Facile Synthesis of Diversely Functionalized Peptoids, Spectroscopic Characterization, and DFT-Based Nonlinear Optical Exploration
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ABSTRACT:
SUBMITTER: Concepcion O
PROVIDER: S-EPMC8515372 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The current research presents the synthesis of novel salicylaldehyde thiosemicarbazones (1-6) and their spectroscopic characterization employing UV-visible, Fourier transform infrared spectroscopy, and NMR techniques. Experimental results are compared and validated with the results obtained theoretically by employing density functional theory at the M06 level with the 6-311G (d,p) basis set. Further, various parameters [natural bond orbital (NBO)], linear and nonlinear optical (NLO) properties, and global reactivity parameters (GRPs) are computationally calculated. The NBO approach has confirmed the stability of compounds on account of charge delocalization and hyper conjugative interaction network. Frontier molecular orbital analysis has explained the charge transfer and chemical reactivity capability, while GRPs have led to the analysis of kinetic stability of the studied molecules. Further, the probability of being NLO-active has been theoretically proved by the HOMO/LUMO energy difference (4.133-4.186 eV) and β values (192.778-501.709 a.u). These findings suggest that the studied compounds possess potential NLO applications as they have shown larger NLO values in comparison with that of the urea molecule, and such distinct properties prove their technological importance.
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Project description:Synthesis of 5-aryl-N-(pyrazin-2-yl)thiophene-2-carboxamides (4a-4n) by a Suzuki cross-coupling reaction of 5-bromo-N-(pyrazin-2-yl)thiophene-2-carboxamide (3) with various aryl/heteroaryl boronic acids/pinacol esters was observed in this article. The intermediate compound 3 was prepared by condensation of pyrazin-2-amine (1) with 5-bromothiophene-2-carboxylic acid (2) mediated by TiCl4. The target pyrazine analogs (4a-4n) were confirmed by NMR and mass spectrometry. In DFT calculation of target molecules, several reactivity parameters like FMOs (EHOMO, ELUMO), HOMO-LUMO energy gap, electron affinity (A), ionization energy (I), electrophilicity index (ω), chemical softness (σ) and chemical hardness (η) were considered and discussed. Effect of various substituents was observed on values of the HOMO-LUMO energy gap and hyperpolarizability. The p-electronic delocalization extended over pyrazine, benzene and thiophene was examined in studying the NLO behavior. The chemical shifts of 1H NMR of all the synthesized compounds 4a-4n were calculated and compared with the experimental values.
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Project description:Herein, a series of indacenodithiophene-based derivatives (TNPD1-TNPD6) were designed having D-π-A architecture via end capped acceptor modulation of a reference molecule (TNPR) to investigate nonlinear optical (NLO) behavior. Quantum chemical calculations were accomplished to examine electronic, structural and optical properties utilizing a density functional theory (DFT) approach at M06 functional with 6-311G(d,p) basis set. For this, natural bond orbitals (NBOs), density of states (DOS), frontier molecular orbitals (FMOs), transition density matrix (TDM) and non-linear optical (NLO) analyses were performed for TNPR and TNPD1-TNPD6. The structural modifications revealed a significant electronic contribution in tuning the HOMOs and LUMOs of the derivatives with lowered energy gaps and wider absorption spectra. FMOs findings revealed that compound TNPD5 was found with the lowest energy gap (1.692 eV) and with the highest softness (0.591 eV-1) among the derivatives. Furthermore, a UV-Vis study also disclosed that maximum absorption (λmax = 852.242 nm) was exhibited by TNPD5 in chloroform solvent. All the derivatives exhibited significant NLO results; in particular, TNPD5 showed the highest first hyper-polarizability (βtot = 4.653 × 10-27 esu) and second hyper-polarizability (γtot = 9.472 × 10-32 esu). These DFT findings revealed that the end-capped substituents play a key role in enhancing the NLO response of these push-pull chromophores and the studied derivatives can be utilized as efficient NLO materials.
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Project description:Organotrifluoroborates are generating increased interest because of their ease of preparation and purification and indefinite shelf life. Herein we report the preparation of organotrifluoroborates bearing functional groups that can be manipulated at different stages of the synthetic route, exploiting the inertness of their carbon-boron bonds. The alkylation of 2,2-dicyanoethyltrifluoroborate with a variety of electrophiles and of (EWG)2CH2 with potassium iodomethyltrifluoroborate resulted in di- and trisubstituted ethyltrifluoroborates in good to excellent yields.
