreticular UiO-67 derivatives was theoretically characterized using Density Functional Theory (DFT) calculations on the ground singlet (S0) and first excited states (singlet and triplet) using Time-Dependent Density Functional Theory (TD-DFT), multiconfigurational post-Hartree-Fock method via Complete Active Space Self-Consistent Field (CASSCF). In addition, the use of periodic DFT calculations suggest that the energy transfer (ET) channel between bpdc and bpydc linkers might generate more luminescence quenching of 1A when compare to 1. Besides, the results suggest that the 1A-R (R: -SH and NH2) can be used under ambient conditions; however, the ET exhibited by 1A, cannot take place in the same magnitude in these systems. These ET can favor the photocatalytic reduction of a potential metal ion, that can coordinate with the bpydc ligand, via LMCT transition. Consequently, the MOF might be photocatalytically active against molecules of interest (such as H2, N2, CO2, among others) with photo-reduced metal ions. These theoretical results serve as a useful tool to guide experimental efforts in the design of new photocatalytic MOF-based systems.

Reversible Capture Mechanism of CO2 as a Zn(II)-Methylcarbonate.

In this study, we elucidate the reaction mechanism for capturing CO2 with the ZnL1(MeOH) complex (L1=diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazinatopyridine)) in a methanol solution, using density functional theory calculations. One pathway involves the protonation of ZnL1(MeOH) by methylcarbonic acid, followed by ligand exchange of MeOH with MeOCO2 -. An alternative mechanism suggests a tautomerization between ZnL1(MeOH) and Zn(HL1)(OMe), followed by CO2 insertion. The latter pathway is energetically more favorable than the former and more complex than initially proposed. In fact, we unveiled that the solvent catalyzes tautomerization, as one explicit methanol molecule acts as a proton transfer agent. Then, Zn(HL1)(OMe) captures CO2, yielding a methylcarbonate bound to the metal center. The final step involves a rearrangement that leads to the cleavage of the Zn-O(Me)(COO) bond and the formation of a new Zn-O(COOMe) bond, along with the rotation of the methylcarbonate group. We consider an additional mechanism that combines tautomerization and ligand exchange but is endergonic and requires a high activation barrier for the ligand exchange. Furthermore, we evaluate the ligand basicity through the pKa calculated values of the Zn(II) complexes, the effects of varying the ligand from 4-methyl-thiosemicarbazone to 4-ethyl (L2), 4-phenethyl (L3), and 4-benzyl (L4) derivatives, and reversibility of the reaction in an argon environment.

UiO-66(Zr) as drug delivery system for non-steroidal anti-inflammatory drugs.

The toxicity for the human body of non-steroidal anti-inflammatory drugs (NSAIDs) overdoses is a consequence of their low water solubility, high doses, and facile accessibility to the population. New drug delivery systems (DDS) are necessary to overcome the bioavailability and toxicity related to NSAIDs. In this context, UiO-66(Zr) metal-organic framework (MOF) shows high porosity, stability, and load capacity, thus being a promising DDS. However, the adsorption and release capability for different NSAIDs is scarcely described. In this work, the biocompatible UiO-66(Zr) MOF was used to study the adsorption and release conditions of ibuprofen, naproxen, and diclofenac using a theoretical and experimental approximation. DFT results showed that the MOF-drug interaction was due to an intermolecular hydrogen bond between protons of the groups in the defect sites, (µ3 - OH, and - OH2) and a lone pair of oxygen carboxyl functional group of the NSAIDs. Also, the experimental results suggest that the solvent where the drug is dissolved affects the adsorption process. The adsorption kinetics are similar between the drugs, but the maximum load capacity differs for each drug. The release kinetics assay showed a solvent dependence kinetics whose maximum liberation capacity is affected by the interaction between the drug and the material. Finally, the biological assays show that none of the systems studied are cytotoxic for HMVEC. Additionally, the wound healing assay suggests that the UiO-66(Zr) material has potential application on the wound healing process. However, further studies should be done.

Unveiling the electronic and structural consequences of removing two electrons from B12H122.

The notion that a regular icosahedron is unattainable in neutral B12H12 has persisted for nearly 70 years. This is because 24 valence electrons are used for B-H bonds, while another 24 electrons are necessary to maintain the deltahedron, unlike the 26 used in the dianion. According to Wade-Mingos rules, the neutral system should be a deltahedron with a capped face. Nevertheless, our exploration of the potential energy surface of B12H12 reveals that the global minimum is a closed-shell form with an H2 unit attached to a boron vertex of B12H10, preserving the deltahedral boron skeleton.

