Search Results (361)

In the present study, two novel donor–acceptor (D–A) conjugated copolymers, PIDTBDI and PIDTTBDI, were successfully synthesized via Stille coupling polymerization. These alternating copolymers incorporate indacenodithiophene and indacenodithienothiophene as donor units, coupled with benzothiadiazole dicarboxylic imide as the electron-deficient acceptor unit. The influence of extended conjugation on the structural, optical, thermal, and electrochemical properties of the copolymers was systematically investigated and confirmed by density functional theory (DFT). XRD analysis confirmed that both polymers are amorphous. Thermogravimetric analysis revealed that both materials possess excellent thermal stability, with decomposition temperatures exceeding 270 °C. The theoretical and experimental values of the energy gap confirmed the thermal stability of the studied polymers. The molecular weight was determined to be 10,673 Da for PIDTBDI and 7149 Da for PIDTTBDI. Despite the variation in molecular weight, both copolymers exhibited comparable optical and electrochemical bandgaps of approximately 1.57 and 1.69 eV, respectively. Electrochemical measurements showed that PIDTBDI has a HOMO energy level of −5.30 eV and a LUMO level of −3.61 eV, while PIDTTBDI displays HOMO and LUMO levels of −5.28 eV and −3.59 eV, respectively. These results indicate that minor structural differences can considerably affect the electronic characteristics of the polymers, thus altering their overall efficacy in solar cell applications. Full article

In this study, we synthesized novel donor–π–acceptor (D–π–A) functional dyes bearing a carbonyl-bridged bithiophene as a π-conjugated spacer and evaluated the absorption and fluorescence properties as well as the photostability. The developed dyes 1-CO–3-CO possess an N,N-diphenylaminophenyl electron donor unit and an electron acceptor unit such as a formyl group (1-CO), an (N,N-diethylthiobarbituryl)methylene moiety (2-CO), or a (3-dicyanomethylidene-1-indanon-2-yl)methylene moiety (3-CO). The absorption spectra of 1-CO–3-CO in dichloromethane at room temperature showed absorption maxima at 569 nm, 631 nm, and 667 nm, respectively, and the stronger acceptors in 2-CO and 3-CO led to enhancement of the ICT character. In addition, 2-CO and 3-CO had a second absorption band in the visible region, showing panchromatic absorption properties. Electrochemical analyses of the developed dyes revealed that the carbonyl bridging group in the π-spacer contributes to stabilization of the frontier orbitals such as the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively), in comparison with the referential dyes bearing a dibutylmethylene-bridged bithiophene spacer, 1-CBu₂–3-CBu₂. The HOMO/LUMO stabilization brought about high photostability in the doped poly(methyl methacrylate) film. Full article

Covalent organic frameworks (COFs) have emerged as unique catalysts for photocatalysis; however, the relationship between their building block units and optoelectronic properties remains elusive. Herein, we explored the influence of building blocks on the optoelectronic properties of benzotrithiophene-based COFs (BTT-COFs) using density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The calculation results suggested that three critical factors—the conjugated structure, planarity, and the introduction of nitrogen heteroatoms—significantly influenced charge separation and transfer within BTT-COFs. Structure–property relationships were established through several critical quantitative parameters, such as Sr, t, and CT. Among seven BTT-COFs, BTT-Tpa (Tpa: 4,4′,4″-triaminotriphenylamine) exhibited the most efficient charge separation and the highest charge transfer capability due to the electronegativity of triphenylamine, the delocalization of its lone pair electrons, and its unique star-shaped configuration. These theoretical results will provide an essential foundation for selecting donor–acceptor units in the design of novel COF materials for photocatalytic reaction applications. Full article

Spondylocostal dysostosis (SCDO) is a group of rare genetic disorders characterized by segmental vertebral defects and rib deformities due to congenital misalignment, fusion, or reduction in the number of ribs. The causes of the disease have been found in seven genes, including DLL3 (SCDO1, OMIM 602768), MESP2 (SCDO2, OMIM 608681), LFNG (SCDO3, OMIM 609813), HES7 (SCDO4, OMIM 608059), TBX6 (SCDO5, OMIM 602427), RIPPLY2 (SCDO6, OMIM 616566), and DLL1 (SCDO7). Among these, SCDO4, characterized by a short trunk, short neck, and mild nonprogressive scoliosis, is a rare form of reported cases. SCDO4 is identified as caused by homozygous or compound heterozygous variants in the HES7 gene (NM_001165967.2; NP_001159439.1). This study reports a novel homozygous HES7 splice variant (c.43-9T>A) detected in an SCDO4 patient by whole-exome sequencing and confirmed by Sanger sequencing. This variant was evaluated as an acceptor loss variant in intron 1 in the HES7 transcript by in silico analysis and was inherited from the patient’s parent. This study also reviews previous reports to provide a comprehensive overview of SCDO and help us to understand the pathogenesis to develop future treatment strategies. Full article

