Nawee Kungwan

Manipulation of Amorphous‐to‐Crystalline Transformation: Towards the Construction of Covalent Organic Framework Hybrid Microspheres with NIR Photothermal Conversion Ability

An approach to transforming amorphous organic networks into crystalline covalent organic frameworks (COFs) with retention of the colloidal nanosize and uniform morphology is presented. Specifically, Fe3 O4 nanoclusters are encapsulated by a disordering polyimine network via the Schiff-base reaction. The formed imine bonds could be reconstructed under thermodynamic control to reform the polyimine networks into imine-linked COFs in situ. Such a core-shell microsphere exhibits the uniform size and spherical shape, controllable COF shell thickness, accessible surface modification, and improved solution dispersibility as well as maintenance of high surface area, periodic micropores, and superior magnetic responsiveness. Additionally, the photothermal conversion effect is demonstrated for the first time on the nanoCOF layers upon exposure to near infrared light, providing convincing evidence for potential use in phototherapy.

Theoretical investigation of novel carbazole-fluorene based D-π-A conjugated organic dyes as dye-sensitizer in dye-sensitized solar cells (DSCs).

The ground state structure and frontier molecular orbital of newly synthesized carbazole‐fluorene based D‐π‐A organic dyes, CFP1A, CFP2A, CFP1CA, and CFP2CA, were theoretically investigated using density functional theory (DFT) at B3LYP/6‐31G(d,p) level. These dye molecules have been constructed based on carbazole‐fluorene as the electron‐donating moiety while introducing benzene units as π‐spacer connected to different anchor groups, such as acrylic acid and cyanoacrylic acid, as acceptors. The electronic vertical excitation energies and absorption wavelength were carried out using time‐dependent DFT (TD‐DFT). Furthermore, the adsorptions of phenylacrylic acid and phenylcyanoacrylic acid on the TiO2 anatase (101) surface were carried out by means of quantum‐chemical periodic calculations employing periodic PBE functional with DNP basis set. The results promise that anchor dyes with strong withdrawing CN group have easier injected electron to the conduction band of semiconductor implying that CFP1CA and CFP2CA show better performance among four dyes. Additionally, the intramolecular charge transfers (ICT) from electron donor group to anchoring group of CFP1CA and CFP2CA have shown better performance. The calculated results provide the efficiency trend of our new dyes as CFP1CA ≈ CFP2CA > CFP1A ≈ CFP2A which are excellently agree with experimental observation.

Excited-State Intermolecular Proton Transfer Reactions of 7-Azaindole(MeOH)n (n = 1 - 3) Clusters in the Gas phase: On-the-Fly Dynamics Simulation

Ultrafast excited-state intermolecular proton transfer (PT) reactions in 7-azaindole(methanol)(n) (n = 1-3) [7AI(MeOH)(n=1-3)] complexes were performed using dynamics simulations. These complexes were first optimized at the RI-ADC(2)/SVP-SV(P) level in the gas phase. The ground-state structures with the lowest energy were also investigated and presented. On-the-fly dynamics simulations for the first-excited state were employed to investigate reaction mechanisms and time evolution of PT processes. The PT characteristics of the reactions were confirmed by the nonexistence of crossings between S(ππ*) and S(πσ*) states. Excited-state dynamics results for all complexes exhibit excited-state multiple-proton transfer (ESmultiPT) reactions via methanol molecules along an intermolecular hydrogen-bonded network. In particular, the two methanol molecules of a 7AI(MeOH)(2) cluster assist the excited-state triple-proton transfer (ESTPT) reaction effectively with highest probability of PT.