Adsorption and Photocatalytic Degradation of Methylene Blue on TiO2 Thin Films Impregnated with Anderson-Evans Al-Polyoxometalates: Experimental and DFT Study.

In this work, we fabricated a TiO2 thin film, and the same film was modified with an Anderson aluminum polyoxometalate (TiO2-AlPOM). Physical-chemical characterization of the catalysts showed a significant change in morphological and optical properties of the TiO2 thin films after surface modification. We applied the kinetic and isothermal models to the methylene blue (MB) adsorption process on both catalysts. The pseudo-second order model was the best fitting model for the kinetic results; qe (mg/g) was 11.9 for TiO2 thin films and 14.6 for TiO2-AlPOM thin films, and k2 (g mg-1 min-1) was 16.3 × 10-2 for TiO2 thin films and 28.2 × 10-2 for TiO2-AlPOM thin films. Furthermore, the Freundlich model was suitable to describe the isothermal behavior of TiO2, KF (5.42 mg/g), and 1/n (0.312). The kinetics of photocatalytic degradation was fitted using the Langmuir-Hinshelwood model; kap was 7 × 10-4 min-1 for TiO2 and 13 × 10-4 min-1 for TiO2-AlPOM. The comparative study showed that TiO2 thin films reach a 19.6% MB degradation under UV irradiation and 9.1% MB adsorption, while the TiO2-AlPOM thin films reach a 32.6% MB degradation and 12.2% MB adsorption on their surface. The surface modification improves the morphological, optical, and photocatalytic properties of the thin films. Finally, the DFT study supports all the previously shown results.

Correction: Structure and bonding of molecular stirrers with formula B7M2- and B8M2 (M = Zn, Cd, Hg).

Correction for 'Structure and bonding of molecular stirrers with formula B7M2- and B8M2 (M = Zn, Cd, Hg)' by Rui Yu et al., Phys. Chem. Chem. Phys., 2020, 22, 12312-12320, https://doi.org/10.1039/D0CP01603A.

The ferryl generation by fenton reaction driven by catechol.

The Fenton and Fenton-like reactions are based on the decomposition of hydrogen peroxide catalyzed by Fe(II), primarily producing highly oxidizing hydroxyl radicals (HO∙). While HO∙ is the main oxidizing species in these reactions, Fe(IV) (FeO2+) generation has been reported as one of the primary oxidants. FeO2+ has a longer lifetime than HO∙ and can remove two electrons from a substrate, making it a critical oxidant that may be more efficient than HO∙. It is widely accepted that the preferential generation of HO∙ or FeO2+ in the Fenton reaction depends on factors such as pH and Fe: H2O2 ratio. Reaction mechanisms have been proposed to generate FeO2+, which mainly depend on the radicals generated in the coordination sphere and the HO∙ radicals that diffuse out of the coordination sphere and react with Fe(III). As a result, some mechanisms are dependent on prior HO∙ radical production. Catechol-type ligands can induce and amplify the Fenton reaction by increasing the generation of oxidizing species. Previous studies have focused on the generation of HO∙ radicals in these systems, whereas this study investigates the generation of FeO2+ (using xylidine as a selective substrate). The findings revealed that FeO2+ production is increased compared to the classical Fenton reaction and that FeO2+ generation is mainly due to the reactivity of Fe(III) with HO∙ from outside the coordination sphere. It is proposed that the inhibition of FeO2+ generation via HO∙ generated from inside the coordination sphere is caused by the preferential reaction of HO∙ with semiquinone in the coordination sphere, favoring the formation of quinone and Fe(III) and inhibiting the generation of FeO2+ through this pathway.

Photophysical characterization of tetrahydroxyphenyl porphyrin Zn(II) and V(IV) complexes: experimental and DFT study.