The novel benzanthrone derivative, 2-bromo-3-aminobenzo[de]anthracene-7-one (2-Br-3-NH₂BA), was synthesized and extensively characterized to investigate its photophysical behavior in various solvents. It was prepared through selective bromination of 3-aminobenzanthrone using N-bromosuccinimide in dimethylformamide at −20 °C. Featuring a donor–π–acceptor (D–π–A) structure, 2-Br-3-NH₂BA exhibits pronounced solvatochromism due to the intramolecular charge transfer (ICT) between the amino donor and the carbonyl acceptor groups. Optical measurements conducted in eight solvents of varying polarity revealed a significant bathochromic shift in both absorption and fluorescence emission, with emission maxima red-shifting by over 110 nm from non-polar to polar environments. Corresponding reductions in the optical band gap energies, as calculated from Tauc plots, further support solvent-induced electronic state modulation. Additionally, quantum yield analysis showed higher fluorescence efficiency in non-polar solvents, while polar solvents induced twisted intramolecular charge transfer (TICT), leading to emission quenching. These findings demonstrate the sensitivity of 2-Br-3-NH₂BA to environmental polarity, making it a promising candidate for color-tunable luminescent applications in optoelectronics and sensing. However, further studies in the solid state are required to validate its applicability in device architectures such as OLEDs. Full article

4H-silicon carbide (4H-SiC) is a cornerstone for next-generation optoelectronic and power devices owing to its unparalleled thermal, electrical, and optical properties. However, its chemical inertness and low dopant diffusivity for most dopants have historically impeded effective doping. This study unveils a transformative laser-assisted boron doping technique for n-type 4H-SiC, employing a pulsed Nd:YAG laser (λ = 1064 nm) with a liquid-phase boron precursor. By leveraging a heat-transfer model to optimize laser process parameters, we achieved dopant incorporation while preserving the crystalline integrity of the substrate. A novel optical characterization framework was developed to probe laser-induced alterations in the optical constants—refraction index ($\mathrm{n}$) and attenuation index ($\mathrm{k}$)—across the MIDIR spectrum (λ = 3–5 µm). The optical properties pre- and post-laser doping were measured using Fourier-transform infrared spectrometry, and the corresponding complex refraction indices were extracted by solving a coupled system of nonlinear equations derived from single- and multi-layer absorption models. These models accounted for the angular dependence in the incident beam, enabling a more accurate determination of $\mathrm{n}$ and $\mathrm{k}$ values than conventional normal-incidence methods. Our findings indicate the formation of a boron-acceptor energy level at 0.29 eV above the 4H-SiC valence band, which corresponds to λ = 4.3 µm. This impurity level modulated the optical response of 4H-SiC, revealing a reduction in the refraction index from 2.857 (as-received) to 2.485 (doped) at λ = 4.3 µm. Structural characterization using Raman spectroscopy confirmed the retention of crystalline integrity post-doping, while secondary ion mass spectrometry exhibited a peak boron concentration of 1.29 × 10¹⁹ cm⁻³ and a junction depth of 450 nm. The laser-fabricated p–n junction diode demonstrated a reverse-breakdown voltage of 1668 V. These results validate the efficacy of laser doping in enabling MIDIR tunability through optical modulation and functional device fabrication in 4H-SiC. The absorption models and doping methodology together offer a comprehensive platform for paving the way for transformative advances in optoelectronics and infrared materials engineering. Full article

