In this review, we emphasize the significance of the Liebeskind-Srogl cross-coupling reaction, a palladium-catalyzed process involving the reaction between a thioester and a boronic acid. This reaction has emerged as a fundamental technique in synthetic methodologies aimed at the development of biologically active compounds. The Liebeskind-Srogl cross-coupling method has become an essential approach in chemistry, facilitating the diversification of complex structures that would be significantly more challenging to synthesize through alternative approaches. In this review, we aim to outline the numerous possibilities for preparing a wide range of derivatives, each with notable biological potential.
- Klíčová slova
- Biological activity, Catalysis, Copper, Cross-coupling, C–C bond formation, Heterocycles, Libeskind-Srogl, Medicinal chemistry, Natural products, Organometallic, Organosulfur, Palladium,
- MeSH
- katalýza MeSH
- kyseliny boronové * chemie MeSH
- molekulární struktura MeSH
- palladium chemie MeSH
- techniky syntetické chemie * metody MeSH
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
- Názvy látek
- kyseliny boronové * MeSH
- palladium MeSH
This study introduces a novel, sustainable method for synthesizing sub-5 nm palladium nanoparticles (PdNPs) and covalently binding them to chitosan nanofibers (CHITs) using fully oxidized dialdehyde cellulose (DAC). Notably, the DAC acts not only as a reducing and stabilizing agent for PdNPs, but also as a linker for their rapid and spontaneous covalent attachment to CHITs via Schiff base chemistry. This unique approach yields PdNPs with a narrow size distribution (4.7 ± 0.4 nm) and enables the preparation of a stable nanofibrous composite with excellent catalytic efficiency for 4-nitrophenol reduction (TOFPdNPs = 75.2 min-1, kPdNPs = 1.34 min-1; TOFPdNPs-CHIT = 1.18 min-1). The composite's high reusability, attributed to strong covalent binding, marks a significant improvement over traditional PdNPs composites that rely on weak interactions. This is demonstrated on a model of a catalytic device, reflecting industrial applications.
- Klíčová slova
- Chitosan nanofibers, Dialdehyde cellulose, Nanocomposite catalyst, Palladium nanoparticles,
- MeSH
- celulosa * chemie analogy a deriváty MeSH
- chitosan * chemie MeSH
- katalýza MeSH
- kovové nanočástice * chemie MeSH
- nanovlákna * chemie ultrastruktura MeSH
- nitrofenoly chemie MeSH
- oxidace-redukce MeSH
- palladium * chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- 2,3-dialdehydocellulose MeSH Prohlížeč
- 4-nitrophenol MeSH Prohlížeč
- celulosa * MeSH
- chitosan * MeSH
- nitrofenoly MeSH
- palladium * MeSH
The acidobasic and complexing properties of 1-methyl-2-mercaptoimidazole (Methimazole, an anti-thyroid drug) were investigated. The pKa 11.49 ± 0.03 was estimated by molecular absorption spectroscopy (I = 0.10 M NaCl, t = 25.0 ± 0.1 °C). This value is in good agreement with the value 11.58 ± 0.05, obtained using the solvent-extraction technique. Theoretical (LFER and quantum chemical calculations) and experimental (1H/13C NMR spectroscopy) methods confirmed that the ligand prefers to be in the thion form, and the proton dissociation takes place on the nitrogen atom. Using glass electrode potentiometry, the complexation of the Pd(II) ion by the methimazole ligand occurs without the participation of protons. The best chemical model considers the [Pd(HL)]2+, [Pd(HL)2]2+ and [Pd(HL)3]2+ complex species, whose stability constants were also determined using spectroscopy and capillary zone electrophoretic (CZE) measurements. The metal complexes dissociate at -log [H+] > 7, where an uncharged palladium(II) hydroxide is formed. The formation kinetics of the palladium(II) complex with methimazole were studied in perchloric and hydrochloric acids (I = 1.00 M, t = 15-40 °C) and the determined rate constants and activation parameters are consistent with literature values determined for the reactions of the Pd(II) ion with thiourea derivatives. The rate constants decrease by two orders of magnitude in both media, which can be assigned to a lower tendency of the chloride ion to dissociate from the [PdCl4]2- complex species than the water molecule from the [Pd(H2O)4]2+ ion. The presented results can be utilized for the design of new Pd and Pt metallodrugs.
