595 results on '"Dithiolane"'
Search Results
2. Stress degradation studies and development of validated stability indicating densitometric method for estimation of alpha lipoic acid in bulk and capsule dosage form.
- Author
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Srivastava, Shruti, Dhaneshwar, Suneela, and Kawathekar, Neha
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LIPOIC acid ,STATISTICAL correlation ,DERIVATIZATION ,TOLUENE - Abstract
A precise, sensitive, specific and accurate stability indicating densitometric method was developed and validated for alpha-lipoic acid (ALA) in bulk and capsule dosage form. The study employed pre-coated silica gel 60F
254 TLC plates as stationary phase and toluene: chloroform: methanol: formic acid (5:3:1:0.05; v/v/v/v) as mobile phase. The developed method furnished compact spots of alpha-lipoic acid (Rf 0.28 ± 0.05) after derivatization, offered good linearity in range 80–400 ng/spot with correlation coefficient of 0.998. The values for detection and quantitation were found 18.022 and 54.612 ng/spot respectively. ALA was subjected to stress degradation studies and total 13 degradation products were resolved. Thus, the proposed method offered good results according to ICH guidelines, and can be used for identification, routine quantitative determination as well as for monitoring the stability of ALA in bulk and in capsules. [ABSTRACT FROM AUTHOR]- Published
- 2023
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3. Synthesis, molecular structure investigation, biological evaluation and docking studies of novel spirothiazolidinones
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Sarvesh Kumar Pandey, Umesh Yadava, M.L. Sharma, Anjali Upadhyay, Munna Prasad Gupt, Ashish Ranjan Dwivedi, and Aaqila Khatoon
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Spiro ,Thiazolidinones ,Dithiolane ,Antimicrobial ,Antitubercular ,DFT ,Chemistry ,QD1-999 - Abstract
A series of 3-substituted-spiro-(1,3-dithiolan-2,2′-thiazolidin)-4-ones(2) designed as antimicrobial agents and have been synthesized by the reaction between [1,3]dithiolan-2-ylidene-(substituted-phenyl)amine (1) and mercaptoacetic acid. The reaction between substituted anilines, sodium hydroxide and carbon disulfide followed by the reaction of 1, 2-dichloroethane gave quantitatively and analytically pure compound (1). The structure of synthesized compound (1) and (2) is based on spectral (IR, 1H NMR, 13C NMR) as well elemental analysis. These compounds have been screened for their antimicrobial and antitubercular activities. Some of them have showed significant inhibition on bacterial and fungal growth. Few of them showed moderate antitubercular profile. Docking studies of the some novel compounds were performed and results showed that these compounds have good binding energy and have better binding affinity towards the active pocket, thus they may be considered as good inhibitors for selective proteins. Furthermore, computational studies of some derivatives were also performed using Gaussian suite of program.
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- 2023
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4. Activated cyanoacetamide in heterocyclic synthesis: Design, synthesis, antitumor activity and docking study of some new pyrimidine derivatives.
- Author
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Emam, Dalia R., Soliman, Nanees N., Fadda, Ahmed A., and Bayoumy, Nesma M.
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PYRIMIDINES , *PYRIMIDINE derivatives , *MOLECULAR docking , *MAMMARY gland cancer , *HETEROCYCLIC compounds synthesis , *ANTINEOPLASTIC agents - Abstract
• Synthesis of new cyanoacetamidopyrimidine compounds and their utility as a starting material for the synthesis of more heterocyclic compounds bearing pyrimidine moiety. • The main objective of this work was to study cytotoxicity and antitumor evaluation of the new pyrimidine derivatives. • Study the structure-activity relationship (SAR) of the newly prepared pyrimidine derivatives. • Study the molecular docking of the newly prepared pyrimidine derivatives. The precursor cyanoacetamide derivatives (6) were achieved by the reaction of pyrimidine derivative 5 with cyanoacetic acid catalyzed by acetic anhydride. The reaction of cyanoacetamide derivative 6 with different reagents afforded many heterocyclic systems such as thioacetic acid (9) , dithiolane derivatives (11) and (12) , 1,8-naphthyridine (14) , quinoline derivatives (17) and (18) , pyridine derivatives 20, 22, 24, 26 , and 27 , pyridazine (30) , pyranopyrimidine (32) , and pyrazolopyrimidine (34). All the newly synthesized compounds were characterized with spectroscopic analyses. Compounds were tested for their anticancer activity against three human cancer cell lines: hepatocellular carcinoma (HepG-2), colon cancer (HCT-116), and mammary gland breast cancer (MCF-7). The studied compound's cytotoxic activity ranged from very strong to very weak. The most active compounds were 9, 10, 11, 27 , and 34. The binding disposition of the docked compounds, in particular 9, 10, 11, 27, and 34 , towards the binding site of AKT complexed with co-crystallized ligand was investigated using molecular docking (PDB = 4EJN). A new approach for the synthesis of some new heterocyclic compounds bearing pyrimidine rings as antitumor agents. [Display omitted] [ABSTRACT FROM AUTHOR]
- Published
- 2024
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5. Synthesis of Conformationally Locked and C-Linked Analogues of Imidazole-Based Ketene Dithioacetal Fungicides.
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Gagnepain, Julien, Jeanmart, Stephane, Bonvalot, Damien, Jacob, Olivier, and Lamberth, Clemens
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KETENES , *IMIDAZOLES , *FUNGICIDES - Abstract
First examples with the unknown tricyclic 4,8b-dihydro-3aHindeno[ 1,2-d][1,3]dithiole ring system have been prepared. Also, imidazoles linked in ring position 5 to a ketene dithioacetal and 1,3-dithiane derivatives with an exocyclic cyano- and imidazole-substituted C-C double bond are completely new. All these compounds are either conformationally locked, C-linked or six-ring analogues of the antifungal agent luliconazole. Synthesis and fungicidal activity of these sterol biosynthesis inhibitors are reported. [ABSTRACT FROM AUTHOR]
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- 2019
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6. One Pot Synthesis of Dithiolane Dendron Functionalized Gold Nanoparticles
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Barbara Freis, Francis Perton, Sylvie Begin-Colin, Damien Mertz, Marlène Palluel, Céline Kiefer, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), and Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS)
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Chemistry ,One-pot synthesis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,[CHIM.THER]Chemical Sciences/Medicinal Chemistry ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Combinatorial chemistry ,0104 chemical sciences ,Dithiolane ,Inorganic Chemistry ,chemistry.chemical_compound ,Colloidal gold ,Dendrimer ,0210 nano-technology ,ComputingMilieux_MISCELLANEOUS - Abstract
International audience
- Published
- 2021
7. Synthesis of an Acyclic Precursor to Epothilone D Analog. Aldol Condensation of (1R)-1-(1,3-Dithiolan-2-yl)-1-(methoxymethoxy)- 2,2-dimethylpentan-3-one with C6‒C21 and C6‒C9 Aldehyde Segments.
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Valeev, R. F., Sunagatullina, G. R., Loza, V. V., and Miftakhov, M. S.
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ACYCLIC acids , *ALDEHYDE synthesis , *ALDOL condensation , *ENOLIZATION , *DITHIOLANE - Abstract
The synthesis of acyclic precursors to epothilone D analogs has been explored. Optimal conditions have been found for enolization of (1R)-1-(1,3-dithiolan-2-yl)-1-(methoxymethoxy)-2,2-dimethylpentan-3-one and its aldol condensation with C6‒C21 and C6‒C9 aldehydes. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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8. Thiophilic ring opening reactions of 3,3-bis(trifluoromethyl)-5-alkoxy-1,2-dithiolanes under action of nucleophiles.