The production of novel oligosaccharides with potential prebiotic effects is of interest to expand the current market and explore the effectiveness of new functional carbohydrate forms. The utilization of glucansucrases is a cost-effective and environmentally friendly biotechnological strategy for producing novel gluco-oligosaccharides through acceptor reactions. In this study, an active glucansucrase (GS53) was used to produce gluco-oligosaccharides via its acceptor reactions with glucose, maltose, and maltotriose, and these oligosaccharides were tested in terms of structure and their gut microbiome modulatory effects. The formations of oligosaccharides were monitored by TLC analysis, and GS53 was active for the three acceptors but not for the other sugars tested. The structural characterization of the gluco-oligosaccharides by ¹H NMR analysis revealed the glycosylation of each acceptor with α-(1 → 3) and α-(1 → 6) linkages, whereas LC-MS analysis demonstrated the formations of DP 8, DP 7, and DP 6 oligosaccharides with acceptors maltose, maltotriose, and glucose, respectively. In vitro fecal fermentation analysis, in which microbial short-chain fatty acids (SCFAs) and microbial compositional changes were assessed using gas chromatography and 16S rRNA sequencing, respectively, demonstrated that the gluco-oligosaccharides formed SCFAs—particularly propionate and butyrate—at levels comparable to those observed with inulin, a well-established prebiotic. Additionally, the gluco-oligosaccharides were found to promote the growth of Bifidobacterium adolescentis and Blautia OTUs, which are known to have important physiological functions beneficial to human health. Overall, these results demonstrate that gluco-oligosaccharides synthesized using GS53 through acceptor reactions exhibit prebiotic potentials and could be utilized in the future as dietary supplements as well as in the development of functional foods targeting colonic health. Full article

A series of novel fluorescent donor–acceptor–donor (D-A-D) dyes containing [1,2,5]oxadiazolo[3,4-d]pyridazine and its 1-oxide as electron-withdrawing groups has been synthesized and thoroughly investigated using X-ray diffraction and molecular spectroscopy methods. This study showed that the introduction of N-oxide into the 1,2,5-oxadiazole ring in the acceptor fragment leads to a significant decrease in the luminescence intensity and quantum yield of the dyes. A comprehensive comparison of the photophysical properties of the obtained compounds containing the 1,2,5-oxadiazole ring with the previously studied [1,2,5]thia- and 1,2,5-selenadiazolo[3,4-d]pyridazine analogs showed that the oxygen substitution in the acceptor fragment shifts the phosphorescence maximum from the NIR region of 980–1100 nm to the red region of 690–770 nm. In contrast, for oxygen- and sulfur-containing dyes, purely red fluorescence with a maximum in the spectral range of 620–900 nm is observed. The crystal structures of furoxan-containing 3d·½CHCl₃ and furazan-containing 4d exhibit a non-planar [1,2,5]oxadiazolo[3,4-d]pyridazine fragment. We have found that short non-covalent interactions of the furoxan system with a lattice chloroform molecule in 3d lead to luminescence quenching. Meanwhile, in the 4d dye, the intermolecular π-π interactions of pyridazine nitrogen atoms with the N-carbazolyl group of the adjacent molecule should facilitate intermolecular charge transfer (ICT) emission. Thus, the luminescence maxima for these dyes can be tuned across a broad range of 700–1100 nm by varying the number of chalcogen atoms, highlighting the potential for tailoring optical properties in optoelectronic applications. Full article

Conductive polymers play a crucial role in the advancement of modern technologies, particularly in the field of organic photovoltaics (OPVs). Due to advantages such as flexibility, low specific weight, ease of processing, and low production costs, polymeric materials present an attractive alternative to traditional photovoltaic materials. This study investigates the properties of a polymer blend composed of PCPDTBT (donor) and PNDI(2HD)2T (acceptor), used as the active layer in bulk heterojunction (BHJ) solar cells. The motivation behind this research was the search for a novel n-type polymer material with potentially better properties than the commonly used P(NDI2OD-T2). Comprehensive characterization of thin films made from the individual polymers and their blend was conducted using Fourier Transform Infrared Spectroscopy (FTIR), Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Ultraviolet-Visible Spectroscopy (UV-Vis), four-point probe conductivity measurements, and photovoltaic testing. The prepared films were continuous, uniform, and exhibited low surface roughness (R_a < 2.5 nm). Spectroscopic analysis showed that the blend absorbs light in a broad range of the spectrum, with slight bathochromic shifts compared to individual polymers. Electrical measurements indicated that the blend’s conductivity (9.1 µS/cm) was lower than that of pure PCPDTBT but higher than that of PNDI(2HD)2T, with an optical band gap of 1.34 eV. Photovoltaic devices fabricated using the blend demonstrated an average power conversion efficiency (PCE) of 6.45%, with a short-circuit current of 14.37 mA/cm² and an open-circuit voltage of 0.89 V. These results confirm the feasibility of using PCPDTBT:PNDI(2HD)2T blends as active layers in BHJ solar cells and provide a promising direction for further optimization in terms of polymer ratio and processing conditions. Full article