- Klíčová slova
- Anti-thyroid drug (methimazol, tapazol): 1-methyl-2-mercaptoimidazole, Complexation properties, Equilibria/kinetics, Metallodrug, Pd(II) ion, Protonation,
- MeSH
- kinetika MeSH
- komplexní sloučeniny * chemie chemická syntéza MeSH
- methimazol * chemie MeSH
- palladium * chemie MeSH
- termodynamika * MeSH
- thyreostatika chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- komplexní sloučeniny * MeSH
- methimazol * MeSH
- palladium * MeSH
- thyreostatika MeSH
A series of new indole-pyrazole hybrids 8a-m were synthesized through the palladium-catalyzed ligandless Heck coupling reaction from easily accessible unsubstituted, methoxy- or fluoro-substituted 4-ethenyl-1H-pyrazoles and 5-bromo-3H-indoles. These compounds exerted cytotoxicity to melanoma G361 cells when irradiated with blue light (414 nm) and no cytotoxicity in the dark at concentrations up to 10 µM, prompting us to explore their photodynamic effects. The photodynamic properties of the example compound 8d were further investigated in breast cancer MCF-7 cells. Evaluation revealed comparable anticancer activities of 8d in both breast and melanoma cancer cell lines within the submicromolar range. The treatment induced a massive generation of reactive oxygen species, leading to different types of cell death depending on the compound concentration and the irradiation intensity.
- Klíčová slova
- cytotoxicity, indole, photodynamic effect, pyrazole, reactive oxygen species,
- MeSH
- fotochemoterapie * MeSH
- fotosenzibilizující látky * farmakologie chemická syntéza chemie MeSH
- indoly * farmakologie chemie chemická syntéza MeSH
- lidé MeSH
- MFC-7 buňky MeSH
- molekulární struktura MeSH
- nádorové buněčné linie MeSH
- nádory prsu farmakoterapie patologie MeSH
- palladium chemie farmakologie MeSH
- protinádorové látky * farmakologie chemická syntéza chemie MeSH
- pyrazoly * farmakologie chemická syntéza chemie MeSH
- reaktivní formy kyslíku * metabolismus MeSH
- viabilita buněk účinky léků MeSH
- vztah mezi dávkou a účinkem léčiva MeSH
- vztahy mezi strukturou a aktivitou MeSH
- Check Tag
- lidé MeSH
- ženské pohlaví MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- fotosenzibilizující látky * MeSH
- indoly * MeSH
- palladium MeSH
- protinádorové látky * MeSH
- pyrazoly * MeSH
- reaktivní formy kyslíku * MeSH
A new Pd(II) complex of formula [Pd(en)(2-pyc)]+ (where, en is ethylenediamine and 2-pyc is 2-pyridinecarboxylate anion) and its reported Pt(II) analogue, i.e. [Pt(en)(2-pyc)]+ have been made by an improved synthetic procedure, yielding above 80%. They have been characterized by FT-IR, UV-Vis, 1H NMR, 13C NMR, conductivity and elemental analysis. Single crystal structural determination of [Pt(en)(2-pyc)]+ displayed that the Pt(II) cation in this complex coordinated by 2-pyc and en each as five member chelate resulting in slightly distorted square-planar array. The time-dependent spectroscopic analysis of these compounds in aqueous medium demonstrated their structural stabilities. The cytotoxic activities of Pd(II) and Pt(II) complexes, free 2-pyc and carboplatin (as standard drug) were assayed in-vitro against the HCT-116 and MCF-7 as cancerous and MCF 10 A and CCD-841 as normal cell lines. They showed the IC50 order of: carboplatin > 2-pyc > Pt(II) > Pd(II) and lower activities against non-cancerous cells. CT-DNA binding of the Pd(II), Pt(II) and 2-pyc free ligand were explored individually. In this relation, UV-Vis and fluorescence titrations disclosed quenching of CT-DNA absorption and emissions by the compounds via dynamic mechanism and formation of H-bonds and van der Waals forces between them. The interaction was further validated and verified by viscosity measurements and gel electrophoresis. Partition coefficient determination showed that all three compounds have more lipophilicity than cisplatin. Furthermore, docking analysis and molecular dynamics simulation were done to evaluate the nature of interaction between aforementioned compounds and CT-DNA. The finding results demonstrated that these agents interact with CT-DNA via groove binding and were in agreement with experimental results.Communicated by Ramaswamy H. Sarma.