- Author
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Petrov, Viacheslav
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DITHIOLANE , *TRIFLUOROMETHYL compounds , *ALKOXY radicals , *HYDROGEN atom , *CYCLOPROPANE - Abstract
The reaction of 3,3-bis(trifluoromethyl)-5-alkoxy-1,2-dithiolanes (RO= OEt or OBu-n) proceeds through thiophilic attack of BuLi leading to the formation of ring-opened product BuSCH(OR)CH 2 C(CF 3 ) 2 SLi, which can be converted into the corresponding thiols or sulfides by the reaction with H + or alkyl halide. Interaction of 3,3-bis(trifluoromethyl)-5-n-butoxy-1,2-dithiolane with CF 3 Si(CH 3 ) 3 resulted in unusual reaction leading to the formation of CF 3 SCH(OBu)CH 2 C(CF 3 )=CF 2 ( 7 ). The treatment of 7 with CsF in the presence pentafluoropyridine led to equimolar mixture of 2-n-butoxy-1,1-bis(trifluoromethyl)cyclopropane and 4-(trifluoromethylthio)tetrafluoropyridine (as a result of interception of liberated in this process CF 3 S- anion by pentafluoropyridine). [ABSTRACT FROM AUTHOR]
- Published
- 2018
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9. Metal‐Free [3+2]‐Cycloaddition of Thiiranes with Isothiocyanates, Isoselenocyanates and Carbodiimides: Synthesis of 2‐Imino‐Dithiolane/Thiaselenolane/Thiazolidines.
- Author
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Satheesh, Vanaparthi, Kumar, Sundaravel Vivek, Vijay, Murugan, Barik, Debashis, and Punniyamurthy, Tharmalingam
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RING formation (Chemistry) ,ISOTHIOCYANATES ,CARBODIIMIDES ,DITHIOLANE ,REGIOSELECTIVITY (Chemistry) - Abstract
Abstract: Metal‐free regioselective [3+2]‐cycloaddition of 2‐aryl/alkylthiiranes with isothiocyanates, isoselenocyanates and carbodiimides is developed using BF
2 OTf⋅OEt2 to produce 2‐imino‐dithiolane/‐thiaselenolane/‐thiazolidine frameworks at room temperature. The selectivity, substrate scope and scale up are the important practical features. [ABSTRACT FROM AUTHOR]- Published
- 2018
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10. Organocatalytic Ring-Opening Copolymerization of Trimethylene Carbonate and Dithiolane Trimethylene Carbonate: Impact of Organocatalysts on Copolymerization Kinetics and Copolymer Microstructures.
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Jingjing Wei, Hao Meng, Beibei Guo, Zhiyuan Zhong, and Fenghua Meng
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ORGANOCATALYSIS , *COPOLYMERIZATION , *CYCLOPROPANE , *DITHIOLANE , *COPOLYMERS , *MICROSTRUCTURE - Abstract
The ring opening copolymerization of trimethylene carbonate (TMC) and dithiolane trimethylene carbonate (DTC) using acidic and basic organocatalysts, i.e., diphenyl phosphate (DPP) and triazabicyclo[4.4.0]dec-5-ene (TBD), was systemically investigated. Interestingly, DPP and TBD gave rise to completely different polymerization kinetics and copolymer sequences. The copolymerization of TMC and DTC using methoxy poly(ethylene glycol) (mPEG–OH) as an initiator and DPP as a catalyst proceeded in a first-order manner and to near completion in 72 h for both monomers, yielding well-controlled copolymers with random sequences, predictable molar mass, and low dispersity (Mw/Mn = 1.09–1.19). By contrast, TBD brought about much faster copolymerization of TMC and DTC under similar conditions (high monomer conversion achieved in 2–4 h), to furnish copolymers with controlled molar mass and moderate dispersity (Mw/Mn = 1.27–1.80). Moreover, polymerization kinetics revealed that DTC was preferentially polymerized followed by first-order polymerization of TMC, leading to blocky copolymers. These results signify that type of organocatalysts has a critical influence on polymerization kinetics of cyclic carbonates, copolymer sequence, and molar mass control. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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11. Transition-Metal-Free Regioselective Cross-Coupling: Controlled Synthesis of Mono- or Dithiolation Indolizines.
- Author
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Bin Li, Zhiyu Chen, Hua Cao, and Hong Zhao
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REGIOSELECTIVITY (Chemistry) , *TRANSITION flow , *DITHIOLANE , *DITHIOLATES , *THIOLATES - Abstract
An efficient transition-metal-free regioselective C–H/S–H cross-coupling of indolizines with thiols has been developed for the first time to describe a workable route to indolizine thioethers. This finding provides a new method and more straightforward pathway for controllable synthesis of mono- or dithiolation indolizines that are otherwise difficult to obtain by the literature methods. The reaction exhibits good functional group tolerance and high efficiency and affords the products in good to excellent yields. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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12. Selective Activation of a Prodrug by Thioredoxin Reductase Providing a Strategy to Target Cancer Cells.
- Author
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Li, Xinming, Hou, Yanan, Meng, Xianke, Ge, Chunpo, Ma, Huilong, Li, Jin, and Fang, Jianguo
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THIOREDOXIN , *CANCER cells , *HOMEOSTASIS , *OXIDATION-reduction reaction , *DITHIOLANE - Abstract
Abstract: Elevated reactive oxygen species and antioxidant defense systems have been recognized as one of the hallmarks of cancer cells. As a major regulator of the cellular redox homeostasis, the selenoprotein thioredoxin reductase (TrxR) is increasingly considered as a promising target for anticancer drug development. The current approach to inhibit TrxR predominantly relies on the modification of the selenocysteine residue in the C‐terminal active site of the enzyme, in which it is hard to avoid the off‐target effects. By conjugating the anticancer drug gemcitabine with a 1,2‐dithiolane scaffold, an unprecedented prodrug strategy is disclosed that achieves a specific release of gemcitabine by TrxR in cells. As overexpression of TrxR is frequently found in different types of tumors, the TrxR‐dependent prodrugs are promising for further development as cancer chemotherapeutic agents. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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13. Synthesis and fungicidal activity of novel imidazole-based ketene dithioacetals.
- Author
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Jeanmart, Stephane, Gagnepain, Julien, Maity, Pulakesh, Lamberth, Clemens, Cederbaum, Fredrik, Rajan, Ramya, Jacob, Olivier, Blum, Mathias, and Bieri, Stephane
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IMIDAZOLES , *DRUG synthesis , *ANTIFUNGAL agents , *KETENE derivatives , *PHYTOPATHOGENIC microorganisms , *STRUCTURE-activity relationships - Abstract
Novel imidazole-based ketene dithioacetals show impressive in planta activity against the economically important plant pathogens Alternaria solani , Botryotinia fuckeliana , Erysiphe necator and Zymoseptoria tritici . Especially derivatives of the topical antifungal lanoconazole, which bear an alkynyloxy or a heteroaryl group in the para -position of the phenyl ring, exhibit excellent control of the mentioned phytopathogens. These compounds inhibit 14α -demethylase in the sterol biosynthesis pathway of the fungi. Synthesis routes starting from either benzaldehydes or acetophenones as well as structure-activity relationships are discussed in detail. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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14. Dodecanoyl isothiocyanate and <italic>N</italic>′-(2-cyanoacetyl) dodecanehydrazide as precursors for the synthesis of different heterocyclic compounds with interesting antioxidant and antitumor activity.
- Author
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Ismail, Mahmoud F. and Elsayed, Galal A.
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HETEROCYCLIC compounds synthesis , *ISOTHIOCYANATES , *HYDRAZIDES , *ANTIOXIDANTS , *ANTINEOPLASTIC agents - Abstract
Dodecanoyl isothiocyanate
1 was utilized for the construction of thioureido, 2-thioxo-2,3-dihydroquinazolin-4(1H )-one, benzo[d ]-1,3-thiazin-4(H )-one and 3-amino quinazolin-4(3H )-one derivatives2, 3, 4 , and5 respectively. However,N ′-(2-cyanoacetyl) dodecanehydrazide6 was also used as a key starting material for the construction of a variety of new pyrazolone, pyrazole, thiadiazole, pyridazine, chromeno[2,3-c ]pyrazole, and dithiolane derivatives7, 9, 12, 15, 18 , and20 , respectively. The newly synthesized compounds were characterized by elemental analyses and spectral data (IR, 1H NMR, and mass spectra). Some of the newly synthesized compounds bearing heterocyclic moieties were tested for antioxidant activity as reflected in their ability to inhibit oxidation in rat brain and kidney homogenates using 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) inhibition. Also, in vitro anticancer activity was examined using the standard (3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide) (MTT) method against a panel of two human tumor cell lines namely; hepatocellular carcinoma HepG2 and mammary gland breast cancer MCF-7. Compounds12 and16b exhibited the highest activities as antioxidant and antitumor agents. Meanwhile, compounds7 and20 showed moderate activities and the rest of the tested compounds showed weak activities. [ABSTRACT FROM AUTHOR]- Published
- 2018
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15. Gas-phase conformations of 2-methyl-1,3-dithiolane investigated by microwave spectroscopy.