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Project description:Currently, we reported the synthesis of six novel salicylaldehyde-based thiosemicarbazones (BHCT1-HBCT6) via condensation of salicylaldehyde with respective thiosemicarbazide. Through various spectroscopic methods, UV-visible and NMR, the chemical structures of BHCT1-HBCT6 compounds were determined. Along with synthesis, a computational study was also performed at the M06/6-31G(d,p) functional. Various analyses such as natural bond orbital (NBO) analysis, natural population analysis, frontier molecular orbital (FMO) analysis, and molecular electrostatic potential surfaces were carried out to understand the nonlinear optical (NLO) characteristics of the synthesized compounds. Additionally, a comparative study was carried out between DFT and experimental results (UV-vis study), and a good agreement was observed in the results. The energy gap calculated through FMOs was found to be in decreasing order as 4.505 (FHCT2) > 4.499 (HBCT6) > 4.497 (BHCT1) = 4.497(HMCT5) > 4.386 (CHCT3) > 4.241(AHCT4) in eV. The global reactivity parameters (GRPs) were attained through E HOMO and E LUMO, which described the stability and hardness of novel compounds. The NBO approach confirmed the charge delocalization and stability of the molecules. Among all the investigated compounds, a larger value (557.085 a.u.) of first hyperpolarizability (βtot) was possessed by CHCT3. The NLO response (βtot) of BHCT1-HBCT6 was found to be 9.145, 9.33, 13.33, 5.43, 5.68, and 10.13 a.u. times larger than that of the standard para-nitroaniline molecule. These findings ascertained the potential of entitled ligands as best NLO materials for a variety of applications in modern technology.
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Project description:Triazoles, nitrogen-containing heterocycles, have gained attention for their applications in medicinal chemistry, drug discovery, agrochemicals, and material sciences. In the current study, we synthesized novel derivatives of N-substituted 2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-phenylpropanamide and conducted a comprehensive investigation using density functional theory (DFT). These novel structural hybrids of 1,2,4-triazole were synthesized through the multi-step chemical modifications of 3-bromobenzoic acid (1). Initially, compound 1 was converted into its methyl-3-bromobenzoate (2) which was then transformed into 3-bromobenzohydrazide (3). The final step involved the cyclization of compound 3, producing its 1,2,4-triazole derivative (4). This intermediate was then coupled with different electrophiles, resulting in the formation of the final derivatives (7a-7c). Additionally, the characterization of these triazole-based compounds (7a, 7b, and 7c) were carried out using techniques such as IR, HNMR, and UV-visible spectroscopy to understand their structural and spectroscopic properties. The DFT study utilized M06/6-311G(d,p) functional to investigate geometrical parameters, HOMO-LUMO energies, natural bond orbital analyses, transition density matrix (TDM), density of states, and nonlinear optical (NLO) properties. The FMO analysis revealed that compound 7c exhibited the lowest band gap value (4.618 eV). Notably, compound 7c exhibited significant linear polarizability (4.195 > × 10-23) and first and second hyperpolarizabilities (6.317 > × 10-30, 4.314 × 10-35), signifying its potential for nonlinear optical applications. These NLO characteristics imply that each of our compounds, especially 7c, plays a crucial part in fabricating materials showing promising NLO properties for optoelectronic applications.
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Project description:The [ferrocene-ene-phenol] motif has been identified as the pharmacophore responsible for the anticancer activity of the family of ferrocene-based molecules coined ferrocifens, owing to its unique redox properties. The addition of imide entities to the historical ferrociphenol scaffold tremendously enhanced the cytotoxic activity of a large panel of cancer cell cultures and preliminary studies showed that the reduction of one of the carbonyl groups of the imide groups to the corresponding α-hydroxylactams only slightly affected the antiproliferative activity. As a continuation to these studies, we took advantage of the facile conversion of α-hydroxylactams to highly electrophilic N-acyliminium ions to graft various substituents to the imide motif of phthalimido ferrocidiphenol. Cell viability studies showed that the newly synthesized compounds showed diverse cytotoxic activities on two breast cancer cell lines, while only one compound was significantly less active on the non-tumorigenic cell line hTERT-RPE1.