- Klíčová slova
- DNA interaction, Pd(II) and Pt(II) complexes, cytotoxicity, molecular docking, molecular dynamics,
- MeSH
- DNA * chemie metabolismus MeSH
- komplexní sloučeniny * chemie farmakologie chemická syntéza MeSH
- krystalografie rentgenová MeSH
- kyseliny pikolinové * chemie farmakologie MeSH
- lidé MeSH
- molekulární modely MeSH
- nádorové buněčné linie MeSH
- palladium * chemie farmakologie MeSH
- platina chemie MeSH
- protinádorové látky * farmakologie chemie chemická syntéza MeSH
- simulace molekulární dynamiky MeSH
- simulace molekulového dockingu MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- calf thymus DNA MeSH Prohlížeč
- DNA * MeSH
- komplexní sloučeniny * MeSH
- kyseliny pikolinové * MeSH
- palladium * MeSH
- picolinic acid MeSH Prohlížeč
- platina MeSH
- protinádorové látky * MeSH
The purine derivative fludarabine is part of frontline therapy for chronic lymphocytic leukaemia (CLL). It has shown positive effects on solid tumours such as melanoma, breast, and colon carcinoma in clinical phase I studies. As the treatment of CLL cells with combinations of fludarabine and metal complexes of antitumoural natural products, e.g., illudin M ferrocene, has led to synergistically enhanced apoptosis, in this research study different complexes of fludarabine itself. Four complexes bearing a trans-[Br(PPh3)2]Pt/Pd fragment attached to atom C-8 via formal η1-sigma or η2-carbene bonds were synthesised in two or three steps without protecting polar groups on the arabinose or adenine. The platinum complexes were more cytotoxic than their palladium analogues, with low single-digit micromolar IC50 values against cells of various solid tumour entities, including cisplatin-resistant ones and certain B-cell lymphoma and CLL, presumably due to the ten-fold higher cellular uptake of the platinum complexes. However, the palladium complexes interacted more readily with isolated Calf thymus DNA. Interestingly, the platinum complexes showed vastly greater selectivity for cancer over non-malignant cells when compared with fludarabine.
- Klíčová slova
- CLL, anticancer drugs, fludarabine, lymphoma, metal–drug synergy, platinum complexes,
- MeSH
- antimetabolity terapeutické užití MeSH
- chronická lymfatická leukemie * farmakoterapie MeSH
- imunosupresiva terapeutické užití MeSH
- lidé MeSH
- palladium chemie MeSH
- platina chemie MeSH
- protinádorové látky * chemie MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- antimetabolity MeSH
- fludarabine MeSH Prohlížeč
- imunosupresiva MeSH
- palladium MeSH
- platina MeSH
- protinádorové látky * MeSH
Cultivation-based assays represent the gold standard for the assessment of virus infectivity; however, they are time-consuming and not suitable for every virus type. Pre-treatment with platinum (Pt) compounds followed by real-time PCR has been shown to discriminate between infectious and non-infectious RNA viruses. This study examined the effect of Pt and palladium (Pd) compounds on enveloped DNA viruses, paying attention to two significant pathogens of livestock - bovine herpesvirus-1 (BoHV-1) and African swine fever virus (ASFV). Native or heat-treated BoHV-1 suspension was incubated with the spectrum of Pt/Pd compounds. Bis(benzonitrile)palladium(II) dichloride (BB-PdCl 2) and dichloro(1,5-cyclooctadiene) palladium(II) (PdCl 2-COD) produced the highest differences found between native and heat- -treated viruses. Optimized pre-treatment conditions (1 mM of Pd compound, 15 min, 4°C) were applied on both virus genera and the heat inactivation profiles were assessed. A significant decrease in the detected quantity of BoHV-1 DNA and ASFV DNA after heat-treatment (60°C and 95°C) and consequent incubation with Pd compounds was observed. BB-PdCl 2 and PdCl 2-COD could help to distinguish between infectious and non-infectious enveloped DNA viruses such as BoHV-1 or ASFV.