Binding mode and free energy prediction of fisetin/β-cyclodextrin inclusion complexes

Summary In the present study, our aim is to investigate the preferential binding mode and encapsulation of the flavonoid fisetin in the nano-pore of β-cyclodextrin (β-CD) at the molecular level using various theoretical approaches: molecular docking, molecular dynamics (MD) simulations and binding free energy calculations. The molecular docking suggested four possible fisetin orientations in the cavity through its chromone or phenyl ring with two different geometries of fisetin due to the rotatable bond between the two rings. From the multiple MD results, the phenyl ring of fisetin favours its inclusion into the β-CD cavity, whilst less binding or even unbinding preference was observed in the complexes where the larger chromone ring is located in the cavity. All MM- and QM-PBSA/GBSA free energy predictions supported the more stable fisetin/β-CD complex of the bound phenyl ring. Van der Waals interaction is the key force in forming the complexes. In addition, the quantum mechanics calculations with M06-2X/6-31G(d,p) clearly showed that both solvation effect and BSSE correction cannot be neglected for the energy determination of the chosen system.

A 3D‐RISM/RISM study of the oseltamivir binding efficiency with the wild‐type and resistance‐associated mutant forms of the viral influenza B neuraminidase

The binding affinity of oseltamivir to the influenza B neuraminidase and to its variants with three single substitutions, E119G, R152K, and D198N, is investigated by the MM/3D‐RISM method. The binding affinity or the binding free energy of ligand to receptor was found to be determined by a subtle balance of two major contributions that largely cancel out each other: the ligand‐receptor interactions and the dehydration free energy. The theoretical results of the binding affinity of the drug to the mutants reproduced the observed trend in the resistivity, measured by IC50; the high‐level resistance of E119G and R152K, and the low‐level resistance of D198N. For E119G and R152K, reduction of the direct drug‐target interaction, especially at the mutated residue, is the main source of high‐level oseltamivir resistance. This phenomenon, however, is not found in the D198N strain, which is located in the framework of the active‐site.

Theoretical investigation of the charge-transfer properties in different meso-linked zinc porphyrins for highly efficient dye-sensitized solar cells

The charge transfer effect of different meso-substituted linkages on porphyrin analogue 1 (A1, B1 and C1) was theoretically investigated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The calculated geometry parameters and natural bond orbital analysis reveal that the twisted conformation between porphyrin macrocycle and meso-substituted linkages leads to blocking of the conjugation of the conjugated backbone, and the frontier molecular orbital plot shows that the intramolecular charge transfer of A1, B1 and C1 hardly takes place. In an attempt to improve the photoinduced intramolecular charge transfer ability of the meso-linked zinc porphyrin sensitizer, a strong electron-withdrawing group (CN) was introduced into the anchoring group of analogue 1 forming analogue 2 (A2, B2 and C2). The density difference plot of A2, B2 and C2 shows that the charge transfer properties dramatically improved. The electron injection process has been performed using TDDFT; the direct charge-transfer transition in the A2-(TiO2)38 interacting system takes place; our results strongly indicated that introducing electron-withdrawing groups into the acceptor part of porphyrin dyes can fine-tune the effective conjugation length of the π-spacer and improve intramolecular charge transfer properties, consequently inducing the electron injection process from the anchoring group of the porphyrin dye to the (TiO2)38 surface which may improve the conversion efficiency of the DSSCs. Our calculated results can provide valuable information and a promising outlook for computation-aided sensitizer design with anticipated good properties in further experimental synthesis.

Efficient bifunctional materials based on pyrene- and triphenylamine-functionalized dendrimers for electroluminescent devices

To realize highly efficient bifunctional blue-light emitting and hole-transporting materials for OLEDs, a series of pyrene- and triphenylamine-peripheral functionalized carbazole dendrimers, namely G1PYR, G2PYR, G1TPA and G2TPA, were designed, synthesized and characterized. Especially, G2PYR having four pyrene units substituted on the 2nd generation carbazole dendritic scaffold exhibited a strong blue emission with high Tg amorphous and good film-forming properties. Simple structured blue OLED (λEL = 463 nm) using G2PYR as emissive layer and Alq3-based green OLED (λEL = 512 nm) using G2PYR as hole-transporting layer with high luminance efficiencies (η) and low turn-on voltages (Von) of 5.89 cd A−1 and 3.1 V, and 5.15 cd A−1 and 2.6 V were attained, respectively.