Photodynamic therapy (PDT) is a promising technique for the treatment of various diseases. In this sense, the singlet oxygen quantum yield (Φ∆) is a physical-chemical property that allows to stablish the applicability of a potential photosensitizers (PS) as a drug for PDT. In the herein report, the Φ∆ of three photosensitizers was determined: metal-free tetrahydroxyphenyl porphyrin (THPP), THPP-Zn and the THPP-V metal complexes. Their biological application was also evaluated. Therefore, the in vitro study was carried out to assess their biological activity against Escherichia coli. The metal-porphyrin complexes exhibited highest activities against the bacterial strain Escherichia coli. at the highest concentration (175 µg/mL) and show better activity than the free base ligand (salts and blank solution). Results indicated a relation between Φ∆ and the inhibitory activity against Escherichia coli, thus, whereas higher is the Φ∆, higher is the inhibitory activity. The values of the Φ∆ and the inhibitory activity follows the tendency THPP-Zn > THPP > THPP-V. Furthermore, quantum chemical calculations allowed to gain deep insight into the electronic and optical properties of THPP-Zn macrocycle, which let to verify the most probable energy transfer pathway involved in the singlet oxygen generation.

The quest for a bidirectional auxetic, elastic, and enhanced fracture toughness material: Revisiting the mechanical properties of the BeH2 monolayers.

Herein we show a density functional theory-based study performed on two recently predicted polymorphs of the BeH2 monolayer, α-BeH2 and ß-BeH2 . The α-BeH2 phase possesses an in-plane negative Poisson's ratio (NPR), introducing it into the unique group of auxetic materials. Our assessment delves into the linear-elastic and finite-strain regimes to understand both polymorphs' structural and mechanical responses to deformation. We find that the in-plane NPR is shown to be only parallel to the bonds in α-BeH2 and remains along the uniaxial tensile path. Concomitantly, an out-of-plane transition toward auxetic is also revealed in regions exhibiting conventional Poisson's ratios, making α-BeH2 a bidirectionally auxetic material. While phase transitions in ß-BeH2 are triggered at very short strains, α-BeH2 displays excellent elasticity against tension, superior to that of most currently known 2D materials.

New Polyaniline Derivative with Two Central Ester Groups: Synthesis, Characterization, and Theoretical Study.

A new polyaniline derivative was prepared to study the formation of quinoid-diimine units in its polymer. The monomer and polymer were experimentally and theoretically characterized. Both polymers have one or two electron-withdrawing groups as side substituents. The polymers' quinoid-diimine unit composition is affected by the electron-withdrawing side groups of aniline. The presence of the quinoid-diimine group diminished for the two electron-withdrawing groups of aniline. The polymer conductivity is different than with respect to polyemeraldine, associated with the quinoid-diimine units' composition. The quinoid-diimine composition is strongly increased in the polymer containing one electron-withdrawing group. Moreover, the polymer presented good solubility in organic solvents and moderate thermal stability.

B3Al4+: A Three-Dimensional Molecular Reuleaux Triangle.

We systematically explore the potential energy surface of the B3Al4+ combination of atoms. The putative global minimum corresponds to a structure formed by an Al4 square facing a B3 triangle. Interestingly, the dynamical behavior can be described as a Reuleaux molecular triangle since it involves the rotation of the B3 triangle at the top of the Al4 square. The molecular dynamics simulations, corroborating with the very small rotational barriers of the B3 triangle, show its nearly free rotation on the Al4 ring, confirming the fluxional character of the cluster. Moreover, while the chemical bonding analysis suggests that the multicenter interaction between the two fragments determines its fluxionality, the magnetic response analysis reveals this cluster as a true and fully three-dimensional aromatic system.

Tuning the visible-NIR absorption of azulenocyanine-based photosensitizers.

A new photosensitizer 1-WS55 (dyad) based on two dyes with excellent properties, azulenocyanine (1) and WS55, is proposed at the density functional theory level (M06/def2-SVP). 1 is a dye having a broad NIR absorption (~ 1000 nm), and WS55 is a metal-free organic dye that presents a huge photoelectric conversion efficiency (PCE) of 9.5%. The dyad presents a panchromatic absorption along the UV-Vis-NIR region. It exhibits two intense Q bands (880, 926 nm) in the NIR region, one strong band (672 nm) in the visible region, and several bands in 300-600 nm. Charge transfer bands in the dyad from 1 to WS55 were found in the visible region, which favors the adsorption on an anatase TiO2 surface. The interaction energies dyad (dye)-TiO2 were calculated as a periodic system and corrected by the basis set superposition error. These show better adsorption for the dyad than fragments 1 and WS55. The electron injection calculated from the dye (dyad) to TiO2 suggests an efficient solar energy conversion because of ΔGinj > 0.2 eV. Additionally, calculations performed for the reorganization energy of electrons and holes indicate that the dyad presents the highest charge mobility. In summary, the dyad proposed 1-WS55 constitutes an excellent candidate to be used as a potential photosensitizer for the DSSCs.