Solid additive engineering is a well-established and effective strategy for enhancing active layer morphology in polymer solar cells (PSCs), thereby improving their power conversion efficiency (PCE). However, the availability of effective solid additive molecules remains limited, especially those combining simple structural units with a large dipole moment to promote strong interactions with active materials. In this study, we introduce 4-iodobenzonitrile (IBZN), a commercially available, low-cost, and structurally simple molecule with a high dipole moment (3.33 debye), as a solid additive for PSCs. Theoretical calculations, ultraviolet–visible (UV-Vis) spectroscopy experiments, and a morphology analysis demonstrate that IBZN forms strong interactions with L8-BO, subsequently enhancing the packing mode and crystallization. The incorporation of IBZN into PM6:L8-BO-based PSCs resulted in an increased fill factor (FF) of 79.54% and a boosted PCE from 17.49% to 18.77%. Furthermore, IBZN has also demonstrated outstanding regulatory effects in systems based on other Y-series acceptors, such as Y6 and BTP-ec9. This study not only introduces a structurally simple solid additive molecule characterized by a large dipole moment but also offers valuable insights for the subsequent development of novel solid additives aimed at enhancing the morphology and efficiency of PSCs. Full article

Novel wide-bandgap ZnO, BeO, and ZnBeO materials have recently gained considerable interest due to their stellar optoelectronic properties. These semiconductors are being used in developing high-resolution, flexible, transparent nanoelectronics/photonics and achieving high-power radio frequency modules for sensors/biosensors, photodetectors/solar cells, and resistive random-access memory applications. Despite earlier evidence of attaining p-type wz ZnO with N doping, the problem persists in achieving reproducible p-type conductivity. This issue is linked to charging compensation by intrinsic donors and/or background impurities. In ZnO: Al (Li), the vibrational features by infrared and Raman spectroscopy have been ascribed to the presence of isolated ${\mathrm{A}\mathrm{l}}_{\mathrm{Z}\mathrm{n}}{(\mathrm{L}\mathrm{i}}_{\mathrm{Z}\mathrm{n}})$ defects, nearest-neighbor (NN) ${[\mathrm{A}\mathrm{l}}_{\mathrm{Z}\mathrm{n}}{-\mathrm{N}}_{\mathrm{O}}$] pairs, and second NN ${[\mathrm{A}\mathrm{l}}_{\mathrm{Z}\mathrm{n}}{-\mathrm{O}-\mathrm{L}\mathrm{i}}_{\mathrm{Z}\mathrm{n}};{\mathrm{V}}_{\mathrm{Z}\mathrm{n}}-\mathrm{O}{-\mathrm{L}\mathrm{i}}_{\mathrm{Z}\mathrm{n}}]$ complexes. However, no firm identification has been established. By integrating accurate perturbation models in a realistic Green’s function method, we have meticulously simulated the impurity vibrational modes of ${\mathrm{A}\mathrm{l}}_{\mathrm{Z}\mathrm{n}}$${(\mathrm{L}\mathrm{i}}_{\mathrm{Z}\mathrm{n}})$ and their bonding to form complexes with dopants as well as intrinsic defects. We strongly feel that these phonon features in doped ZnO will encourage spectroscopists to perform similar measurements to check our theoretical conjectures. Full article

Developing novel gas-sensing materials is critical for overcoming the limitations of current metal oxide semiconductor technologies, which, despite their widely commercial use, require high operating temperatures to achieve optimal performance. In this context, integrating graphene with molecular organic layers provides a promising platform for next-generation gas-sensing materials. In this work, we systematically explore the gas-sensing properties of metal phthalocyanine/graphene (MPc/Gr) interfaces using density functional theory calculations. Specifically, we examine the role of different MPcs (FePc, CoPc, NiPc, and CuPc) and Gr doping levels (p-doped, neutral, and n-doped) in the detection of NH₃ and NO₂ molecules, used as representative electron-donor and -acceptor testing gases, respectively. Our results reveal that a p-doped Gr is necessary for NH₃ detection, while the choice of metal cation plays a crucial role in determining sensitivity, following the trend FePc/Gr > CoPc/Gr > NiPc/Gr, with CuPc/Gr exhibiting no response. Remarkably, FePc/Gr demonstrates sensitivity down to the limit of a single NH₃ molecule per FePc. Conversely, NO₂ detection is possible under both neutral and n-doped Gr, with the strongest response observed for n-doped FePc/Gr and CoPc/Gr. Crucially, we identify the d_z2 orbital of the MPc as a key factor in mediating charge transfer between the gas molecule and Gr, governing the electronic interactions that drive the sensing response. These insights provide valuable guidelines for the rational design of high-sensitivity graphene-based gas sensors. Full article

