Search

In this study, the washing performance of Western Anatolia clinoptilolite zeolite in detergent formulations was investigated as a single builder or in binary or ternary builder combinations. In all the experiments the remaining part of the detergent compositions were the same and consisted of alcohol ethoxylate, sodium carbonate and sodium sulphate. The washing test was performed at 60 deg. C by using coffee soiled swatches. For binary builder systems, clinoptilolite was combined with either a synthetic zeolite (NaA or NaX)or a complex-making co-builder (Na citrate or Na EDTA). clinoptilolite/NaA/co-builder, clinoptilolite/NaX/co-builder ternary systems were also tested. Results indicated that binary or ternary systems formed by the addition of clinoptilolite have synergistic interactions. [ABSTRACT FROM AUTHOR]

The synthesis of 5-aryl- or 5,6-diaryl-11 H -benzo[ a ]carbazoles has been achieved from 3-styryl indoles through catalyst-free photoinitiated dehydrogenative cyclization transformation, providing a range of structurally diverse products in excellent yields under mild conditions. The protocol is also applicable to furan and thiophene samples. This Mallory-type reaction takes place in an argon atmosphere without external oxidants. Finally, detailed mechanistic studies were performed, and kinetic isotope effect experiments indicate that dehydrogenative annulation reaction involves photoinduced 6π-electrocyclic ring-closing and hydrogen evolution cascade processes.

Modulation of existing drugs is an attractive strategy to achieve improved activity in cancer therapy by lowering their effective dose. Preparation of relatives has been suggested and explored to improve the therapeutic effect of anticancer agents. In the current study, we attempted to modulate tamoxifen (TMX) by replacing the C -phenyl ring in its backbone with an indole or oxindole. In addition, it was possible to convert indole-modified tamoxifens to the corresponding 3,3'-bis(indolyl)methanes (BIMs) via an electrophilic substitution reaction with various benzaldehydes. We analyzed the anticancer potential of these indole-modified tamoxifens against various breast cancer cell lines and identified certain tamoxifen relatives with the potential to treat estrogen receptor (ER)-positive breast cancers, based on preliminary results of cell viability and caspase activity assays. The indole-modified tamoxifen BIM- Z , Z -35b , BIM- Z , Z -35f , and E -33 selectively reduced the viability of receptor-sensitive breast cancer cells more effectively than tamoxifen and suppressed the expression of ER-regulated genes. Moreover, Caspase-8 activity showed a specific increase in MCF-7 cells treated with these compounds. Our results indicate that these compounds may be an alternative to tamoxifen for the treatment of breast cancer., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Indium-catalyzed, solvent-enabled regioselective C6- or N1-alkylations of 2,3-disubstituted indoles with para -quinone methides are developed under mild conditions. Notably, highly selective and switchable alkylations were selectively achieved by adjusting the reaction conditions. Moreover, scalability and further transformations of the alkylation products are demonstrated, and this operationally simple methodology is amenable to the late-stage C6-functionalization of the indomethacin drug. The reaction pathways were explained with the support of experimental and density functional theory studies.

Pd(II)-catalyzed C-H arylations of free (NH) indoles including different carbonyl directing groups on C3-position with aryl iodides are demonstrated. Importantly, the reactions are carried out using the same catalyst system without any additional transient directing group (TDG). In this study, the formyl group as a directing group gave the C4-arylated indoles versus C2-arylation. Using this catalyst system, C-H functionalization of 3-acetylindoles provided domino C4-arylation/3,2-carbonyl migration products. This transformation involves the unusual migration of the acetyl group to the C2-position following C4-arylation in one pot. Meanwhile, migration of the acetyl group could be simply controlled and N -protected 3-acetylindoles afforded C4-arylation products without migration of the acetyl group. Functionalization of indole-3-carboxylic acid (or methyl ester) with aryl iodides using the present Pd(II)-catalyst system resulted in decarboxylation followed by the formation of C2-arylated indoles. Based on the control experiments and the literature, plausible mechanisms are proposed. The synthetic utilities of these acetylindole derivatives have also been demonstrated. Remarkably, C4-arylated acetylindoles have allowed the construction of functionalized pityiacitrin (a natural product).