Expanding the Knowledge of the Selective-Sensing Mechanism of Nitro Compounds by Luminescent Terbium Metal-Organic Frameworks through Multiconfigurational ab Initio Calculations.

The current research shows that the excited-state dynamics of the antenna ligand, both in the interacting system sensor/analyte and in the sensor without analyte, is a safe tool for elucidating the detection principle of the luminescent lanthanide-based metal-organic framework sensors. In this report the detection principle of the luminescence quenching mechanism in two Tb-based MOFs sensors is elucidated. The first system is a luminescent Tb-MOF [Tb(BTTA)1.5(H2O)4.5]n (H2BTTA = 2,5-bis(1H-1,2,4-triazol-1-yl) terephthalic acid) selective to nitrobenzene (NB), labeled as Tb-1. The second system is {[Tb(DPYT)(BPDC)1/2(NO3)]·H2O}n (DPYT = 2,5-di(pyridin-4-yl) terephthalic acid, BPDC = biphenyl-4,4'-dicarboxylic acid), reported as a selective chemical sensor to nitromethane (NM) in situ, labeled as Tb-2. The luminescence quenching of the MOFs is promoted by intermolecular interactions with the analytes that induce destabilization of the T1 electronic state of the linker "antenna", altering thus the sensitization pathways of the Tb atoms. This study demonstrates the value of host-guest interaction simulations and the rate constants of the radiative and nonradiative processes in understanding and elucidating the sensing mechanism in Ln-MOF sensors.

Influence of LiTaO3 (0001) and KTaO3 (001) Perovskites Structures on the Molecular Adsorption of Styrene and Styrene oxide: A Theoretical Insight by Periodic DFT Calculations.

In this research, the adsorption of styrene and styrene oxide, both biomass derivatives, on KTaO3 (001) and LiTaO3 (0001) perovskite-like structures was studied from a theoretical point of view. The study was carried out using density functional theory (DFT) calculations. The adsorption phenomenon was deeply studied by calculating the adsorption energies (Eads ), adsorbate-surface distances (Å) and evaluating the differences of charge density and charge transfer (ΔCT). For complexes adsorbed on KTaO3 (TaO2 , KO and K(OH)2 exposed layers), the highest Eads was found for styrene oxide, attributed to the oxygen reactivity of the epoxy group describing a strong interaction with the surface. However, when evaluating a K(O)2 model, a more favorable interaction of styrene with the surface is observed, resulting in a high Eads of -9.9 eV and a ΔCT of 3.1e. For LiTaO3 , more favorable interactions are found for both adsorbates compared to KTaO3 , evidenced by the higher adsorption energies and charge density differences, particularly for the styrene complex adsorbed on TaO2 exposed layer (Eads : -10.2 eV). For the LiO termination, the surface exposed oxygens are fundamental for the adsorption of styrene and styrene oxide, leading to a considerable structural distortion. The obtained results thus provide understanding of the structural features, surface reactivity and adsorption sites of LiTaO3 and KTaO3 perovskite in the context of a heterogeneous catalytic process, such as the oxidation of styrene.

Understanding the Deactivating/Activating Mechanisms in Three Optical Chemosensors Based on Crown Ether with Na+ /K+ Selectivity Using Quantum Chemical Tools.

The optical properties and transduction mechanisms in three reported optical chemosensors based on crown ether with selectivity turn-on luminescence toward Na+ over K+ , were investigated using Density Functional Theory/Time-Dependent Density Functional Theory (DFT/TD-DFT). The analysis of the structural stability of the conformers enables us to understand the optical properties of the sensors and their selectivity toward Na+ . The UV-Vis absorption and the radiative channels of the adiabatic S1 excited state were assessed. In these reported sensors, the Photoinduced Electron Transfer (PET) from the nitrogen and the oxygen (O-atoms of the substituted N-phenylaza group) lone pairs to fluorophore groups lead to a nonradiative deactivation process in the fluorophore to p-conjugated anilino-1,2,3-triazol ionophore. This Intramolecular Charge Transfer (ICT) deactivation produced the luminescence quenching in the free sensors and K+ /C1 complexes. The Na+ /sensor interaction produced a Chelation Enhanced Fluorescence (CHEF) due to the inhibition of the PET and ICT, which was confirmed via the calculated oscillator strength of the emission process. The K+ /sensor interaction displayed the possibility of PET in C3; however, this fact was inconclusive to affirm the quenching of luminescence, the CHEF in C2 and C3 and the selectivity toward Na+ over K+ in these systems. For this reason, simulation of the absorption and emissions spectra (calculated oscillator strength), calculation of the kinetic parameters (in charge transfers and radiative deactivations process), analysis of the metal-ligand interaction character, and the analysis of the structural stability of the conformers were determinant factors to understand the selectivity and the optical properties of these chemosensors. The results suggest that these theoretical tools can also be used to predict the optical properties and Na+ /K+ selectivity of optical chemosensors.

