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1.
J Biol Inorg Chem ; 28(6): 591-611, 2023 09.
Artículo en Inglés | MEDLINE | ID: mdl-37498326

RESUMEN

A series of novel Ga(III)-pyridine carboxylates ([Ga(Pic)3]·H2O (GaPic; HPic = picolinic acid), H3O[Ga(Dpic)2]·H2O (GaDpic; H2Dpic = dipicolinic acid), [Ga(Chel)(H2O)(OH)]2·4H2O (GaChel; H2Chel = chelidamic acid) and [Ga(Cldpic)(H2O)(OH)]2 (GaCldpic; H2Cldpic = 4-chlorodipicolinic acid)) have been synthesized by simple one-step procedure. Vibrational spectroscopy (mid-IR), elemental analysis, thermogravimetric analysis and X-ray diffraction confirmed complexes molecular structure, inter and intramolecular interactions and their influence to spectral and thermal properties. Moreover, complex species speciation was described in Ga(III)-HPic and Ga(III)-H2Dpic systems by potentiometry and 1H NMR spectroscopy and mononuclear complex species were determined; [Ga(Pic)2]+ (logß021 = 16.23(6)), [Ga(Pic)3] (logß031 = 20.86(2)), [Ga(Dpic)2]- (logß021 = 15.42(9)) and [Ga(Dpic)2(OH)]2- (logß-121 = 11.08(4)). To confirm the complexes stability in 1% DMSO (primary solvent for biological testing), timescale 1H NMR spectra were measured (immediately after dissolution up to 96 h). Antimicrobial activity evaluated by IC50 (0.05 mM) is significant for GaDpic and GaCldpic against difficult to treat and multi-resistant P. aeruginosa. On the other hand, the GaPic complex is most effective against Jurkat, MDA-MB-231 and A2058 cancer cell lines and significantly also decreases the HepG2 cancer cells viability at 75 and 100 µM concentrations in a relatively short time (up to 48 h). In addition, fluorescence measurements have been used to elucidate bovine serum albumin binding activity between ligands, Ga(III) complexes and bovine serum albumin.


Asunto(s)
Complejos de Coordinación , Neoplasias , Humanos , Albúmina Sérica Bovina/metabolismo , Piridinas/farmacología , Estructura Molecular , Línea Celular , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Ligandos
2.
Chemistry ; 29(58): e202301491, 2023 Oct 18.
Artículo en Inglés | MEDLINE | ID: mdl-37306545

RESUMEN

Catalytic cyclotrimerization routes to symmetrical [9]helical indenofluorene were explored by using different transition-metal complexes and thermal conditions. Depending on the reaction conditions, the cyclotrimerizations were accompanied by dehydro-Diels-Alder reaction giving rise to another type of aromatic compounds. Structures of both symmetrical [9]helical cyclotrimerization product as well as the dehydro-Diels-Alder product were confirmed by single-crystal X-ray diffraction analyses. Limits of enantioselective cyclotrimerization were assessed as well. DFT calculations shed light on the reaction course and the origin of diminished enantioselectivity.

3.
Bioorg Chem ; 141: 106907, 2023 12.
Artículo en Inglés | MEDLINE | ID: mdl-37844541

RESUMEN

Diseases caused by various microorganisms accompany humans (as well as animals) throughout their whole lives. After germs penetration to the body, the incubation period and infection developing, an infection can cause mild or severe symptoms, not infrequently even death. The immune system naturally defends itself against pathogens with various mechanisms. One of them is the synthesis of antimicrobial peptides. In the case of serious and severe infections, it is currently possible to help the natural immunity by administration of antimicrobial drugs (AMB) with good success since their discovery at the beginning of the last century. However, their excessive use leads to the development of pathogenic microorganisms' resistance to AMB drugs. Based on this, it is necessary to constantly develop new classes of AMB drugs that will be effective against pathogens, even resistant ones. The field of bioinorganic chemistry, similarly to other biological, chemical, or pharmaceutical sciences, discovers various options and approaches for antimicrobial treatment, from the development of new drugs to drug delivery systems. One of the approaches is the design and preparation of potential drugs based on metal ions and antimicrobial peptides. Various metal ions and amino acid or peptide ligands are used for this purpose. In this mini review, we focused on a reliable comparison of the chemical structure and biological properties of selected silver(I) complexes based on amino acids and dipeptides.


