The fields of phototherapy and inorganic chemotherapy both have long histories. Inorganic photoactivated (PACT) offers temporal spatial control over drug activation has remarkable potential for the treatment cancer. Following photoexcitation, a number different decay pathways (both photophysical photochemical) are available to metal complex. These can result in radiative energy release, loss ligands or transfer another species, such as triplet oxygen. We discuss features which need be...

The low-spin 5d6 IrIII organometallic half-sandwich complexes [(η5-Cpx)Ir(XY)Cl]0/+, Cpx = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cpxph), or tetramethyl(biphenyl)cyclopentadienyl (Cpxbiph), XY 1,10-phenanthroline (4−6), 2,2′-bipyridine (7−9), ethylenediamine (10 and 11), picolinate (12−14), hydrolyze rapidly. Complexes with N,N-chelating ligands readily form adducts 9-ethylguanine but not 9-ethyladenine; bind to both purines. Cytotoxic potency toward A2780 human ovarian cancer cells...

Activating platinum with light: An inert platinum(IV) diazido complex trans, trans,trans-[Pt(N3)2(OH)2(py)2] becomes potently cytotoxic to cancer cells when activated by low doses of visible light. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted the authors. Please note: The publisher is responsible for content functionality any supporting information supplied...

Organometallic half-sandwich complexes [M(p-cymene)(azo/imino-pyridine)X]+ where M = RuII or OsII and X ═ Cl I, exhibit potent antiproliferative activity toward a range of cancer cells. Not only are the iodido more than chlorido analogues, but they not cross-resistant with clinical platinum drugs cisplatin oxaliplatin. They also selective for cells versus normal (fibroblasts) show high accumulation in cell membranes. arrest growth G1 phase contrast to (S phase) incidence late-stage...

A photoactivated ruthenium(II) arene complex has been conjugated to two receptor-binding peptides, a dicarba analogue of octreotide and the Arg-Gly-Asp (RGD) tripeptide. These peptides can act as "tumor-targeting devices" since their receptors are overexpressed on membranes tumor cells. Both ruthenium-peptide conjugates stable in aqueous solution dark, but upon irradiation with visible light, pyridyl-derivatized were selectively photodissociated from ruthenium complex, inferred by UV-vis NMR...

Abstract Six substitutionally inert [Ru II (bipy) 2 dppz] 2+ derivatives (bipy=2,2′‐bipyridine, dppz=dipyrido[3,2‐a:2′,3′‐c]phenazine) bearing different functional groups on the dppz ligand [NH ( 1 ), OMe OAc 3 OH 4 CH 5 Cl 6 )] were synthesized and studied as potential photosensitizers (PSs) in photodynamic therapy (PDT). As also confirmed by DFT calculations, all complexes showed promising O production quantum yields, well comparable with PSs available market. They can efficiently...

A series of four photodissociable Ru polypyridyl complexes general formula [Ru(bpy)2L2](2+), where bpy = 2,2'-bipyridine and L 4-aminopyridine (1), pyridine (2), butylamine (3), gamma-aminobutyric acid (4), was studied by density functional theory (DFT) time-dependent (TDDFT). DFT calculations (B3LYP/LanL2DZ) were able to predict elucidate singlet triplet excited-state properties 1-4 describe the photodissociation mechanism one monodentate ligand. All derivatives display a -->...

Replacing the N,N-chelating ligand 2,2′-bipyridine (bpy) in IrIII pentamethylcyclopentadienyl (Cp*) complex [(η5-C5Me5)Ir(bpy)Cl]+ (1) with C,N-chelating 2-phenylpyridine (phpy) to give [(η5-C5Me5)Ir(phpy)Cl] (2) switches on cytotoxicity toward A2780 human ovarian cancer cells (IC50 values of >100 μM for 1 and 10.8 2). Ir–Cl hydrolysis is rapid both complexes (hydrolysis equilibrium reached <5 min at 278 K). Complex 2 forms adducts 9-ethylguanine (9-EtG) 9-methyladenine (9-MeA), but...

The synthesis and characterization of a family piano-stool RuII arene complexes the type [(η6-arene)Ru(N,N′)(L)][PF6]2, where is p-cymene (p-cym), hexamethylbenzene (hmb), or indane (ind), N,N′ 2,2′-bipyrimidine (bpm), 1,10-phenanthroline (phen), 1,10-phenanthroline-5,6-dione (phendio), 4,7-diphenyl-1,10-phenanthroline (bathophen), L pyridine (Py), 4-methylpyridine (4-MePy), 4-methoxypyridine (4-MeOPy), 4,4′-bipyridine (4,4′-bpy), 4-phenylpyridine (4-PhPy), 4-benzylpyridine (4-BzPy),...

The novel photoactive ruthenium(ii) complex cis-[Ru(bpy)2(INH)2][PF6]2 (1·2PF6, INH = isoniazid) was designed to incorporate the anti-tuberculosis drug, isoniazid, that could be released from Ru(ii) cage by photoactivation with visible light. In aqueous solution, 1 rapidly two equivalents of isoniazid and formed photoproduct cis-[Ru(bpy)2(H2O)2]2+ upon irradiation 465 nm blue We screened for activity against bacteria containing three major classes cell envelope: Gram-positive Bacillus...