- Author
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Van, Vinh, Stahl, Wolfgang, Schwell, Martin, and Nguyen, Ha Vinh Lam
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DITHIOLANE , *CONFORMATIONAL analysis , *GAS phase reactions , *MICROWAVE spectroscopy , *QUANTUM chemistry - Abstract
The conformational analysis of 2-methyl-1,3-dithiolane using quantum chemical calculations at some levels of theory yielded only one stable conformer with envelope geometry. However, other levels of theory indicated two envelope conformers. Analysis of the microwave spectrum recorded using two molecular jet Fourier transform microwave spectrometers covering the frequency range from 2 to 40 GHz confirms that only one conformer exists under jet conditions. The experimental spectrum was reproduced using a rigid-rotor model with centrifugal distortion correction within the measurement accuracy of 1.5 kHz, and molecular parameters were determined with very high accuracy. The gas phase structure of the title molecule is compared with the structures of other related molecules studied under the same experimental conditions. [ABSTRACT FROM AUTHOR]
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- 2018
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16. A Rotaxane Scaffold Bearing Multiple Redox Centers: Synthesis, Surface Modification and Electrochemical Properties.
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Steffenhagen, Marie, Latus, Alina, Trinh, Thi Minh Nguyet, Nierengarten, Iwona, Lucas, Ivan T., Joiret, Suzanne, Landoulsi, Jessem, Delavaux‐Nicot, Béatrice, Nierengarten, Jean‐François, and Maisonhaute, Emmanuel
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ROTAXANES , *DITHIOLANE , *FERROCENE , *CHEMICAL synthesis , *OXIDATION-reduction reaction , *ATOMIC force microscopy - Abstract
Abstract: A rotaxane scaffold incorporating two dithiolane anchoring units for the modification of gold surfaces has been functionalized with multiple copies of a redox unit, namely ferrocene. Surface modification has been first assessed at the single molecule level by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) imaging, while tip enhanced Raman spectroscopy (TERS) provided the local vibrational signature of the ferrocenyl subunits of the rotaxanes grafted onto the gold surface. Finally, oxidation of the redox moieties within a rotaxane scaffold grafted onto gold microelectrodes has been investigated by ultrafast cyclic voltammetry. Intramolecular electron hopping is indeed extremely fast in this system. Moreover, the kinetics of charge injection depends on the molecular coverage due to the influence of intermolecular contacts on molecular motions. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
17. Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers.
- Author
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Margulis, Katherine, Zhang, Xiangyi, Joubert, Lydia‐Marie, Bruening, Karsten, Tassone, Christopher J., Zare, Richard N., and Waymouth, Robert M.
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POLYMERIC nanocomposites , *MOLECULAR self-assembly , *DITHIOLANE , *BLOCK copolymers , *CROSSLINKING (Polymerization) - Abstract
Template-free fabrication of non-spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self-assembly from aqueous solutions at room temperature. Nanocubes with edges of 40-200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self-assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol- or photo-induced crosslinking was developed. The ability to solubilize a model hydrophobic drug, curcumin, was also explored. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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18. Synthesis of the Core Ring System of the Antiosteoporotic Citrofulvicin
- Author
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Kalina Doytchinova and Jeffrey D. Winkler
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010405 organic chemistry ,Organic Chemistry ,Intramolecular cyclization ,Core (manufacturing) ,010402 general chemistry ,Ring (chemistry) ,01 natural sciences ,Biochemistry ,Combinatorial chemistry ,0104 chemical sciences ,Dithiolane ,chemistry.chemical_compound ,chemistry ,Physical and Theoretical Chemistry - Abstract
Synthesis of the octacyclic ring system of citrofulvicin is described in nine steps from readily available starting materials. Blocking undesired intramolecular cyclization of a reactive β-diketone intermediate by transient incorporation of a dithiolane ring led to the formation of the requisite 1-hydroxy-2,4,6-trioxaadamantane ring system of citrofulvicin.
- Published
- 2021
19. R-enantiomer of α-lipoic acid. Opportunities and prospects for clinical use
- Author
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I.P. Dunaieva, N.A. Kravchun, and P.P. Kravchun
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Antioxidant ,Thioctic Acid ,α-lipoic acid r-enantiomer, arterial hypertension, metabolic syndrome, review ,medicine.medical_treatment ,Pharmacology ,medicine.disease ,RC648-665 ,Diseases of the endocrine glands. Clinical endocrinology ,Dithiolane ,chemistry.chemical_compound ,Lipoic acid ,chemistry ,Dihydrolipoic acid ,Carbohydrate Metabolism Disorder ,medicine ,lipids (amino acids, peptides, and proteins) ,Metabolic syndrome ,Enantiomer - Abstract
The paper presents an analysis of current literature data on the use of the R-enantiomer of α-lipoic acid as an antihypertensive treatment in patients with hypertension and metabolic syndrome. An analysis of the literature was carried out on its use as an antiinflammatory agent in inflammatory diseases. Currently, a very important aspect of researches is the possibility of using R-α-lipoic acid as a micronutrient and therapeutic agent for the treatment of diabetic polyneuropathy and neurodegenerative diseases, especially Alzheimer’s disease, carbohydrate metabolism disorders and metabolic syndrome. Lipoic acid has now become an important ingredient in multivitamin formulas, anti-aging supplements. R-α-lipoic acid is a metabolic antioxidant, its molecule contains a dithiolane ring in oxidized form, this ring has the ability to cleave with formation of dihydrolipoic acid. And since α-lipoic acid, a physiological form of thioctic acid, is a strong antioxidant that relieves the symptoms of diabetic neuropathy, the literature review analyzed data from various authors on the antioxidant effects of the R-enantiomer of α-lipoic acid and found that it had strong antioxidant effects, and its dose of 300 mg is bioequivalent to 600 mg of racemic α-lipoic acid. As presented in a sufficient number of analyzed sources, the biological role of lipoic acid is quite diverse. It is important to determine the exact causal relationship between lipoic acid and its immediate cellular targets. Lipoic acid can have a number of important and diverse physiological effects on the stimulation of neurohormonal function and, thus, indirectly affect multiple cellular signaling pathways in peripheral tissues.
- Published
- 2021
20. Spatial and Temporal Modulation of Cell Instructive Cues in a Filamentous Supramolecular Biomaterial
- Author
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Tong, Ciqing, Wondergem, Joeri A.J., van den Brink, Marijn, Kwakernaak, Markus C., Chen, Ying, Hendrix, Marco M.R.M., Voets, Ilja K., Danen, Erik H.J., Le Dévédec, Sylvia, Heinrich, Doris, Kieltyka, Roxanne E., Tong, Ciqing, Wondergem, Joeri A.J., van den Brink, Marijn, Kwakernaak, Markus C., Chen, Ying, Hendrix, Marco M.R.M., Voets, Ilja K., Danen, Erik H.J., Le Dévédec, Sylvia, Heinrich, Doris, and Kieltyka, Roxanne E.
- Abstract
Supramolecular materials provide unique opportunities to mimic both the structure and mechanics of the biopolymer networks that compose the extracellular matrix. However, strategies to modify their filamentous structures in space and time in 3D cell culture to study cell behavior as encountered in development and disease are lacking. We herein disclose a multicomponent squaramide-based supramolecular material whose mechanics and bioactivity can be controlled by light through co-assembly of a 1,2-dithiolane (DT) monomer that forms disulfide cross-links. Remarkably, increases in storage modulus from ∼200 Pa to >10 kPa after stepwise photo-cross-linking can be realized without an initiator while retaining colorlessness and clarity. Moreover, viscoelasticity and plasticity of the supramolecular networks decrease upon photo-irradiation, reducing cellular protrusion formation and motility when performed at the onset of cell culture. When applied during 3D cell culture, force-mediated manipulation is impeded and cells move primarily along earlier formed channels in the materials. Additionally, we show photopatterning of peptide cues in 3D using either a photomask or direct laser writing. We demonstrate that these squaramide-based filamentous materials can be applied to the development of synthetic and biomimetic 3D in vitro cell and disease models, where their secondary cross-linking enables mechanical heterogeneity and shaping at multiple length scales.