Asunto(s)
Antiinfecciosos , Plata , Humanos , Animales , Plata/farmacología , Plata/química , Dipéptidos/farmacología , Aminoácidos , Antiinfecciosos/química , Péptidos Antimicrobianos , Iones , Antibacterianos/farmacología , Antibacterianos/química
4.
Molecules ; 28(5)2023 Feb 26.
Artículo en Inglés | MEDLINE | ID: mdl-36903423

RESUMEN

Total synthesis of the 2-formylpyrrole alkaloid hemerocallisamine I is presented, both in racemic and enantiopure form. Our synthetic strategy involves (2S,4S)-4-hydroxyglutamic acid lactone as the key intermediate. Starting from an achiral substrate, the target stereogenic centers were introduced by means of crystallization-induced diastereomer transformation (CIDT) in a highly stereoselective fashion. A Maillard-type condensation was crucial to constructing the desired pyrrolic scaffold.

5.
Chemistry ; 27(44): 11279-11284, 2021 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-33830567

RESUMEN

The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time in good yields with high er values (er up to 99 : 1). The crucial step of the whole reaction sequence was the enantioselective intramolecular [2+2+2] cycloaddition of tethered triynediols to indenofluorenediols, which was catalyzed by a Rh/SEGPHOS® complex. Further transformations led to the corresponding DSF-IFs. The prepared helically chiral DSF-IFs combine circularly polarized luminescence (CPL) activity (glum =∼10-3 ) with exceptionally high fluorescence quantum yields (up to Φlum =0.97).


Asunto(s)
Rodio , Catálisis , Fluorenos , Luminiscencia , Estereoisomerismo
6.
Inorg Chem ; 60(10): 7315-7328, 2021 May 17.
Artículo en Inglés | MEDLINE | ID: mdl-33945274

RESUMEN

Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(C6F5)4]- salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)═N-κN}MCl] (M = Ti, Zr, Hf; R = t-Bu, Ph) by PhNMe2H+[B(C6F5)4]- to give [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)═NH-κN}MCl]+[B(C6F5)4]- or by chloride ligand abstraction from the complexes [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N)MCl2] (M = Ti, Zr) by Li[B(C6F5)4]·2.5Et2O to give [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N-κN)MCl]+[B(C6F5)4]-. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (3LMCT) excited states with lifetimes up to 62 µs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.

7.
Int J Mol Sci ; 22(16)2021 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-34445122

RESUMEN

Seven inorganic salts containing N-phenylbiguanide as a prospective organic molecular carrier of nonlinear optical properties were prepared and studied within our research of novel hydrogen-bonded materials for nonlinear optics (NLO). All seven salts, namely N-phenylbiguanidium(1+) nitrate (C2/c), N-phenylbiguanidium(1+) perchlorate (P-1), N-phenylbiguanidium(1+) hydrogen carbonate (P21/c), bis(N-phenylbiguanidium(1+)) sulfate (C2), bis(N-phenylbiguanidium(1+)) hydrogen phosphate sesquihydrate (P-1), bis(N-phenylbiguanidium(1+)) phosphite (P21), and bis(N-phenylbiguanidium(1+)) phosphite dihydrate (P21/n), were characterised by X-ray diffraction (powder and single-crystal X-ray diffraction) and by vibrational spectroscopy (FTIR and Raman). Two salts with non-centrosymmetric crystal structures-bis(N-phenylbiguanidium(1+)) sulfate and bis(N-phenylbiguanidium(1+)) phosphite-were further studied to examine their linear and nonlinear optical properties using experimental and computational methods. As a highly SHG-efficient and phase-matchable material transparent down to 320 nm and thermally stable to 483 K, bis(N-phenylbiguanidium(1+)) sulfate is a promising novel candidate for NLO.