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Project description:A comprehensive theoretical study was carried out on a series of aryldimesityl borane (DMB) derivatives using Density Functional theory. Optimized geometries and electronic parameters like electron affinity, reorganization energy, frontiers molecular contours, polarizability and hyperpolarizability have been calculated by employing B3PW91/6-311++G (d, p) level of theory. Our results show that the Hammett function and geometrical parameters correlates well with the reorganization energies and hyperpolarizability for the series of DMB derivatives studied in this work. The orbital energy study reveals that the electron releasing substituents increase the LUMO energies and electron withdrawing substituents decrease the LUMO energies, reflecting the electron transport character of aryldimesityl borane derivatives. From frontier molecular orbitals diagram it is evident that mesityl rings act as the donor, while the phenylene and Boron atom appear as acceptors in these systems. The calculated hyperpolarizability of secondary amine derivative of DMB is 40 times higher than DMB (1). The electronic excitation contributions to the hyperpolarizability studied by using TDDFT calculation shows that hyperpolarizability correlates well with dipole moment in ground and excited state and excitation energy in terms of the two-level model. Thus the results of these calculations can be helpful in designing the DMB derivatives for efficient electron transport and nonlinear optical material by appropriate substitution with electron releasing or withdrawing substituents on phenyl ring of DMB system.
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Project description:The present work reports on the synthesis and characterization of iridium (Ir)-based nanohybrids with variable chemical compositions. More specifically, highly stable polyvinylpyrrolidone (PVP) nanohybrids of the PVP-IrO2 and PVP-Ir/IrO2 types, as well as non-coated Ir/IrO2 nanoparticles, are synthesized using different synthetic protocols and characterized in terms of their chemical composition and morphology via X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM), respectively. Furthermore, their nonlinear optical (NLO) response and optical limiting (OL) efficiency are studied by means of the Z-scan technique, employing 4 ns laser pulses at 532 and 1064 nm. The results demonstrate that the PVP-Ir/IrO2 and Ir/IrO2 systems exhibit exceptional OL performance, while PVP-IrO2 presents very strong saturable absorption (SA) behavior, indicating that the present Ir-based nanohybrids could be strong competitors to other nanostructured materials for photonic and optoelectronic applications. In addition, the findings denote that the variation in the content of IrO2 nanoparticles by using different synthetic pathways significantly affects the NLO response of the studied Ir-based nanohybrids, suggesting that the choice of the appropriate synthetic method could lead to tailor-made NLO properties for specific applications in photonics and optoelectronics.
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Project description:In the present study, pyrazole-thiophene-based amide derivatives were synthesized by different methodologies. Here, 5-Bromothiophene carboxylic acid (2) was reacted with substituted, unsubstituted, and protected pyrazole to synthesize the amide. It was observed that unsubstituted amide (5-bromo-N-(5-methyl-1H-pyrazol-3-yl)thiophene-2-carboxamide (7) was obtained at a good yield of about 68 percent. The unsubstituted amide (7) was arylated through Pd (0)-catalyzed Suzuki-Miyaura cross-coupling, in the presence of tripotassium phosphate (K3PO4) as a base, and with 1,4-dioxane as a solvent. Moderate to good yields (66-81%) of newly synthesized derivatives were obtained. The geometry of the synthesized compounds (9a-9h) and other physical properties, like non-linear optical (NLO) properties, nuclear magnetic resonance (NMR), and other chemical reactivity descriptors, including the chemical hardness, electronic chemical potential, ionization potential, electron affinity, and electrophilicity index have also been calculated for the synthesized compounds. In this study, DFT calculations have been used to investigate the electronic structure of the synthesized compounds and to compute their NMR data. It was also observed that the computed NMR data manifested significant agreement with the experimental NMR results. Furthermore, compound (9f) exhibits a better non-linear optical response compared to all other compounds in the series. Based on frontier molecular orbital (FMO) analysis and the reactivity descriptors, compounds (9c) and (9h) were predicted to be the most chemically reactive, while (9d) was estimated to be the most stable among the examined series of compounds.
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