- Published
- 2022
21. Molecularly Engineered Cyclopenta[2,1-b;3,4-b′]dithiophene-Based Hole-Transporting Materials for High-Performance Perovskite Solar Cells with Efficiency over 19%
- Author
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Kun-Mu Lee, Hsin-Cheng Chung, Chien-Chun Chou, Tahsin J. Chow, Tsung-Yu Tsai, Shih-Sheng Sun, Heng-Yu Chen, Sheng Hsiung Chang, and Yan-Duo Lin
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Materials science ,Carbazole ,Energy Engineering and Power Technology ,Ring (chemistry) ,Dithiolane ,Organic semiconductor ,chemistry.chemical_compound ,Crystallography ,chemistry ,Materials Chemistry ,Electrochemistry ,Chemical Engineering (miscellaneous) ,Electrical and Electronic Engineering ,Perovskite (structure) - Abstract
Three cyclopenta[2,1-b;3,4-b′]dithiophene (CPDT)-based organic semiconductors LYC-1-LYC-3 consisting of a central dithiolane ring with triarylamine-based side groups were prepared and utilized as h...
- Published
- 2021
22. The effect of tether groups on the spin states of iron(<scp>ii</scp>)/bis[2,6-di(pyrazol-1-yl)pyridine] complexes
- Author
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Malcolm A. Halcrow, Miguel Clemente-León, Izar Capel Berdiell, Víctor García-López, and Mark J. Howard
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Inorganic Chemistry ,chemistry.chemical_classification ,chemistry.chemical_compound ,Acetic acid ,Perchlorate ,chemistry ,Spin states ,Carboxylic acid ,Pyridine ,Functional group ,Ring (chemistry) ,Medicinal chemistry ,Dithiolane - Abstract
The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(ii) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 whose complex remains predominantly high-spin. Crystalline [Fe(L6)2][ClO4]2·2MeCN contains three unique cation sites which alternate within hydrogen-bonded chains, and undergo gradual SCO at different temperatures upon warming. The SCO midpoint temperature (T1/2) of the complexes in CD3CN solution ranges between 208-274 K, depending on the functional group linking the tether groups to the pyridyl ring. This could be useful for predicting how these complexes might behave when deposited on gold or silica surfaces.
- Published
- 2021
23. Spatial and temporal modulation of cell instructive cues in a filamentous supramolecular biomaterial
- Author
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Ciqing Tong, Joeri A. J. Wondergem, Marijn van den Brink, Markus C. Kwakernaak, Ying Chen, Marco M. R. M. Hendrix, Ilja K. Voets, Erik H. J. Danen, Sylvia Le Dévédec, Doris Heinrich, Roxanne E. Kieltyka, and Self-Organizing Soft Matter
- Subjects
Cell Culture Techniques ,General Materials Science ,Biocompatible Materials ,Hydrogels ,Photopatterning ,Cues ,Aupramolecular ,3D Cell Culture ,Extracellular Matrix ,Dithiolane - Abstract
Supramolecular materials provide unique opportunities to mimic both the structure and mechanics of the biopolymer networks that compose the extracellular matrix. However, strategies to modify their filamentous structures in space and time in 3D cell culture to study cell behavior as encountered in development and disease are lacking. We herein disclose a multicomponent squaramide-based supramolecular material whose mechanics and bioactivity can be controlled by light through co-assembly of a 1,2-dithiolane (DT) monomer that forms disulfide cross-links. Remarkably, increases in storage modulus from ∼200 Pa to >10 kPa after stepwise photo-cross-linking can be realized without an initiator while retaining colorlessness and clarity. Moreover, viscoelasticity and plasticity of the supramolecular networks decrease upon photo-irradiation, reducing cellular protrusion formation and motility when performed at the onset of cell culture. When applied during 3D cell culture, force-mediated manipulation is impeded and cells move primarily along earlier formed channels in the materials. Additionally, we show photopatterning of peptide cues in 3D using either a photomask or direct laser writing. We demonstrate that these squaramide-based filamentous materials can be applied to the development of synthetic and biomimetic 3D in vitro cell and disease models, where their secondary cross-linking enables mechanical heterogeneity and shaping at multiple length scales.
- Published
- 2022
24. Synthesis and antimicrobial evaluation of some novel dithiolane, thiophene, coumarin, and 2-pyridone derivatives.
- Author
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Mahmoud, Mahmoud R., Abu El-Azm, Fatma S. M., Ali, Amira T., and Ali, Yasmeen M.
- Subjects
- *
NAPHTHA , *ETHYLENE dichloride , *PYRIDONE derivatives , *DITHIOLANE , *ANTI-infective agents - Abstract
Novel 2-cyano-N-[1-(naphtha-2-yl)ethylidene] acetohydrazide1was utilized as key intermediate for the synthesis of some new dithiolane, thiophene, coumarin, 2-pyridone, and other related products containing a hydrazide moiety. Newly synthesized compounds were characterized by elemental analyses and spectral data (IR,1H NMR and mass spectra). The antimicrobial activity of the synthesized compounds was evaluated. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
25. 1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers.
- Author
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Raghuvanshi, Abhinav, Dargallay, Nakaw, Knorr, Michael, Viau, Lydie, Knauer, Lena, and Strohmann, Carsten
- Subjects
- *
LIGAND analysis , *MOLECULAR self-assembly , *DITHIOLANE , *MOLECULAR clusters , *COPPER spectra , *COORDINATION polymers - Abstract
The parent compound 1,3-dithiolane L1 reacts with CuI providing the 2D coordination polymer (CP) [{Cu(μ-I)Cu}(μ- L1)] ( CP1). The Cu⋯Cu distance within the Cu(μ-I)Cu rhomboid is temperature-dependent and shrinks from 2.9081(7) (294 K) to 2.8743(5) (100 K). The 1D polymeric compound [{Cu(μ-Br)}(μ- L1)] ( CP2) was isolated upon treatment of CuBr with L1 in MeCN solution. Likewise, treatment of L1 with CuCl in a 1:1 ratio results in formation of the unusual 1D CP [{Cu(μ-Cl)}(μ- L1)] ( CP3). In contrast to CP1 incorporating dinuclear Cu(μ-I)Cu units as connection nodes, the isolated Cu atoms of CP2 and CP3 are bridged by a single μ-Br or μ-Cl ligand giving rise to infinite [Cu(μ-X)Cu] ribbons. Reaction of ferrocenecarbaldehyde with 1,2-ethanedithiol affords the crystallographically characterized ferrocenyl-dithiolane Fc-C(H)SCH ( L2). L2 was used as organometallic dithioether ligand to assemble, upon treatment with CuI, the original luminescent 1D CP [{Cu(μ-I)(μ-I)}(μ- L2)] ( CP4), in which both S atoms of one L2 molecule span two copper centers of a meander-shaped infinite (CuI) ribbon. Upon reaction of L2 with CuBr in a 1:2 ratio, the discrete tetranuclear cluster [{Cu(μ-Br)(μ-Br)}(μ- L2)(MeCN)] ( CL1) is formed. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
26. 1,2-Dithiolane-Derived Dynamic, Covalent Materials: Cooperative Self-Assembly and Reversible Cross-Linking.
- Author
-
Xiangyi Zhang and Waymouth, Robert M.