Asunto(s)
Sales (Química)/química , Cristalización/métodos , Cristalografía por Rayos X/métodos , Óptica y Fotónica/métodos , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Espectrometría Raman/métodos , Termogravimetría/métodos , Difracción de Rayos X/métodos
8.
Molecules ; 26(21)2021 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-34770744

RESUMEN

Three silver(I) dipeptide complexes [Ag(GlyGly)]n(NO3)n (AgGlyGly), [Ag2(GlyAla)(NO3)2]n (AgGlyAla) and [Ag2(HGlyAsp)(NO3)]n (AgGlyAsp) were prepared, investigated and characterized by vibrational spectroscopy (mid-IR), elemental and thermogravimetric analysis and mass spectrometry. For AgGlyGly, X-ray crystallography was also performed. Their stability in biological testing media was verified by time-dependent NMR measurements. Their in vitro antimicrobial activity was evaluated against selected pathogenic microorganisms. Moreover, the influence of silver(I) dipeptide complexes on microbial film formation was described. Further, the cytotoxicity of the complexes against selected cancer cells (BLM, MDA-MB-231, HeLa, HCT116, MCF-7 and Jurkat) and fibroblasts (BJ-5ta) using a colorimetric MTS assay was tested, and the selectivity index (SI) was identified. The mechanism of action of Ag(I) dipeptide complexes was elucidated and discussed by the study in terms of their binding affinity toward the CT DNA, the ability to cleave the DNA and the ability to influence numbers of cells within each cell cycle phase. The new silver(I) dipeptide complexes are able to bind into DNA by noncovalent interaction, and the topoisomerase I inhibition study showed that the studied complexes inhibit its activity at a concentration of 15 µM.


Asunto(s)
Antiinfecciosos/química , Antiinfecciosos/farmacología , Antineoplásicos/química , Antineoplásicos/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Dipéptidos/química , Plata/química , Antiinfecciosos/síntesis química , Antineoplásicos/síntesis química , Ciclo Celular/efectos de los fármacos , Línea Celular Tumoral , Fenómenos Químicos , Técnicas de Química Sintética , Complejos de Coordinación/síntesis química , Cristalografía por Rayos X , Relación Dosis-Respuesta a Droga , Estabilidad de Medicamentos , Humanos , Conformación Molecular , Simulación de Dinámica Molecular , Análisis Espectral , Relación Estructura-Actividad , Termogravimetría
9.
Angew Chem Int Ed Engl ; 60(13): 6992-6996, 2021 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-33336839

RESUMEN

AuI complexes combining hard oxygen and soft (diphenylphosphanyl)ferrocene (L) ligands in their molecules were synthesized, viz. the gold hydroxides [Au(OH)(L-κP)] (5) and [{Au(L-κP)}2 (µ-OH)][BF4 ] (4), and the oxonium cluster [{Au(L-κP)}3 (µ3 -O)][BF4 ] (1). In-situ auration of 1 produced [{Au(L-κP)}4 (µ4 -O)][BF4 ]2 (2), which spontaneously converted into a dimeric tetragold complex featuring bridging phosphanylferrocenyl groups geminally diaurated in position 2 of the ferrocene scaffold. The same complex and its isomer incorporating ferrocene-1,1'-diyl bridges resulted similarly from 4. Upon crystallization, compound 5 underwent a redox reaction, producing a structurally unique, crown-like, mixed-valent Au0 /AuI cluster, [Au7 (L-κP)6 ]OH. Compounds 1 and 5 were used to prepare the analogous, N-bridged complexes, [{Au(L-κP)}3 (µ3 -NFc)][BF4 ] (Fc=ferrocenyl) and [{Au(L-κP)}4 (µ4 -N)][BF4 ]. The compounds were structurally characterized and further studied by DFT calculations.