Aggregation-induced emission (AIE) is an extraordinary photochemical phenomenon described by Tang's group in 2001, where the aggregation of some organic molecules enhances their light emission by limiting intramolecular activity in the aggregate state. This phenomenon offers new opportunities for researchers due to its potential applications in optoelectronics, energy, and biophysics. Tetraphenylethylenes (TPEs) are reliable AIE luminogens with a wide range of successful applications in material chemistry. To expand the library of AIE-active TPEs, both a series of TPE analogues, in which the phenyl rotor has been replaced by the indole ring, and indole-substituted TPE derivatives were designed and synthesized through vinyl-aryl and aryl-aryl bond formations using the Suzuki coupling reaction. Efficient synthetic routes that delivered indole-modified and indole-substituted TPEs have been developed, and almost all heterocyclic TPE analogues have demonstrated AIE behavior. Furthermore, to test whether the indole ring can be diversified, two title compounds were converted to a series of bis(indolyl)methane (BIM), and these BIM-TPE materials showed typical AIE properties. Interestingly, two compounds indicated a solvent vapor fuming reversible switch between bright blue emission and greenish-yellow emission. Upon fuming with dichloromethane, their fluorescence spectra showed 8 and 32 nm red-shift and could return to the original state after fuming with hexane. Furthermore, we have explored the effects of replacing the phenyl ring in TPE with indole together with the substitution of TPE with indole ring(s) on the performance of organic light-emitting diode (OLED) device applications. In addition, density functional theory calculations; the optical, electrochemical, light emission, electroluminescence characteristics; and admittance spectroscopic analysis of OLED devices of four representative TPEs have been investigated in detail. As a result, the indole-TPEs are potential blue emitters with AIE features for conventional OLEDs, which is a significant color in displays and lighting., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

In the present study, new peripheral substituted Zn(II) and Cu(II) phthalocyanine derivatives (p-ZnPc and p-CuPc) bearing bulky aromatic triphenylamine groups were synthesized as alternative hole-transporting materials (HTMs). The structures of the new phthalocyanine derivatives (p-ZnPc and p-CuPc) were illuminated by various spectroscopic techniques such as mass spectrometry and 1 H, and 13 C-NMR. After structural analysis, their photophysical properties in solution and the solid phase were examined by UV-Vis absorption and fluorescence spectroscopy. Using p-ZnPc and p-CuPc as HTMs, highly stable perovskite-based solar cells with the structure of FTO/SnO 2 /perovskite/p-ZnPc and p-CuPc/Ag have been developed and characterized. It was observed that our devices with p-ZnPc as the HTM maintain over 93% of the initial performance for more than 960 h under atmospheric conditions (22-27 °C) with 35-45% relative humidity. In addition, some strategies such as using various methylammonium iodide (MAI) and lead iodide (PbI 2 ) blend ratios between 1 : 0.4 and 1 : 1.8 were employed to test the effect of the blend ratios on the long term stability of the perovskite-based solar cells. Our findings demonstrated that the spin-coated p-ZnPc based HTM demonstrated competitive power conversion efficiency and exhibited superior stability without encapsulation compared to commonly used HTMs.

Solvent-promoted and -controlled regioselective bond alkylation reactions of para -quinone methides ( p -QMs) with N -H free-indoline and 1,2,3,4-tetrahydroquinoline (THQ) under metal-free conditions have been developed. In the presence of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as the solvent, 1,6-addition alkylation reactions of p -QMs with NH-free indolines and THQs efficiently gave C5-alkylated indolines and C6-alkylated THQs. Using catalytic amounts of HFIP in DCM, the reaction of indolines and p -QMs resulted in the alkylation of indolines at the N1-position. HFIP plays two roles in the reactions: converting the indoline and THQ into bidentate nucleophiles and activating the p -QMs to achieve the 1,6-addition alkylation via hydrogen bond clusters. The indoline and THQ act as a C-nucleophile due to the H-bond clusters between HFIP and the nitrogen atom, whereas upon using catalytic amounts of HFIP, the compounds act as an N -nucleophile. All alkylation products were transformed into the corresponding indoles and quinolines via oxidation in the presence of diethyl azodicarboxylate (DEAD). Furthermore, the synthetic utilities have been showcased with both the removal of the tert -butyl groups from the C5-alkylated indole products and submission to their Suzuki coupling reactions.

Functionalization from nonperipheral positions of triazatruxene is representing a challenge. Triarylation of the nonperipheral positions (1, 6, and 11) in triazatruxene scaffold has been achieved for the first time via two approaches. The transformations involve arylation/cyclotrimerization and cyclotrimerization/arylation sequences. POCl 3 -mediated direct cyclotrimerization of oxindoles containing electron-deficient substituents on the aryl group at the C7-position resulted in the formation of 2-chloroindoles, whereas oxindoles containing electron-donating substituents gave the triazatruxenes. Furthermore, desired triazatruxenes were achieved through cyclotrimerization of 7-bromooxindole followed by coupling with arylboronic acids. NMR structural analysis exhibited that two of the suitably substituted oxindole and triazatuxene may have atropisomerism at room temperature. As a representative triazatruxene scaffold, the optoelectronic properties of 9a have also been studied via ultraviolet-visible (UV-vis) absorption spectra and fluorescence spectra of 9a thin films. Also, density functional theory calculation was realized to get knowledge about frontier molecular orbitals. In the light of the information obtained, an organic light-emitting diode (OLED) device utilizing 9a as an emissive layer was applied to obtain white emission. In brief, this study provides the first examples of the synthesis of triazatruxenes bearing aryl substituents at the nonperipheral positions as candidate compounds for organic electronics, optoelectronics, and material chemistry.