Nuclear factor-κB (NF-κB) signaling plays a pivotal role in regulating immune responses and is strongly implicated in cancer progression and inflammation-related diseases. The inhibitory κB kinases (IKKs), particularly IKKα, are central to modulating NF-κB activity, with distinct roles in the canonical and non-canonical signaling pathways. This study investigates the potential of selectively targeting IKKα to develop novel therapeutic strategies. A receptor–ligand interaction pharmacophore model was generated based on the co-crystallized structure of IKKα, incorporating six key features, two hydrogen bond acceptors, two hydrogen bond donors, one hydrophobic region, and one hydrophobic aromatic region. This model was used to virtually screen a diverse natural compound library of 5540 molecules, yielding 82 candidates that matched the essential pharmacophore features. Molecular docking and molecular dynamics simulations were subsequently employed to evaluate binding conformations, stability, and dynamic behavior of the top hits. The end-state free energy calculations (gmx_MMPBSA) further validated the interaction strength and stability of selected compounds. To experimentally confirm their inhibitory potential, key compounds were tested in LPS-stimulated RAW 264.7 cells, where they significantly reduced IκBα phosphorylation. These findings validate the integrative computational-experimental approach and identify promising natural compounds as selective IKKα inhibitors for further therapeutic development in cancer and inflammatory diseases. Full article

In this work, we present a study on the thermal/transport properties of a novel deep eutectic solvent (DES) obtained by using N-methyltrifluoroacetamide (FNMA) as the hydrogen bond donor (HBD) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the hydrogen bond acceptor (HBA). The binary phase diagram, thermal stability, flammability, viscosity and ionic conductivity of the as-prepared DESs were investigated at atmospheric pressure. The binary phase diagram shows a range of eutectic molar ratios (x_LiTFSI = 0.2~0.33), with the lowest deep eutectic temperature of −84 °C. At x_LiTFSI = 0.2 (i.e., FNMA:LiTFSI = 4:1 and denoted as DES-4:1). The as-prepared DES composition exhibits high thermal stability (onset temperature of weight loss = 78 °C), a low viscosity (η = 48.9 mPa s at 25 °C), relatively high ionic conductivity (σ = 0.86 mS cm⁻¹ at 25 °C) and non-flammability. The transport properties, including ionic conductivity and viscosity, as a function of temperature are in accordance with the Vogel–Fulcher–Tammann (VFT) equations. With increasing molar ratio of HBD vs. HBA, the viscosity decreases, and the ionic conductivity increases at a given temperature between 25 °C and 80 °C. The roughly equal pseudo-activation energies for ion transport and viscous flow in each composition imply a strong coupling of ion transport and viscous flow. Walden plots indicate vehicular transport as the main ion transport mechanism for the DES-4:1 and DES-3:1 compositions; meanwhile, it was confirmed that the ionic conductivity and viscous flow are strictly coupled. The present work is expected to provide strategies for the development of wide-temperature-range and safer electrolytes with low salt concentrations. Full article

This work is a continuation of our recent work on the prediction of hydrogen-bonding (HB) interaction enthalpies. In the present work, a simple method is proposed for the prediction of the HB interaction free energies. Quantum chemical (QC) calculations are combined with the Linear Solvation Energy Relationship (LSER) approach for the determination of novel QC-LSER molecular descriptors and the development of the method. Each hydrogen-bonded molecule is characterized by an acidity or proton donor capacity, ${\alpha }_G$, and/or a basicity or proton acceptor capacity, ${\beta }_G$. These descriptors suffice for the prediction of HB interaction free energy when the interacting molecules possess one acidic and or one basic site. In this case of two interacting molecules, 1 and 2, their overall HB interaction free energy is $c\left({\alpha }_{G1}{\beta }_{G2}+{\beta }_{G1}{\alpha }_{G2}\right)$, where c is a universal constant equal to (ln10)RT = 5.71 kJ/mol at 25 °C. This holds true over the full composition range, that is, regardless of which molecule is solute and which solvent. In the case of complex multi-sited molecules possessing more than one distant acidic site and/or more than one type of distant basic sites, two sets of ${\alpha }_G$ and ${\beta }_G$ descriptors are needed, one for the molecule as solute in any solvent and one for the same molecule as the solvent of any solute. Descriptors ${\alpha }_G$ and ${\beta }_G$ are reported for a number of common hydrogen-bonded molecules but they may be obtained for any other hydrogen-bonded molecule of interest from its molecular surface charge distribution already available or easily obtained via relatively cheap DFT/basis-set QC calculations. The new predictive scheme is validated against corresponding estimations of the widely used Abraham’s LSER model. The developments in the present work and the previous one are useful for solvation studies in chemical and biochemical systems and, particularly, for equation-of-state developments in molecular thermodynamics. The strengths and limitations of the new predictive method are critically discussed. Full article