Inclusion complexation of pinostrobin with various cyclodextrin derivatives.

Pinostrobin (PNS) is one of the important flavonoids and can be abundantly found in the rhizomes of fingerroot (Boesenbergia rotrunda) and galangal (Alpinia galangal and Alpinia officinarum), the herbal basis of Southeast Asian cooking. Similar to other flavonoids, PNS exhibits anti-oxidative, anti-inflammatory and anti-cancer properties. However, this compound has an extremely low water solubility that limits its use in pharmaceutical applications. Beta-cyclodextrin (βCD) and its derivatives, 2,6-dimethyl-βCD (2,6-DMβCD) and the three hydroxypropyl-βCDs (2-HPβCD, 6-HPβCD and 2,6-DHPβCD), have unique properties that enhance the stability and solubility of such low-soluble guest molecules. In the present study, molecular dynamics simulations were applied to investigate the dynamics and stability of PNS inclusion complexes with βCD and its derivatives (2,6-DMβCD, 2,6-DHPβCD, 2-HPβCD and 6-HPβCD). PNS was able to form complexes with βCD and all four of its derivatives by either the chromone (C-PNS) or phenyl (P-PNS) ring dipping toward the cavity. According to the molecular mechanics-generalized Born surface area binding free energy values, the stability of the different PNS/βCD complexes was ranked as 2,6-DHPβCD>2,6-DMβCD>2-HPβCD>6-HPβCD>βCD. These theoretical results were in good agreement with the stability constants that had been determined by the solubility method.

Physical properties and biological activities of hesperetin and naringenin in complex with methylated β-cyclodextrin

Summary The aim of this work is to improve physical properties and biological activities of the two flavanones hesperetin and naringenin by complexation with β-cyclodextrin (β-CD) and its methylated derivatives (2,6-di-O-methyl-β-cyclodextrin, DM-β-CD and randomly methylated-β-CD, RAMEB). The free energies of inclusion complexes between hesperetin with cyclodextrins (β-CD and DM-β-CD) were theoretically investigated by molecular dynamics simulation. The free energy values obtained suggested a more stable inclusion complex with DM-β-CD. The vdW force is the main guest–host interaction when hesperetin binds with CDs. The phase solubility diagram showed the formation of a soluble complex of AL type, with higher increase in solubility and stability when hesperetin and naringenin were complexed with RAMEB. Solid complexes were prepared by freeze-drying, and the data from differential scanning calorimetry (DSC) confirmed the formation of inclusion complexes. The data obtained by the dissolution method showed that complexation with RAMEB resulted in a better release of both flavanones to aqueous solution. The flavanones-β-CD/DM-β-CD complexes demonstrated a similar or a slight increase in anti-inflammatory activity and cytotoxicity towards three different cancer cell lines. The overall results suggested that solubilities and bioactivities of both flavanones were increased by complexation with methylated β-CDs.

Modification of D-A-π-A configuration toward a high-performance triphenylamine-based sensitizer for dye-sensitized solar cells: A theoretical investigation

In an attempt to shed light on how the addition of a benzothiadiazole (BTD) moiety influences the properties of dyes, a series of newly designed triphenylamine-based sensitizers incorporating a BTD unit as an additional electron-withdrawing group in a specific donor-acceptor-π-acceptor architecture has been investigated. We found that different positions of the BTD unit provided significantly different responses for light absorption. Among these, it was established that the further the BTD unit is away from the donor part, the broader the absorption spectra, which is an observation that can be applied to improve light-harvesting ability. However, when the BTD unit is connected to the anchoring group a faster, unfavorable charge recombination takes place; therefore, a thiophene unit was inserted between these two acceptors, providing redshifted absorption spectra as well as blocking unfavorable charge recombination. The results of our calculations provide valuable information and illustrate the potential benefits of using computation-aided sensitizer design prior to further experimental synthesis.