10.
Bioorg Med Chem Lett ; 30(13): 127206, 2020 07 01.
Artículo en Inglés | MEDLINE | ID: mdl-32354569

RESUMEN

Four gallium(III) complexes, [Ga(ClQ)3]⋅MeOH (1 - MeOH), [Ga(ClQ)3] (1), [Ga(BrQ)3] (2), [Ga(dIQ)3] (3) and [Ga(CQ)3] (4), were prepared (H-ClQ = 5-chloro-8-quinolinol, H-BrQ = 7-bromo-8-quinolinol, H-dIQ = 5,7-diiodo-8-quinolinol, H-CQ = 5-chloro-7-iodo-8-quinolinol) and characterised by elemental analysis, IR and NMR spectroscopy. Single crystal structure analysis of 1 - MeOH confirmed that the complex has a molecular structure with gallium(III) metal ion coordinated in mer-fashion by N- and O-donor atoms of three ClQ ligands. Stability of all complexes in DMSO was proved by 1H NMR spectroscopy. The in vitro antiproliferative activity of 1 was evaluated against the A2780, MBA-MB-231 and HCT116 cell lines. Complex 1 displays higher antiproliferative activity (IC50 values in the range 2.1-6 µm) compared to the ClQ ligand and cisplatin; and a significant selective antiproliferative potency (IC50 = 136 µm, for normal MRC5pd30 cell line). Radical scavenging experiments revealed that complex 1 exhibits the highest antioxidant activity of the prepared complexes as well as the ligands.


Asunto(s)
Antineoplásicos/farmacología , Proliferación Celular/efectos de los fármacos , Complejos de Coordinación/farmacología , Quinolinas/farmacología , Antineoplásicos/síntesis química , Línea Celular Tumoral , Complejos de Coordinación/síntesis química , Ensayos de Selección de Medicamentos Antitumorales , Depuradores de Radicales Libres/síntesis química , Depuradores de Radicales Libres/farmacología , Galio/química , Humanos , Quinolinas/síntesis química
11.
Inorg Chem ; 59(23): 17162-17170, 2020 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-33180504

RESUMEN

A new mononuclear vanadium peroxido complex [VO(O2)(phen)(quin)]·H2O (1) exhibiting an unprecedented isomerism of its ligands was isolated from a two-component water-acetonitrile solvent system. DFT computations aimed at inspecting the stability of all possible isomers of complexes [VO(O2)(L1)(L2)], where L1 and L2 are NN+ON, OO+ON, NN+OO, and ON+ON donor atom set ligands, suggested that every complex characterized so far was the one preferred thermodynamically. However, the particular case of complex [VO(O2)(phen)(quin)] reported herein poses a notable exception to this rule, as this complex yielded single crystals of the isomer with total energy above the anticipated isomer, although both of these isomers could be observed concurrently in solution and also in the solid state. 51V NMR spectroscopy suggested these isomers to be present both in the crystallization solution and in the acetonitrile solution of 1. The coexistence of two isomers is a consequence of their small computed energy difference of 2.68 kJ mol-1, while the preferential crystallization favoring the unexpected isomer is likely to be triggered by solvent effects and the effects of different solubility and/or crystal packing. The coordination geometry of the unusual isomer also manifests itself in FT-IR and Raman spectra, which were corroborated with DFT computations targeted at band assignments.

12.
Angew Chem Int Ed Engl ; 58(48): 17169-17174, 2019 11 25.
Artículo en Inglés | MEDLINE | ID: mdl-31539185

RESUMEN

This work presents a general approach for synthesis of substituted [5]-helical dispiroindeno[2,1-c]fluorenes based on Rh-catalyzed intramolecular cyclotrimerization of triynes. This approach was further extended for the first synthesis of configurationally stable [7]-helical dispiroindeno[2,1-c]fluorenes. A series of variously substituted derivatives was prepared and their photophysical and electrochemical properties were evaluated. Their fluorescence emission maxima were in the region of 351-428 nm and quantum yields up to 88 % are the highest measured among the full-carbon helical compounds.