- Subjects
- *
DITHIOLANE , *MACROMOLECULES , *LIPOIC acid , *ANTIOXIDANTS , *CARBOXYLIC acids - Abstract
The use of dithiolane-containing polymers to construct responsive and dynamic networks is an attractive strategy in material design. Here, we provide a detailed mechanistic study on the self-assembly and gelation behavior of a class of ABA triblock copolymers containing a central poly(ethylene oxide) block and terminal polycarbonate blocks with pendant 1,2-dithiolane functionalities. In aqueous solution, these amphiphilic block copolymers self-assemble into bridged flower micelles at high concentrations. The addition of a thiol initiates the reversible ring-opening polymerizations of dithiolanes in the micellar cores to induce the cross-linking and gelation of the micellar network. The properties of the resulting hydrogels depend sensitively on the structures of 1,2-dithiolanes. While the methyl asparagusic acid-derived hydrogels are highly dynamic, adaptable, and self-healing, those derived from lipoic acid are rigid, resilient, and brittle. The thermodynamics and kinetics of ring-opening polymerization of the two dithiolanes were investigated to provide important insights on the dramatically different properties of the hydrogels derived from the two different dithiolanes. The incorporation of both dithiolane monomers into the block copolymers provides a facile way to tailor the properties of these hydrogels. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
27. Green synthesis of novel isatin thioketal derivatives under solvent-free conditions.
- Author
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Imanzadeh, Gholamhassan, Banaei, Alireza, Fathi, Taarof, and Soltanzadeh, Zahra
- Subjects
- *
ISATIN , *INDOLE , *MICHAEL reaction , *ALKYLATION , *DITHIOLANE - Abstract
A new series of spiro[[1,3]dithiolane-2,3′-indolines]-2′-one derivatives was synthesized using Michael addition reaction of spiro[[1,3]dithiolane-2,3′-indolin]-2′-one to various α,β-unsaturated esters as well as direct alkylation of this compound with alkyl dihalides. Michael reaction of spiro[[1,3]dithiolane-2,3′-indolin]-2′-one and α,β-unsaturated esters produced related Michael adduct in the presence of tetrabutylammonium bromide and base 1,4-diazabicyclo[2.2.2]octane in good to excellent yields at 80°C under solvent-free conditions. Also, direct alkylation of spiro[[1,3]dithiolane-2,3′-indolin]-2′-one by dihaloalkanes in the presence of base K2CO3afforded the corresponding products in good yields under the same conditions. [ABSTRACT FROM PUBLISHER]
- Published
- 2017
- Full Text
- View/download PDF
28. The reactivity of (Me3Si)3SiH with sulfoxides under free radical conditions.
- Author
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Chatgilialoglu, Chryssostomos and Ferreri, Carla
- Subjects
- *
REACTIVITY (Chemistry) , *SULFOXIDES , *FREE radicals , *DITHIOLANE , *ABSTRACTION reactions - Abstract
The radical-initiated reaction of (Me 3 Si) 3 SiH with a variety of sulfoxides has been investigated. The reactivity varies significantly with the nature of the starting materials. The reactions of diaryl sulfoxides provide the corresponding sulfides in high yields while the related reactions with dialkyl sulfoxides occur more slowly and in moderate yields. The rate constant for the addition of (Me 3 Si) 3 Si radical with dibutyl sulfoxide is in the range 10 3 –10 4 M −1 s −1 at 80 °C. The reactivity of (Me 3 Si) 3 SiH with 1,3-dithiolane derivatives has also been investigated in a comparative study. The 2,2-dimethyl-1,3-dithiolane and the corresponding 1,1-dioxide give very smooth reaction with (Me 3 Si) 3 Si radical attack at sulfur followed by the ring opening at S–CMe 2 bond and subsequent H-abstraction from the silane in very high yield, whereas the 2,2-dimethyl-1,3-dithiolane-1-oxide behaves quite differently and unexpectedly. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
29. Dithiolane-Crosslinked Poly(ε-caprolactone)-Based Micelles: Impact of Monomer Sequence, Nature of Monomer, and Reducing Agent on the Dynamic Crosslinking Properties
- Author
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Liu, Yanna, Van Steenbergen, Mies J., Zhong, Zhiyuan, Oliveira, Sabrina, Hennink, Wim E., Van Nostrum, Cornelus F., Afd Pharmaceutics, and Afd Pharmaceutics
- Subjects
Polymers and Plastics ,Reducing agent ,Sequence (biology) ,02 engineering and technology ,macromolecular substances ,010402 general chemistry ,01 natural sciences ,Micelle ,Article ,Dithiolane ,Inorganic Chemistry ,chemistry.chemical_compound ,Polymer chemistry ,Copolymer ,Materials Chemistry ,chemistry.chemical_classification ,Organic Chemistry ,technology, industry, and agriculture ,Polymer ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Monomer ,chemistry ,0210 nano-technology ,Caprolactone - Abstract
Dithiolanes are used to obtain dynamic and reversible crosslinks between polymer chains. Copolymers of two different dithiolane-containing cyclic carbonate monomers and ϵ-caprolactone (CL) were synthesized by ring-opening polymerization using a methoxy-poly(ethylene glycol) (mPEG) initiator and different catalysts (diphenyl phosphate (DPP), methanesulfonic acid (MSA), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), or Sn(Oct)2). Each catalyst required a different temperature, which had a pronounced influence on the reactivity ratio of the monomers and occurrence of transesterification reactions and, therefore, the monomer sequence. Self-crosslinkable copolymers were obtained when the dithiolane units were connected closely to the polymer backbone, whereas the presence of a linker unit between the dithiolane and the backbone prevented self-crosslinking. The former amphiphilic PEGylated block copolymers formed micelles by nanoprecipitation in the aqueous environment and crosslinked spontaneously by disulfide exchange during subsequent dialysis. These dithiolane-crosslinked micelles showed reduction-responsive dissociation in the presence of 10 mM glutathione, making them promising drug delivery systems for the intracellularly triggered cargo release.
- Published
- 2020
30. Polyethersulfone microfiltration membrane modified by an amphiphilic dithiolane‐containing copolymer for improving anti‐protein‐fouling performance and rejection of nanoparticles
- Author
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Tong Wu, Lizong Dai, Birong Zeng, Chen Ting, Weiang Luo, Yiting Xu, Liu Xinyu, Hong Shen, Conghui Yuan, Guorong Chen, and Wang Xiao
- Subjects
chemistry.chemical_compound ,Materials science ,Polymers and Plastics ,chemistry ,Chemical engineering ,Fouling ,Microfiltration ,Microfiltration membrane ,Amphiphile ,Copolymer ,Nanoparticle ,Dithiolane - Published
- 2020
31. Crystal structure of the coordination polymer catena-poly[[[(acetonitrile-κN)copper(I)]-μ3-1,3-dithiolane-κ3S:S:S′] hexafluoridophosphate]
- Author
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Carsten Strohmann, Lena Knauer, Lydie Viau, Michael Knorr, Technische Universität Dortmund [Dortmund] (TU), Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), and Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)
- Subjects
crystal structure ,Coordination polymer ,chemistry.chemical_element ,Crystal structure ,c—h...f hydrogen bonding ,010402 general chemistry ,010403 inorganic & nuclear chemistry ,01 natural sciences ,thioether ,Dithiolane ,chemistry.chemical_compound ,[CHIM.CRIS]Chemical Sciences/Cristallography ,General Materials Science ,Acetonitrile ,copper complex ,Crystallography ,Hydrogen bond ,Ligand ,Cationic polymerization ,C-H…F hydrogen bonding ,General Chemistry ,Condensed Matter Physics ,Copper ,3. Good health ,0104 chemical sciences ,Thioether ,coordination polymer ,chemistry ,QD901-999 - Abstract
The polymeric title compound, [Cu2(C2H3N)2(C3H6S2)2](PF6)2, represents an example of a one-dimensional coordination polymer resulting from the reaction of [Cu(MeCN)4][PF6] with 1,3-dithiolane. The cationic one-dimensional ribbon consists of two copper(I) centers each ligated by one acetonitrile molecule and interconnected through two bridging 1,3-dithiolane ligands. One S-donor site of each ligand is κ1-bound to Cu, whereas the second S atom acts as a four-electron donor, bridging two Cu atoms in a κ4-bonding mode. The positive charge of each copper cation is compensated for by a hexafluoridophosphate counter-ion. In the crystal, the polymer chains are linked by a series of C—H...F hydrogen bonds, forming a supramolecular framework, Acta Acta crystallographica / IUC, International Union of Crystallography. Section E, Crystallographic communications;(2020). E76, 38-41
- Published
- 2020
32. Dithiolane quartets: thiol-mediated uptake enables cytosolic delivery in deep tissue
- Author
-
Javier López-Andarias, Quentin Laurent, Stefan Matile, Rémi Martinent, Dimitri Moreau, and Salman Tawffik
- Subjects
chemistry.chemical_classification ,Streptavidin ,Supramolecular chemistry ,Transferrin receptor ,General Chemistry ,Amino acid ,Dithiolane ,chemistry.chemical_compound ,Chemistry ,chemistry ,Transcytosis ,Covalent bond ,ddc:540 ,Biophysics ,Peptide sequence - Abstract
The cytosolic delivery of various substrates in 3D multicellular spheroids by thiol-mediated uptake is reported. This is important because most orthodox systems, including polycationic cell-penetrating peptides, fail to deliver efficiently into deep tissue. The grand principles of supramolecular chemistry, that is the pH dependence of dynamic covalent disulfide exchange with known thiols on the transferrin receptor, are proposed to account for transcytosis into deep tissue, while the known but elusive exchange cascades along the same or other partners assure cytosolic delivery in kinetic competition. For quantitative detection in the cytosol, the 2D chloroalkane penetration assay (CAPA) is translated to 3D deep tissue. The targeted delivery of quantum dots, otherwise already troublesome in 2D culture, and the controlled release of mechanophores are realized to exemplify the power of thiol-mediated uptake into spheroids. As transporters, dithiolane quartets on streptavidin templates are introduced as modular motifs. Built from two amino acids only, the varied stereochemistry and peptide sequence are shown to cover maximal functional space with minimal structural change, i.e., constitutional isomers. Reviving a classic in peptide chemistry, this templated assembly of β quartets promises to expand streptavidin biotechnology in new directions, while the discovery of general cytosolic delivery in deep tissue as an intrinsic advantage further enhances the significance and usefulness of thiol-mediated uptake., Cytosolic delivery in multicellular 3D spheroids is shown to be an intrinsic advantage of thiol-mediated uptake, which is compatible with proteins and QDs, achieving targeting and controlled release.