- Klíčová slova
- African swine fever virus, bovine herpesvirus-1, molecular methods, palladium compounds, viability PCR,
- MeSH
- biotest veterinární MeSH
- bovinní herpesvirus 1 * MeSH
- DNA viry MeSH
- kvantitativní polymerázová řetězová reakce veterinární MeSH
- palladium farmakologie MeSH
- prasata MeSH
- virus afrického moru prasat * genetika MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- palladium MeSH
Single-benzene fluorophores are bright and the smallest fluorochromes known so far. In single-benzene fluorophores, the fluorescence is mediated by the push/pull effect of substituting groups. Despite a plethora of advantageous properties, this group of molecules has not been extensively studied for design of high-performance fluorescent sensors of catalytic or enzymatic activities. Thus, herein, new fluorescent probes based on the Tsuji-Trost reaction were developed for the selective detection of palladium and other transition metals (platinum and gold) in an aqueous/organic mixed solvent with the sensitivity down to 2.5 nM (for palladium). The relative flexibility in the synthesis of these probes allows for facile color tuning of the emitted fluorescence. In this study, we have successfully utilized a yellow emission variant for sensitive detection of palladium under cell-free conditions and in living cells, validating its possible applicability for high-throughput optical sensing of catalysts for bioorthogonal chemistry under physiological conditions.
- MeSH
- benzen MeSH
- fluorescenční barviva chemie MeSH
- palladium * chemie MeSH
- přechodné kovy * MeSH
- rozpouštědla MeSH
- viabilita buněk MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- benzen MeSH
- fluorescenční barviva MeSH
- palladium * MeSH
- přechodné kovy * MeSH
- rozpouštědla MeSH
Palladium-catalyzed Suzuki reactions of brominated flavin derivatives (5-deazaflavins, alloxazines, and isoalloxazines) with boronic acids or boronic acid esters that occur readily under mild conditions were shown to be an effective tool for the synthesis of a broad range of 7/8-arylflavins. In general, the introduction of an aryl/heteroaryl group by means of a direct C-C bond has been shown to be a promising approach to tuning the photophysical properties of flavin derivatives. The aryl substituents caused a bathochromic shift in the absorption spectra of up to 52 nm and prolonged the fluorescence lifetime by up to 1 order of magnitude. Moreover, arylation of flavin derivatives decreased their ability to generate singlet oxygen.
Two novel palladium(II)-amino acid complexes, [Pd(Ala)2]·H2O (PA) and [Pd(Val)2].H2O (PV) (Ala = alanine; Val = valine) were synthesized and characterized through FTIR, UV/Vis, 1H-NMR spectroscopies, CHN analysis, X-ray crystallography and molar conductivity measurement. Furthermore, cytotoxicity of Pd(II) complexes against human leukemia cancer cell line, MOLT4 showed promising cancer cell death (CC50 = 0.71 ± 0.046 µM for PA; CC50 = 0.85 ± 0.063 µM for PV) that were less than cisplatin (1.59 ± 0.25 µM). Moreover, the interaction of both the complexes with DNA and BSA was studied using UV-Vis absorption and emission spectroscopic techniques that demonstrated the bindings occurred via van der Waals forces and hydrogen bond. Furthermore, the fluorescence titration showed that static quenching mechanism plays predominate role in binding process. All results showed that both complexes have more binding tendency to DNA in compared to BSA that can be a significant achievement for further medical purposes as a potential antitumor candidate. Finally, molecular docking simulation was performed for PA and PV complexes with DNA and BSA and demonstrated both complexes bind to the groove of DNA mainly by hydrogen bond and interact with site I of BSA via hydrogen bond as well.
- Klíčová slova
- Palladium(II) complex, amino acid, binding, cytotoxicity, mechanism, molecular docking, thermodynamic,
- MeSH
- alanin * chemie MeSH
- DNA * metabolismus chemie MeSH
- komplexní sloučeniny chemie farmakologie chemická syntéza metabolismus MeSH
- lidé MeSH
- nádorové buněčné linie MeSH
- palladium * chemie MeSH
- protinádorové látky * farmakologie chemická syntéza chemie metabolismus MeSH
- sérový albumin hovězí * chemie metabolismus MeSH
- simulace molekulového dockingu * MeSH
- skot MeSH
- valin * chemie MeSH
- vazba proteinů MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- skot MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- alanin * MeSH
- DNA * MeSH
- komplexní sloučeniny MeSH
- palladium * MeSH
- protinádorové látky * MeSH
- sérový albumin hovězí * MeSH
- valin * MeSH