Photophysical characterization and in vitro anti-leishmanial effect of 5,10,15,20-tetrakis(4-fluorophenyl) porphyrin and the metal (Zn(II), Sn(IV), Mn(III) and V(IV)) derivatives.

In this report 5 compounds were synthesized and structural and their photophysical characterization was performed (ΦΔ and Φf). Furthermore, in this in vitro study, their biological activity against Leishmania panamensis was evaluated. The photophysical behavior of these compounds was measured and high ΦΔ and low Φf was observed. Besides, DFT quantum calculations on the electronic structures were performed. Finally, the biological activity was determined by means of the compounds capacity to inhibit the viability of parasites using the MTT assay. The inclusion of the metal ions substantially modified the photophysical and biological properties in comparison with the free metal porphyrin (1). In fact, Zn2+ porphyrin derivative (2) showed a marked decrease of Φf and increase of ΦΔ. In this sense, using TDDFT approaches, a luminescent process for Sn4+ derivative (3) was described, where emissive states involve the ML-LCT transition. So, this led to a decrease in the singlet oxygen production (0.82-0.67). Biological results showed that all compounds inhibit the viability of L. panamensis with high efficiency; the decrease in the viability was greater as the concentration of exposure increased. Finally, under light irradiation the IC50 of L. panamensis against the Zn(II)-porphyrin (2) and V(IV)-porphyrin (5) was lower than the IC50 of the Glucantime control (IC50 = 2.2 and 6.95 µM Vs IC50 = 12.7 µM, respectively). We showed that the use of porphyrin and metalloporphyrin-type photosensitizers with exceptional photophysical properties can be successful in photodynamic therapy (PDT) against L. panamensis, being the diamagnetic ion Zn2+ a candidate for the preparation of metalloporphyrins with high singlet oxygen production.

A novel series of pyrazole derivatives toward biological applications: experimental and conceptual DFT characterization.

A new series of 13 pyrazole-derivative compounds with potential antifungal activity were synthetized with good yields. The series have the (E)-2-((1-(R)-3,5-dimethyl-1H-pyrazol-4-yl)diazenyl)phenol general structure and were characterized by means of X-ray diffraction, UV-Vis, FTIR, 1H-NMR, 13C-NMR, and two-dimensional NMR experiments. This experimental characterization was complemented by DFT simulations. A deep insight regarding molecular reactivity was accomplished employing a conceptual DFT approach. In this sense, dual descriptors were calculated at HF and DFT level of theory and GGV spin-density Fukui functions. The main reactive region within the molecules was mapped through isosurface and condensed representations. Finally, chemical descriptors that have previously shown to be close related to biological activity were compared within the series. Thus, higher values of chemical potential ω and electrophilicity χ obtained for compounds 10, 9, 8, 6 and 7, in this order, suggest that these molecules are the better candidates as biological agents.

Organotin Schiff bases as halofluorochromic dyes: green synthesis, chemio-photophysical characterization, DFT, and their fluorescent bioimaging in vitro.

Fluorescent bioimaging is an excellent tool in cellular biology, and it will be a powerful technique in modern medicine as a noninvasive imaging technology where tumoral and normal cells must be distinguished. One of the differences between normal and cancer cells is the intracellular pH. Therefore, the design and synthesis of pH-responsive fluorescent materials are required. Organotin Schiff bases showed halofluorochromic behavior in solution. Microwave-assisted synthesis showed better reaction times and chemical yields compared with conventional heating. All compounds were fully characterized by spectroscopic and spectrometric techniques. The halofluorochromism study showed that some molecules in acidic media have the maximum luminescence intensity due to protonation. All the fluorescent tin complexes showed cell staining on hepatocyte and MCF-7 cells by confocal microscopy. The theoretical study has enabled us to rationalize the optical properties and the halofluorochromism for compounds 1 and 2 synthesized in this work. Our results showed that the emission decrease, in the acid and basic media for compounds 1 and 2, respectively, is caused by intramolecular charge transfer (ICT) deactivation.