13.
Inorg Chem ; 57(4): 1774-1786, 2018 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-29377678

RESUMEN

A novel microporous metal-organic framework, {[Pb4(µ8-MTB)2(H2O)4]·5DMF·H2O}n (1; MTB = methanetetrabenzoate and DMF = N,N'-dimethylformamide), was successfully synthesized by a solvothermal reaction and structurally characterized by single-crystal X-ray diffraction. The framework exhibits a unique tetranuclear [Pb4(µ3-COO)(µ2-COO)6(COO)(H2O)4] secondary building unit (SBU). The combination of the SBU with the tetrahedral symmetry of MTB results in a three-dimensional network structure, with one-dimensional jarlike cavities having sizes of about 14.98 × 7.88 and 14.98 × 13.17 Å2 and propagating along the c axis. Due to the presence of four coordinately unsaturated sites per one metal cluster, an activated form of compound 1 (i.e., desolvated form denoted as 1') was tested in gas adsorption and catalytic experiments. The studies of gas sorption revealed that 1' exhibits a surface area (Brunauer-Emmett-Teller) of 980 m2·g-1. This value is the highest reported for any compound from the MTB group. Interactions of carbon dioxide (CO2) molecules with the framework, confirmed by density functional theory calculations, resulted in high CO2 uptake and significant selectivity of CO2 adsorption with respect to methane (CH4) and dinitrogen (N2) when measured from atmospheric pressure to 21 bar. The high selectivity of CO2 over N2 is mostly important for capturing CO2 from the atmosphere in attempts to decrease the greenhouse effect. Moreover, compound 1' was tested as a heterogeneous catalyst in Knoevenagel condensation of active methylene compounds with aldehydes. Excellent catalytic conversion and selectivity in the condensation of benzaldehyde and cyclohexanecarbaldehyde with malononitrile was observed, which suggests that accessible lead(II) sites play an important role in the heterogeneous catalytic process.

14.
Inorg Chem ; 54(13): 6306-11, 2015 Jul 06.
Artículo en Inglés | MEDLINE | ID: mdl-26067575

RESUMEN

The first peroxidovanadium trimer was prepared in the form of its tetrabutylammonium salt, (NBu4)3[V3O3(O2)6]·2H2O. Its X-ray structure analysis revealed a unique cyclic structure of the [V3O3(O2)6](3-) ion incorporating the yet unobserved µ3-η(2):η(1):η(1) coordination mode of one of its peroxido ligands. While relatively stable in nonaqueous solvents, the [V3O3(O2)6](3-) ion quickly decomposes in diluted aqueous solutions. A higher vanadium concentration or a higher CH3CN content in the mixed CH3CN/H2O solvent facilitates the formation of oligomers [V2O2(O2)4(H2O)](2-) and [V3O3(O2)6](3-). (51)V NMR investigations indicated that the trinuclear species is incorporated in vanadium-catalyzed oxidations in the presence of H2O2.

15.
Chemistry ; 20(29): 8872-5, 2014 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-24938223

RESUMEN

Reported herein is a simple synthetic and crystallization procedure for sequential isolation of two stereoisomers of isoleucine-derived vanadium(V) complexes from a racemic mixture with three stereogenic centers and therefore eight hypothetical species. The products of this crystallization were characterized by electronic and vibrational circular dichroism, NMR spectroscopy, and polarimetry to compare the chiroptic properties of the enantiomerically pure analogues prepared from L-isoleucine and D-allo-isoleucine. NMR studies pointed to the yet unobserved phenomenon of vanadium-catalyzed epimerization of isoleucine.

16.
Inorg Chem ; 53(10): 5037-43, 2014 May 19.
Artículo en Inglés | MEDLINE | ID: mdl-24801123

RESUMEN

Two novel heterometallic complexes [Cd(NH3)6][{VO(O2)2(OH)}2{µ-Cd(NH3)4}] (2) and [{VO(O2)2(Im)}2{µ-Cu(Im)4}] (3) (Im = imidazole) containing peroxidovanadium complexes as metalloligands were prepared and characterized by spectral methods. X-ray single-crystal analysis revealed the presence of unique trinuclear complexes in the crystal structures of 2 and 3. The structure of 2 contains an anionic complex, whose two {VO(O2)2(OH)}(2-) ions are interconnected by a {µ-Cd(NH3)4}(2+) group. Compound 3 is a trinuclear neutral complex comprising two {VO(O2)2(Im)}(-) ions and a single bridging {µ-Cu(Im)4}(2+) group. The bonding via an equatorial OH(-) ligand in 2 and via a doubly bonded apical oxygen atom in 3 represents coordination modes previously unobserved for diperoxidovanadium complexes. Compared with complex 2, density functional theory studies reported decreased Cu-µ-O bond orders and increased µ-O-V bond orders in 3, in accordance with the expected Jahn-Teller distortion of the latter complex.

