Theoretical Study of the Structural Stability, Chemical Reactivity, and Protein Interaction for NMP Compounds as Modulators of the Endocannabinoid System

The cannabinoid receptors (CB1/CB2) and the T-type calcium channels are involved in disorders associated with both physiological pain and depressive behaviors. Valuable pharmacological species carbazole derivatives such as the NMP-4, NMP-7, and NMP-181 (Neuro Molecular Production) regulate both biological entities. In this work, DFT calculations were performed to characterize theoretically their structural and chemical reactivity properties using the BP86/cc-pVTZ level of theory. The molecular orbital contributions and the chemical reactivity analysis reveal that a major participation of the carbazole group is in the donor-acceptor interactions of the NMP compounds. The DFT analysis on the NMP compounds provides insights into the relevant functional groups involved during the ligand-receptor interactions. Molecular docking analysis is used to reveal possible sites of interaction of the NMP compounds with the Cav3.2 calcium channel. The interaction energy values and reported experimental evidence indicate that the site denominated as “Pore-blocking”, which is formed mainly by hydrophobic residues and the T586 residue, is a probable binding site for the NMP compounds.

Synthesis and Characterization of Compounds Based on Carbazole and Sulfone Groups

Two compounds containing carbazole and sulfone groups with different alkyl chain lengths have been designed and synthesized. The sulfone group has strong absorption characteristics and the alkoxy chain and carbazole group are electron-rich, forming D-δ-A-type symmetrical molecules. The molecules have the characteristics of charge transfer and high thermal stability, and the molecules stack to form a layered staggered stack, reducing the intermolecular π–π interactions. The target compounds also exhibit strong ultraviolet-fluorescent emission in the solid state at room temperature, and they are expected to be good luminescent materials.

Influence of Electronic Environment on the Radiative Efficiency of 9-Phenyl-9H-carbazole-Based ortho-Carboranyl Luminophores

The photophysical properties of closo-ortho-carboranyl-based donor–acceptor dyads are known to be affected by the electronic environment of the carborane cage but the influence of the electronic environment of the donor moiety remains unclear. Herein, four 9-phenyl-9H-carbazole-based closo-ortho-carboranyl compounds (1F, 2P, 3M, and 4T), in which an o-carborane cage was appended at the C3-position of a 9-phenyl-9H-carbazole moiety bearing various functional groups, were synthesized and fully characterized using multinuclear nuclear magnetic resonance spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of 1F and 4T were determined by X-ray diffraction crystallography. For all the compounds, the lowest-energy absorption band exhibited a tail extending to 350 nm, attributable to the spin-allowed π–π* transition of the 9-phenyl-9H-carbazole moiety and weak intramolecular charge transfer (ICT) between the o-carborane and the carbazole group. These compounds showed intense yellowish emission (λem = ~540 nm) in rigid states (in tetrahydrofuran (THF) at 77 K and in films), whereas considerably weak emission was observed in THF at 298 K. Theoretical calculations on the first excited states (S1) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the o-carborane. Furthermore, photoluminescence experiments in THF‒water mixtures demonstrated that aggregation-induced emission was responsible for the emission in rigid states. Intriguingly, the quantum yields and radiative decay constants in the film state were gradually enhanced with the increasing electron-donating ability of the substituent on the 9-phenyl group (‒F for 1F < ‒H for 2P < ‒CH3 for 3M < ‒C(CH3)3 for 4T). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9H-carbazole group. Consequently, the efficient ICT-based radiative decay of o-carboranyl compounds can be achieved by appending the o-carborane cage with electron-rich aromatic systems.