- Published
- 2021
33. Electro-assisted Deposition of Binary Self-Assembled 1,2-Dithiolane Monolayers on Gold with Predictable Composition.
- Author
-
Capitao, Dany, Sahli, Rihab, Raouafi, Noureddine, Limoges, Benoit, Fave, Claire, and Schöllhorn, Bernd
- Subjects
GOLD electrodes ,DITHIOLANE ,TRANSITION metals ,MONOMOLECULAR films ,CHEMICAL derivatives - Abstract
A reproducible electro-assisted method was proposed for the fast and well-controlled formation of mixed binary 1,2-dithiolane-based self-assembled monolayers (SAMs) on a gold electrode from micromolar adsorbate solution concentrations. This was made possible by the combined use of 1,2-dithiolane derivatives having comparable surface binding affinities and the application of a moderate cathodic potential to the electrode until an equilibrium binary SAM coverage was reached. Dithiolane derivatives containing distinct redox-active ferrocenyl groups were synthesized and used for simultaneous and quantitative electrochemical monitoring of the formation of the binary SAMs. The corresponding separate electrochemical responses of each component in the mixed layer allowed for the determination of the adsorbate ratio, which afforded the overall and the individual chemisorption kinetics. Regardless of the different adsorption kinetics, the resulting adsorbate ratios at equilibrium in the SAM were found to be the same as those in solution. Upon reporting the equilibrium surface concentration of the adsorbate as a function of its mole fraction in solution, a clear-cut linear relationship was obtained, which makes this method particularly useful for controlling and predicting the chemical composition of functional binary SAMs on gold surfaces. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
34. Gd(III)-Dithiolane Gold Nanoparticles for T1-Weighted Magnetic Resonance Imaging of the Pancreas.
- Author
-
Holbrook, Robert J., Rammohan, Nikhil, Rotz, Matthew W., MacRenaris, Keith W., Preslar, Adam T., and Meade, Thomas J.
- Subjects
- *
DITHIOLANE , *GOLD nanoparticles , *MAGNETIC resonance imaging , *PANCREAS , *ADENOCARCINOMA - Abstract
Pancreatic adenocarcinoma has a 5 year survival of approximately 3% and median survival of 6 months and is among the most dismal of prognoses in all of medicine. This poor prognosis is largely due to delayed diagnosis where patients remain asymptomatic until advanced disease is present. Therefore, techniques to allow early detection of pancreatic adenocarcinoma are desperately needed. Imaging of pancreatic tissue is notoriously difficult, and the development of new imaging techniques would impact our understanding of organ physiology and pathology with applications in disease diagnosis, staging, and longitudinal response to therapy in vivo. Magnetic resonance imaging (MRI) provides numerous advantages for these types of investigations; however, it is unable to delineate the pancreas due to low inherent contrast within this tissue type. To overcome this limitation, we have prepared a new Gd(III) contrast agent that accumulates in the pancreas and provides significant contrast enhancement by MR imaging. We describe the synthesis and characterization of a new dithiolane-Gd(III) complex and a straightforward and scalable approach for conjugation to a gold nanoparticle. We present data that show the nanoconjugates exhibit very high per particle values of r1 relaxivity at both low and high magnetic field strengths due to the high Gd(III) payload. We provide evidence of pancreatic tissue labeling that includes MR images, post-mortem biodistribution analysis, and pancreatic tissue evaluation of particle localization. Significant contrast enhancement was observed allowing clear identification of the pancreas with contrast-to-noise ratios exceeding 35:1. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
35. New application of cross-linked poly( N -bromoacrylamide) and poly( N -bromosuccinimide) as highly efficient and chemoselective heterogeneous polymeric catalysts for deprotection of 1,3-dithianes and 1,3-dithiolanes under mild conditions.
- Author
-
Ebrahimzadeh, Farzaneh
- Subjects
- *
CROSSLINKED polymers , *BROMOSUCCINIMIDE , *HETEROGENEOUS catalysis , *CHEMOSELECTIVITY , *DITHIANE , *DITHIOLANE - Abstract
Cross-linked poly(N-bromoacrylamide) (PNBA) and poly(N- bromosuccinimide) as the mild and efficient heterogeneous polymeric catalysts were applied for selective deprotection of 1,3-dithianes and 1,3-dithiolanes to their corresponding carbonyl compounds. They were also effective as a reagent in aqueous media. These methods are very simple and the polymer catalysts could be recycled several times. Deprotection of thioacetal and thioketal without enolizable hydrogens proceeded very well to give only the corresponding aldehyde and ketone in high to excellent yield. Nevertheless, in the case of thioketals carrying enolizable hydrogens, deprotection accompanied with the formation of a minor ring-expanded product is observed. However, using the PNBA/H2O system, ring expansion of these thiolketals with enolizable hydrogen was not detected. These methods provide advantages, such as chemoselectivity, easy preparation, simple work up, excellent yields, and the ability to recycle the catalyst, which makes this method more useful compared to other known methodologies. [ABSTRACT FROM PUBLISHER]
- Published
- 2016
- Full Text
- View/download PDF
36. Switchable and reversible superhydrophobic and oleophobic surfaces by redox response using covalent S–S bond.
- Author
-
Godeau, Guilhem, Darmanin, Thierry, and Guittard, Frédéric
- Subjects
- *
SUPERHYDROPHOBIC surfaces , *OXIDATION-reduction reaction , *COVALENT bonds , *SULFUR , *DITHIOLANE , *POLYTHIOPHENES - Abstract
Here we report for the first time the use of dithiolane as a platform for reversible surface functionalization with switchable water and oil-wettability. That platform allows the preparation of switchable superhydrophobic/hydrophilic surfaces and oleophobic/oleophilic surfaces. Based on a poly(3,4-ethylenedioxythiophene) surface bearing dithiolane groups, this strategy allows the obtainment of reversible functionalization of surfaces with various thiol compounds. Interestingly, the use of fluorinated thiols also highly changes the surface morphology and porosity leading to superhydrophobic properties and highly oleophobic properties with water and oil reversibility. Dithiolane surfaces are the key platforms in order that switchable surfaces are prepared for a large range of applications. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
37. Covalent Adaptable Liquid Crystal Networks Enabled by Reversible Ring-Opening Cascades of Cyclic Disulfides
- Author
-
Hari Krishna Bisoyi, Shuai Huang, Yikang Shen, Zhong-Cheng Liu, Hong Yang, Meng Wang, Quan Li, and Yu Tao
- Subjects
chemistry.chemical_classification ,Depolymerization ,Soft robotics ,Nanotechnology ,General Chemistry ,Polymer ,Metathesis ,Biochemistry ,Catalysis ,Dithiolane ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,chemistry ,Polymerization ,Liquid crystal ,Covalent bond - Abstract
The development of covalent adaptable liquid crystal networks (LCNs) enabled by introducing dynamic covalent bonds has endowed liquid crystal actuators with self-healing properties and reversible shape programmability, broadening their applications in diverse soft robotic devices. However, the finite molecular design strategy limits the recyclability and the architectural diversity of these materials. Here, a strategy is first reported for fabricating photoresponsive polydisulfide-based covalent adaptable LCNs by ring-opening polymerization of cyclic dithiolane groups. Based on the disulfide metathesis, the resulting materials are self-healable, reshapable, and reprogrammable. Importantly, the equilibrium between the polymer backbones and the dithiolane-functionalized monomers enables catalytic depolymerization to recycle monomers, which could significantly weaken the disadvantage of subtractive manufacturing of photomechanical devices. This work rooted in chemistry would provide an economical and environmentally friendly strategy for the fabrication of functional soft robotics with excellent programmability and renewability and beyond.
- Published
- 2021
38. A Convenient Synthesis of Dithiolane and Benzyloximates Derivatives for Ligand Studies
- Author
-
Michael B. Jacobsson, Chinwon Rim, David Y. Son, and Sudershan R. Gondi
- Subjects
chemistry.chemical_compound ,chemistry ,Hydroquinone ,Ligand ,medicine ,Organic chemistry ,Moiety ,Halide ,Ether ,Alkylation ,Chloride ,Dithiolane ,medicine.drug - Abstract
We report the synthesis of new aromatic derivatives containing the 1,3-dithiolane ether and benzyloximino moiety which are attached by simple alkylation and esterification reaction by treating 1,3-dithiolane-2-methanol and a-benzyloximino acid chloride respectively with various aromatic halides and alcohols, respectively. The isolated yields of these compounds range from 65 to 85%. 1,3-dithiolane ether and the benzyloxy substituted hydroquinone are white solids or residual oil and stable to air and moisture.
- Published
- 2021
39. A Convenient Synthesis and Spectral Studies of Diamines Derivatives
- Author
-
Gondi, David Y. Son, Rissing Cj, and Jacobsson Mb
- Subjects
Steric effects ,Electron transfer ,chemistry.chemical_compound ,chemistry ,Amide ,Diamine ,Moiety ,Amine gas treating ,Absorption (chemistry) ,Medicinal chemistry ,Dithiolane - Abstract
A new series of substituted anthranilic esters derivatives linked with a 1,3-dithiolane andbenzyloximino moiety was synthesized using the simple esterfication reaction and products werefully characterized. The isolated yields of these compounds range from 59 to 96%. 1,3-dithiolane ester and the benzyloxy substituted diamine derivatives are white solids and stable toair and moisture. The synthesized compounds can be exhibits UV-vis absorption properties bytheir structures with a amine or amide group, It is observed that absorption maximum is excellentfor 2,6-disubstituted benzyloxy esters which can be explained by electron transfer or conjugationis steric effect in ortho substitution from the amino group and the amide group.
- Published
- 2021
40. Site-Specific Incorporation of a Dithiolane Containing Amino Acid into Proteins
- Author
-
Chenguang Yu, Hyeon-Yeol Cho, Sei-hyun Choi, Peter G. Schultz, Ki-Bum Lee, and Minseob Koh
- Subjects
Stereochemistry ,Green Fluorescent Proteins ,Mutant ,Biomedical Engineering ,Metal Nanoparticles ,Pharmaceutical Science ,Bioengineering ,02 engineering and technology ,Protein Engineering ,medicine.disease_cause ,01 natural sciences ,Dithiothreitol ,Dithiolane ,Green fluorescent protein ,Amino Acyl-tRNA Synthetases ,chemistry.chemical_compound ,Escherichia coli ,medicine ,Amino Acids ,Pharmacology ,chemistry.chemical_classification ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Amino acid ,Transfer RNA ,Mutagenesis, Site-Directed ,Gold ,0210 nano-technology ,Biotechnology ,Cysteine - Abstract
We have genetically encoded a dithiolane containing amino acid (dtF) in Escherichia coli (E. coli) using a polyspecific aminoacyl-tRNA synthetase (aaRS)/amber suppressor tRNA pair. To demonstrate the utility of dtF for bioapplications, we synthesized gold nanoparticle (AuNP) constructs with a mutant superfolder green fluorescent protein (sfGFP) [sfGFP-AuNP] as a model for the protein-metal conjugation. The resulting sfGFP-AuNP constructs show directional homogeneity and enhanced chemical durability compared to their cysteine analogues toward excess environmental 1,4-dithiothreitol (DTT).
- Published
- 2019
41. Study on Corrosion Inhibition Performance of 1,2-Dithiolane-3- pentanoicacid on X65 Steel in 0.5 M Sulfuric Acid
- Author
-
Shiying Tao
- Subjects
chemistry.chemical_compound ,chemistry ,Electrochemistry ,Sulfuric acid ,Corrosion ,Nuclear chemistry ,Dithiolane - Published
- 2019
42. Preparation 2-(anthracen-9-yl)-1,3-dithiolane as a novel dual-channel AIE-active fluorescent probe for mercury (II) ion with excellent performance
- Author
-
Cuihong Zhang, Weiguo Zheng, Manman Zhang, Yao Xiao, Shuping Zhang, Qingyang Wang, and Jie Ma
- Subjects
General Chemical Engineering ,Metal ions in aqueous solution ,General Physics and Astronomy ,chemistry.chemical_element ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,Fluorescence ,0104 chemical sciences ,Mercury (element) ,Ion ,Dithiolane ,Solvent ,chemistry.chemical_compound ,chemistry ,Molecule ,0210 nano-technology ,Selectivity - Abstract
A novel fluorescent probe molecule, 2-(anthracen-9-yl)-1,3-dithiolane (AADT), is designed and synthesized for Hg2+ detection successfully, based on a good aggregation induced emission (AIE) fluorescent mechanism and a specific reaction type. DMF-H2O mixed solvent (Fw 80% V/V) is suitable to disperse AADT for forming 1 × 10−5 mol L−1 solution with an AIE-active fluorescence probe system. Meanwhile, 9-Anthraldehyde also presents good fluorescence at same condition. With the increase of trace Hg (II), the AADT probe shows dual-channel, (turn-off at 429 nm, and turn–on at 511 nm) fluorescence probe character. (R2 > 0.994), which does not interfere each other. The probe demonstrates excellent selectivity, anti-inference properties, and several metal ions and acid ions hardly affect its performance. The LOD of the AADT probe is lower than 2.34 × 10−8 mol L−1, and proper to many common AIE-active probes.
- Published
- 2019
43. Evaluating the role of dithiolane rich fraction of Ferula asafoetida (apiaceae) for its antiproliferative and apoptotic properties: in vitro studies
- Author
-
Pinakin Khambhala, Kothari, Joshi S, Sriram Seshadri, Shailja Verma, and Patel T
- Subjects
Cancer Research ,Apoptosis ,law.invention ,Dithiolane ,Transforming Growth Factor beta1 ,03 medical and health sciences ,chemistry.chemical_compound ,0302 clinical medicine ,law ,Cell Line, Tumor ,Oils, Volatile ,Humans ,Plant Oils ,Essential oil ,Adaptor Proteins, Signal Transducing ,Cell Proliferation ,Apiaceae ,biology ,Caspase 3 ,Chemistry ,Liver Neoplasms ,NF-kappa B ,NF-kappa B p50 Subunit ,Proteins ,Hep G2 Cells ,biology.organism_classification ,In vitro ,Ferula ,Reverse transcription polymerase chain reaction ,Oncology ,Biochemistry ,Phytochemical ,Cell culture ,030220 oncology & carcinogenesis ,Resins, Plant ,Signal Transduction - Abstract
Asafoetida resin has been reported for various biological activities but its use has been widely restricted owing to its pungent smell and pool water solubility. AIM In vitro study of the anticancer potential of microwave-extracted essential oil (EO) of Ferula asafoetida. MATERIALS AND METHODS The phytochemical investigation and in vitro cytotoxicity assessment was carried out in two human liver cancer cell lines. The expression of NFKB1, TGFB1, TNF, CASP3 was analyzed by reverse transcription polymerase chain reaction. RESULTS Ferula asafoetida EO contains high concentrations of dithiolane, which possess antiproliferative activity in human liver carcinoma cell lines (HepG2 and SK-Hep1) in a dose-dependent manner. The bioactive compounds in F. asafoetida are capable of induction of apoptosis and altered NF-kB and TGF-β signalling with increase in caspase-3 and TNF-α expression. CONCLUSION Further elucidation of bioactive molecules and underlying mechanisms could lead to potential intervention in liver cancer in animal models. The safety and efficacy as well as the mode of EO action in animal models would be highly crucial.