Cyclopentadienyl (Cp) Ru(IV) quinoline complexes are known for their role in bioorthogonal catalysis within cellular environments, where they use endogenous GSH to deprotect profluorescent and prodrug substrates. However, reactivity toward potential redox-mediated therapies remain underexplored. This study presents RuQ-TARF, a Cp-Ru(IV) complex with ligand linked 2',3',4',5'-tetraacetylriboflavin (TARF) as redox-active moiety. Its catalytic activity oxidizing activating Pt(IV) of oxaliplatin...

Three new Re(CO)3Cl complexes (ReL1−ReL3) containing the N,N-bidentate ligands 1-(2-pyridyl)-3-phenylimidazo[1,5-a]pyridine (L1), 1-(2-pyridyl)-3-(4-tert-butylphenyl)imidazo[1,5-a]pyridine (L2), and 1-(2-pyridyl)-3-(4-dimethylaminophenyl)imidazo[1,5-a]pyridine (L3) were synthetized fully characterized. Photophysical properties of L1−L3 ReL1−ReL3 studied with absorption emission spectroscopy. The X-ray structure ReL3 was determined. Time-dependent DFT (TDDFT) calculations performed in order...

The complex [(p-cym)Ru(bpm)(py)][PF6]2 (where p-cym = para-cymene, bpm 2,2′-bipyrimidine and py pyridine) is the first ruthenium(II) arene that can selectively photodissociate a monodentate ligand (py) when excited with visible light form reactive aqua derivative able to bind DNA base.

Abstract Platinum diam(m)ine complexes, such as cisplatin, are successful anticancer drugs, but suffer from problems of resistance and side‐effects. Photoactivatable Pt IV prodrugs offer the potential targeted drug release new mechanisms action. We report synthesis, X‐ray crystallographic spectroscopic properties photoactivatable diazido complexes trans , ‐[Pt(N 3 ) 2 (OH) (MA)(Py)] ( 1 ; MA=methylamine, Py=pyridine) (MA)(Tz)] Tz=thiazole), interpret their photophysical by TD‐DFT modelling....

Abstract Polypyridyl metal complexes have optical properties that been exploited in a wide range of biological and technological applications. Their structural diversity, chemical redox provide unique opportunity for designing new anticancer agents. Despite this great potential, relatively little is known about the cytotoxic effects polypyridyl complexes, at least comparison with other classes coordination organometallic compounds. This review uses selected examples to illustrate most recent...

Abstract Photoactivatable PtIV diazido complexes have unusual photobiologic properties. We show here that trans,trans,trans-[PtIV(N3)2(OH)2(py)(NH3)] complex 3 is a potent photoactivated cytotoxin toward human cancer cells in culture, with an average IC50 value 13 cell lines of 55 ± 28 μmol/L after 30 minutes (0.12 mW/cm2) photoactivation UVA, although visible light was also effective. Photoactivated noncross-resistant to cisplatin 4 resistant lines. Cell swelling but very little blebbing...

Abstract Organometallic gold complexes with N‐heterocyclic carbene (NHC) ligands have been demonstrating promising properties as novel anticancer agents. Gold(I) NHC containing different phosphanes secondary were shown to trigger strong cytotoxic effects in cancer cells, and their effective uptake into the cells was quantified by atomic absorption spectroscopy. Moreover, new compounds strongly inhibited activity of seleno‐enzyme thioredoxin reductase (TrxR) zinc‐finger enzyme...

Recent advances in bioorthogonal catalysis promise to deliver new chemical tools for performing chemoselective transformations complex biological environments. Herein, we report how FAD (flavin adenine dinucleotide), FMN mononucleotide), and four flavoproteins act as unconventional photocatalysts capable of converting PtIV RuII complexes into potentially toxic PtII or -OH2 species. In the presence electron donors low doses visible light, mini singlet oxygen generator (miniSOG) NADH oxidase...

Riboflavin acts as bioorthogonal photocatalyst to activate a Pt^IV anticancer prodrug in the biological environment.

In situ activation of Pt(IV) to Pt(II) species is a promising strategy control the anticancer activity and overcome off-target toxicity linked classic platinum chemotherapeutic agents. Herein, we present design synthesis two new asymmetric derivatives cisplatin oxaliplatin (1·TARF 2·TARF, respectively) bearing covalently bonded 2',3',4',5'-tetraacetylriboflavin moiety (TARF). 1H 195Pt NMR spectroscopy shows that 1·TARF 2·TARF can be effectively activated into toxic species, when incubated...

The new complex [Ru(bpy)(4AP)4]2+ (1), where bpy = 2,2′-bipyridine and 4AP 4-aminopyridine, undergoes selective photodissociation of two 4APs upon light excitation the metal−ligand-to-ligand charge-transfer (MLLCT) band at 510 nm. photoproducts reaction are mer-[Ru(bpy)(4AP)3(H2O)]2+ (2a) trans-(4AP)[Ru(bpy)(4AP)2(H2O)2]2+ (3a). Photodissociation occurs in consecutive steps with quantum yields φ1 (6.1 ± 1.0) × 10−3 φ2 (1.7 0.1) 10−4, respectively. Complex 1 was characterized by combined...

The Pt(IV) complex cis,cis,trans-[Pt(NH3)2(Cl)2(O2CCH2CH2CO2H)2] is photoactivated by near infrared light (980 nm) using NaYF4:Yb(3+)/Tm(3+)@NaYF4 core-shell upconversion nanoparticles. Coupling of this cisplatin precursor with the biocompatible PEGylated phospholipid DSPE-PEG(2000)-NH2 affords a valuable approach to decorate surface nanoparticles, providing novel photoactivatable nanomaterials capable releasing Pt(II) species upon NIR excitation.