The self-assembly and coordination of amphiphiles comprised of naphthalenediimide (NDI) and bis(indolyl)methane (BIM) chromophores were investigated as a function of pH and metal. As observed by TEM, SEM and AFM imaging, the self-assembly of NDI-BIM 1 produced irregular nanostructures at neutral pH in CH3CN-H2O (1 : 1); whereas, well-defined nanotubes were observed at pH 2. Conversely, Fmoc-protected, NDI-BIM 2 formed nanotubes at neutral pH and nonspecific aggregates at pH 2. Upon coordination of Cu2+ ions to the bis(indoyl)methane moiety, a reorganization from nanotubes to vesicular structures was observed.

The self-assembly of bolaamphiphiles comprised of a central photochromic dithienylethene (DTE) chromophore was investigated in aqueous media. Irradiation at 254 nm induced a conversion from the open to closed states of the DTE chromophores. Whereas, in water, irradiation produced a photostationary state of 20 : 80 (open/closed), in methanol the ratio improved to 10 : 90 (open/closed). The open → closed transition was accompanied by the formation of 1D nanofibers during incubation in darkness.

The electrophilic substitution reaction of 4,7-dihydroindole with aryl-aldehydes as an electrophilic partner followed by an oxidation step to deliver 2,2'-bis(indolyl)arylmethanes was studied for the first time. The reaction afforded regioselectivity at the 2,2'-positions of indole in an operationally simple and inexpensive procedure with a variety of substrates. To the best of our knowledge, this is the first set of examples of 2,2'-bis(indolyl)arylmethanes obtained in a substituent-free manner. A facile method from dipyrromethanes to the corresponding 2-benzylindoles was also reported. In addition, 2,2'-bis(indolyl)arylmethanes were converted to 5,7-dihydroindolo[2,3- b ]carbazoles.

A straightforward synthetic route toward C5-alkylated indolines/indoles has been developed. The strategy is composed of Zn(OTf) 2 -catalyzed Friedel-Crafts alkylation of N-benzylindolines with nitroolefins, and a series of diverse indolines was first obtained in up to 99% yield. This reaction provides a direct and practical route to a variety of the C5-alkylated indolines which were also utilized for accessing corresponding indoles. Indoline derivatives with free NH groups could be obtained through an N-deprotection reaction. Moreover, the primary alkyl nitro groups in both indolines and indoles are amenable to further synthetic elaborations, thereby broadening the diversity of the products.

This review focuses on the chemistry of benzo-annulated tropones and tropolones reported since the beginning of the 20th century, which are currently used as tools by the synthetic and biological communities.

An efficient synthesis of 5,10-dihydroindeno[1,2-b]indoles (3a-t) containing substituents such as methoxy, hydroxyl, and halogen (F, Cl, and Br) on indeno part was described. Antioxidant and radical scavenging activities of synthesized compounds (3a-t) were determined by various in vitro assays such as 1,1-diphenyl-2-picryl-hydrazyl free radicals (DPPH(*)), 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid radicals (ABTS(*+)), N,N-dimethyl-p-phenylenediamine dihydrochloride radicals (DMPD(*+)), and superoxide anion radicals (O(2)(*-)) scavenging, reducing ability determination by the Fe(3+)-Fe(2+) and Cu(2+)-Cu(+) (CUPRAC method) transformation methods, H(2)O(2) scavenging, and ferrous ion (Fe(2+)) chelating activities. Moreover, these activities were compared to synthetic and standard antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), alpha-tocopherol, and trolox. The results showed that the synthesized compounds (3a-t) had effective antioxidant power.

[reaction: see text] endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters have been synthesized, and their Diels-Alder cycloaddition reactions with maleic anhydride, dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of four adducts indicated the pyramidalization of the central double bond. Density functional theory calculations on the isolated products and model compounds showed excellent agreement between the experimental and theoretical determined butterfly angles. Furthermore, it has been shown that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the pyramidalization which is attributed to the steric interactions between the cyclopropyl group and ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their X-ray analysis could not be carried out. DFT calculations on model compounds showed increased bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester.