Related Experiment Video
Updated: Jun 14, 2025
10:51
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
12.1K
Fine-tuning the Photochemistry of Sulfur-Based Linkages with Ruthenium(II) Polypyridyl Complexes for Optimal PACT
Ramranjan Mishra1, Pritha Chatterjee1, Madhu Verma2
1Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, 208016, India.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|June 12, 2025
Summary
Thioether ligands in ruthenium(II)-polypyridyls show enhanced photorelease and photocytotoxicity for photoactivated chemotherapy (PACT). These complexes offer improved options for photocaging prodrugs compared to sulfoxide-based systems.
Area of Science:
- Coordination Chemistry
- Photochemistry
- Medicinal Chemistry
Background:
- Thioether ligands are effective in Ru(II)-photocages for photoactivated chemotherapy (PACT).
- Systematic studies comparing photochemical behavior of sulfur linkages (sulfoxides, thioethers) in Ru(II)-polypyridyls are lacking.
Purpose of the Study:
- To synthesize and investigate the photophysical and photochemical properties of Ru(II)-polypyridyls with sulfoxide (DMSO) and thioether (DAS) linkages.
- To compare the photorelease kinetics and photocytotoxicity of these complexes for PACT applications.
Main Methods:
- Synthesis of two Ru(II)-polypyridyl complexes: [Ru(ttpy)(phen)(DMSO)](PF6)2 and [Ru(ttpy)(phen)(DAS)](PF6)2.
- Photolysis studies using UV-vis and 1H NMR spectroscopy.
- In vitro cytotoxicity and photocytotoxicity assays using HeLa and Caco2 cell lines.
Main Results:
- Photosolvolysis studies in MeCN indicated slower substitution of DMSO (sulfoxide) than DAS (thioether).
- Water-soluble complexes showed facile photorelease of DAS compared to DMSO from Ru(II)-photocages.
- [Ru(ttpy)(phen)(DAS)] complexes exhibited significantly higher photocytotoxicity and photoindices than DMSO-based counterparts.
Conclusions:
- Thioether-based Ru(II)-polypyridyls demonstrate superior photorelease kinetics and photocytotoxicity compared to sulfoxide-based systems.
- These findings highlight the potential of thioether-based Ru(II)-polypyridyls as promising candidates for prodrug photocaging and PACT.
- The facile photorelease of DAS contributes to the enhanced photocytotoxicity, supporting their application in targeted cancer therapy.
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
Related Concept Videos
02:26Preparation and Reactions of Sulfides
4.7K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
4.7K
01:26Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
02:33Preparation and Reactions of Thiols
6.0K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.0K
01:22Electrophilic Aromatic Substitution: Sulfonation of Benzene
5.9K
Sulfonation of benzene is a reaction wherein benzene is treated with fuming sulfuric acid at room temperature to produce benzenesulfonic acid. Fuming sulfuric acid is a mixture of sulfur trioxide and concentrated sulfuric acid.
5.9K
01:26Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
1.8K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
1.8K
02:17Structure and Nomenclature of Thiols and Sulfides
4.6K
Thiols and sulfides are sulfur analogs of alcohols and ethers, respectively, where the sulfur atom takes the place of the oxygen atom. Thus, thiols are generally represented as RSH, where R is an alkyl substituent and —SH is the functional group. On the other hand, in sulfides, the central sulfur atom is bonded to two hydrocarbon groups on either side. Depending upon the type of group, sulfides can be either symmetrical or asymmetrical. Both thiols and sulfides display a bent geometry,...
4.6K