- Published
- 2019
44. Synthesis and Biological Evaluation of Some New Thiophene, Thiazole, Dithiolane Derivatives and Related Compounds
- Author
-
Ahmed A. Fadda, Eman H. Tawfik, and Yasser A. Selim
- Subjects
Polymers and Plastics ,010405 organic chemistry ,Organic Chemistry ,Sulfanilamide ,010402 general chemistry ,Mass spectrometry ,01 natural sciences ,0104 chemical sciences ,Dithiolane ,chemistry.chemical_compound ,chemistry ,Elemental analysis ,Materials Chemistry ,medicine ,Thiophene ,Proton NMR ,Organic chemistry ,Thiazole ,medicine.drug ,Biological evaluation - Abstract
A series of novel of heterocycles containing thiazole, thiophene moieties, and dithiolane derivatives were designed, synthesized, and characterized by 1H NMR, IR, elemental analysis, and mass spect...
- Published
- 2018
45. Synthesis of Conformationally Locked and C-Linked Analogues of Imidazole-Based Ketene Dithioacetal Fungicides
- Author
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Olivier Jacob, Stephane Jeanmart, Clemens Lamberth, Julien Daniel Henri Gagnepain, and Damien Bonvalot
- Subjects
chemistry.chemical_classification ,Double bond ,010405 organic chemistry ,Stereochemistry ,Luliconazole ,Organic Chemistry ,Ketene ,010402 general chemistry ,Ring (chemistry) ,01 natural sciences ,0104 chemical sciences ,Dithiolane ,chemistry.chemical_compound ,chemistry ,Imidazole ,Sterol biosynthesis ,Tricyclic - Abstract
First examples with the unknown tricyclic 4,8b-dihydro-3aH-indeno[1,2-d][1,3]dithiole ring system have been prepared. Also, imidazoles linked in ring position 5 to a ketene dithioacetal and 1,3-dithiane derivatives with an exocyclic cyano- and imidazole-substituted C–C double bond are completely new. All these compounds are either conformationally locked, C-linked or six-ring analogues of the antifungal agent luliconazole. Synthesis and fungicidal activity of these sterol biosynthesis inhibitors are reported.
- Published
- 2018
46. Synthesis and spectroscopic characterization of 5-diaminomethylidene barbiturates
- Author
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Figueroa-Villar José D., Clemente Fábio C., and Silva Ana C. C. da
- Subjects
macrocycles ,diaminomethylidene barbiturates ,dithiocyclohexylidenes ,dithiolane ,Chemistry ,QD1-999 - Abstract
The reaction of amines with dithiocyclohexylidenes is a general reaction for the synthesis of diaminomethylidene barbiturates. When diamines of the type H2N-(CH2)n-NH 2 are used as nucleophiles bicyclic compounds are the major reaction products, with yields increasing as n decreases, n = 2, 3, 4. When n = 6, macrocyclic compounds, novel 18 and 27 member rings, are obtained in very good yields. The ¹H and 13C NMR assignment for all products is discussed.
- Published
- 2001
47. Electrogenerated base-promoted synthesis and antimicrobial activity of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiolan-2-ylidene)-2-arylacetonitrile.
- Author
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Hamrouni, Kaouthar, Saied, Taieb, El Abed, Nariman, Ahmed, Sami Ben Hadj, Boujlel, Khaled, and Khoud, Mohamed Lamine Ben
- Subjects
- *
ANTI-infective agents , *DITHIANE , *ACETONITRILE synthesis , *DITHIOLANE , *CHEMICAL sample preparation , *ELECTROLYTIC reduction - Abstract
The new preparation of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiol-2-ylidene)-2-arylacetonitrile is described. The electrogenerated cyanomethyl base/anion obtained from the electroreduction of acetonitrile promotes reactions between arylacetonitrile, carbon disulfide and 1-bromo-3-chloropropane or 1,2-dibromoethane. Obtained products have been identified according to their spectroscopic data (IR and1H NMR and13C NMR) and elemental analysis. The possible antibacterial activities of some of these compounds were investigated. Promising results were found against few types of bacteria. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
48. Chemo- and stereo-selectivity in oxidation of fluorinated cyclic sulfides by m-chloroperoxybenzoic acid.
- Author
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Petrov, Viacheslav A. and Marshall, Will
- Subjects
- *
STEREOSELECTIVE reactions , *CHEMOSELECTIVITY , *FLUORINATION , *BENZOIC acid , *DITHIOLANE , *ISOMERS - Abstract
Controlled oxidation of various hexafluorothioacetone cycloadducts by m -chloroperoxybenzoic acid (MCPBA) at low temperature led to the formation of the corresponding cyclic sulfoxides in 56–82% yield. The oxidation of 5-ethoxy-3,3-bis(trifluoromethyl)-1,2-dithiolane proceeded selectively leading to trans -5-ethoxy-3,3-bis(trifluoromethyl)-1,2-dithiolane-1-oxide, which underwent selective isomerization into the cis -isomer at higher temperature. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
49. Organic-Inorganic Azafullerene-Gold C59N-Au Nanohybrid: Synthesis, Characterization, and Properties.
- Author
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Rotas, Georgios, Niemi, Marja, Tkachenko, Nikolai V., Zhao, Sihan, Shinohara, Hisanori, and Tagmatarchis, Nikos
- Subjects
- *
FULLERENES , *GOLD compound synthesis , *MANNICH reaction , *GOLD nanoparticles , *SURFACE plasmons , *PHOTOLUMINESCENCE , *DITHIOLANE - Abstract
Azafullerene (C59N) was functionalized using a Mannich-type reaction and then subsequently condensed with lipoic acid to yield dithiolane-modified C59N. In the following step, the extended dithiolane moiety from the C59N core was utilized to decorate the azafullerene sphere with gold nanoparticles (Au NPs). The latter were initially stabilized with dodecanothiol (DT ⋅Au) and then integrated on azafullerene through a ligand exchange reaction with the dithiolane-functionalized C59N to produce the C59N/DT ⋅Au nanohybrid. The nanohybrid was fully characterized by spectroscopy and microscopy, revealing the formation of spherical nanoparticles with a diameter in the range of 2-5 nm, as imaged by HR-TEM. In the electronic absorption spectrum of C59N/DT ⋅Au nanohybrid, the characteristic surface plasmon band (SPB) of Au NPs was observed, however, it was redshifted compared with that of DT ⋅Au. The redshift of the SPB is indicative of closer interparticle proximity of Au NPs, in accordance with the formation of aggregated NPs as observed by TEM, in C59N/DT ⋅Au nanohybrid. Excited-state interactions in C59N/DT ⋅Au were probed by photoluminescence assays. It was found that the weak emission of C59N at 819 nm was blueshifted by 14 nm in C59N/DT ⋅Au, but was stronger in intensity, thus suggesting energy transfer to C59N, within the organic-inorganic C59N/DT ⋅Au nanohybrid. Finally, with the aid of pump-probe measurements and transient absorption spectroscopy, the formation of the singlet excited state of C59N was identified. [ABSTRACT FROM AUTHOR]
- Published
- 2014
- Full Text
- View/download PDF
50. The importance of 1,2-dithiolane structure in a-lipoic acid for the downregulation of cell surface ßl-integrin expression of human bladder cancer cells.
- Author
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Masao Yamasaki, Shozen Soda, Yoichi Sakakibara, Masahito Suiko, and Kazuo Nishiyama
- Subjects
- *
DITHIOLANE , *DOWNREGULATION , *CELL adhesion inhibition , *INTEGRIN genetics , *CELL migration , *GENETIC regulation , *MEMBRANE glycoproteins , *LIPOIC acid , *PREVENTION - Abstract
The article discusses research which examines the importance of 1,2-dithiolane structure in a-lipoic acid for downregulating cell surface βl-integrin expression of human bladder cancer cells. It reports on inhibition of gene expression of cell surface protein βl-integrin, cell adhesion to fibronectin, migration, and invasion by α-lipoic acid. It also discusses on role of 1,2-dithiolane structure in determining the action of α-lipoic acid.
- Published
- 2014
- Full Text
- View/download PDF
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