Pyridyl-Anchored Type BODIPY Sensitizer-TiO2 Photocatalyst for Enhanced Visible Light-Driven Photocatalytic Hydrogen Production

Dye-sensitized photocatalytic hydrogen production using a boron-dipyrromethene (BODIPY) organic material having a pyridyl group at the anchor site was investigated. Phenyl, carbazole, and phenothiazine derivatives were introduced into BODIPY dyes, and their photocatalytic activities were examined. Identification was performed by nuclear magnetic resonance (NMR), infrared (IR), mass (MS) spectra, and absorption spectra, and catalyst evaluation was performed by using visible-light irradiation and photocatalytic hydrogen production and photocurrent. These dyes have strong absorption at 600–700 nm, suggesting that they are promising as photosensitizers. When the photocatalytic activity was examined, stable catalytic performance was demonstrated, and the activity of the Pt-TiO2 photocatalyst carrying a dye having a carbazole group was 249 μmol/gcat·h. Photocurrent measurements suggest that dye-sensitized photocatalytic activity is occurring. This result suggests that BODIPY organic materials with pyridyl groups as anchor sites are useful as novel dye-sensitized photocatalysts.

Research on Long-Lived Room-Temperature Phosphorescence of Carbazole-Naphthalimide Polylactides

Two types of naphthalimide derivatives were synthesized by introducing a carbazole group and an n-butyl, respectively, into the naphthalimide system. The electron-donating ability of two kinds of derivatives was investigated by the electrochemical method. These two types of derivatives were used as initiators for the polymerization of d and l-lactide polymerization. Here, the emission and UV-vis absorption serve as the main focus. Compared with solely donor-initiated polylactide (PLA), the PLA with a donor-acceptor structure has a more efficient phosphorescence emission, of which the longest phosphorescence lifetime is up to 407 ms. The experimental results reveal the existence of charge-transfer states in the donor-acceptor-ended polymer. Due to the role of charge-transfer states, a red phosphorescent polymer was developed. Theoretically, these desirable advantages render synthesized PLAs a potential candidate for bioimaging and anti-counterfeiting.

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Poly(ethylmethacrylate) with Pendant Carbazole Groups

Carbazole containing polymers have captured the interest of researchers for use in optoelectronics. For an important material to exhibit its optoelectronic properties intrinsic uniformity in the molecular level is required. Thus, a monomer of ethyl methacrylate with pendant carbazole group was synthesized and polymerized via Reversible Addition-Fragmentation Chain Transfer (RAFT) to produce polymers with controlled molecular weight distribution and narrow polydispersity index (PDI). This method of polymerization was compared with that of free radical polymerization by gel permeation chromatography (GPC). The RAFT’s polymerization kinetics was observed to follow a plot of number average molecular weight (Mn) versus % conversion, characteristic of living polymerization. It was also shown to possess polymer chain extension capability. The structure of the monomer and the polymers were characterized by Fourier-Transform Infrared Spectroscopy (FT-IR) and Nuclear Magnetic Resonance (NMR).

Synthesis and characterization of blue light emitting redox-active polyimides bearing a noncoplanar fused carbazole–triphenylamine unit

Photoactive organosoluble polyimides containing a fused triphenylamine–carbazole group were synthesized. These polyimides demonstrated significant potential for optoelectronic devices.

Highly Isotactic Poly(N-butenyl-carbazole): Synthesis, Characterization, and Optical Properties

The synthesis of isotactic poly(N-butenyl-carbazole) (i-PBK) by using homogeneous isospecific Ziegler-Natta catalytic system is reported. The achieved polymer is crystalline and shows, to DSC and X-ray analysis, two distinct crystalline phases.i-PBK FTIR spectrum and X-ray diffraction pattern are compared with those of poly(N-vinylcarbazole) (PVK). The observed differences are tentatively associated with higher flexibility of thei-PBK chains due to the alkylene group connecting the carbazole group to the main chain.i-PBK optical properties are also compared with those of PVK and isotactic poly(N-pentenyl-carbazole) (i-PPK), a higher homologue ofi-PBK recently used as emitting layer in organic light emitting diodes (OLEDs) showing white light emission. The close similarity of the fluorescence spectra ofi-PBK andi-PPK is a promising basis for optical applications of this polymer.