17.
Org Lett ; 26(3): 619-624, 2024 Jan 26.
Artículo en Inglés | MEDLINE | ID: mdl-38206052

RESUMEN

A facile silver(I)-catalyzed reaction of benzothiazol-2(3H)-ones with NaNO2, or using AgNO2 directly, enables a single-step transformation to the corresponding benzo[1,2,3]thiadiazoles in moderate to excellent yields, with wide functional group compatibility. It can also be performed in a one-pot manner from readily available 2-halobenzothiazoles. This intriguing transformation involving an atom replacement in the S,N-heteroarene ring thus provides rapid access to isobenzothiadiazoles (while avoiding the usage of unstable precursors) and also expands the toolbox of modern skeletal editing reactions.

18.
J Photochem Photobiol B ; 255: 112906, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38688040

RESUMEN

New functionalities were added to biocompatible polycaprolactone nanofiber materials through the co-encapsulation of chlorin e6 trimethyl ester (Ce6) photogenerating singlet oxygen and absorbing light both in the blue and red regions, and using 4-(N-(aminopropyl)-3-(trifluoromethyl)-4-nitrobenzenamine)-7-nitrobenzofurazan, NO-photodonor (NOP), absorbing light in the blue region of visible light. Time-resolved and steady-state luminescence, as well as absorption spectroscopy, were used to monitor both photoactive compounds. The nanofiber material exhibited photogeneration of antibacterial species, specifically nitric oxide and singlet oxygen, upon visible light excitation. This process resulted in the efficient photodynamic inactivation of E. coli not only close to nanofiber material surfaces due to short-lived singlet oxygen, but even at longer distances due to diffusion of longer-lived nitric oxide. Interestingly, nitric oxide was also formed by processes involving photosensitization of Ce6 during irradiation by red light. This is promising for numerous applications, especially in the biomedical field, where strictly local photogeneration of NO and its therapeutic benefits can be applied using excitation in the "human body phototherapeutic window" (600-850 nm). Generally, due to the high permeability of red light, the photogeneration of NO can be achieved in any aqueous environment where direct excitation of NOP to its absorbance in the blue region is limited.


Asunto(s)
Antibacterianos , Escherichia coli , Luz , Nanofibras , Óxido Nítrico , Porfirinas , Oxígeno Singlete , Oxígeno Singlete/química , Oxígeno Singlete/metabolismo , Óxido Nítrico/química , Óxido Nítrico/metabolismo , Nanofibras/química , Antibacterianos/química , Antibacterianos/farmacología , Escherichia coli/efectos de los fármacos , Escherichia coli/efectos de la radiación , Porfirinas/química , Porfirinas/farmacología , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Clorofilidas , Poliésteres/química
19.
Dalton Trans ; 53(26): 10834-10850, 2024 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-38661536

RESUMEN

Silver(I) complexes with proline and hydroxyproline were synthesized and structurally characterized and crystal structure analysis shows that the formulas of the compounds are {[Ag2(Pro)2(NO3)]NO3}n (AgPro) (Pro = L-proline) and {[Ag2(Hyp)2(NO3)]NO3}n (AgHyp) (Hyp = trans-4-hydroxy-L-proline). Both complexes crystallize in the monoclinic lattice with space group P21 with a carboxylate bidentate-bridging coordination mode of the organic ligands Pro and Hyp (with NH2+ and COO- groups in zwitterionic form). Both complexes have a distorted seesaw (C2v) geometry around one silver(I) ion with τ4 values of 58% (AgPro) and 51% (AgHyp). Moreover, the results of spectral and thermal analyses correlate with the structural ones. 1H and 13C NMR spectra confirm the complexes species' presence in the DMSO biological testing medium and their stability in the time range of the bioassays. In addition, molar conductivity measurements indicate complexes' behaviour like 1 : 1 electrolytes. Both complexes showed higher or the same antibacterial activity against Bacillus cereus, Pseudomonas aeruginosa and Staphylococcus aureus as AgNO3 (MIC = 0.063 mM) and higher than silver(I) sulfadiazine (AgSD) (MIC > 0.5 mM) against Pseudomonas aeruginosa. In addition, complex AgPro exerted a strong cytotoxic effect against the tested MDA-MB-231 and Jurkat cancer cell lines (IC50 values equal to 3.7 and 3.0 µM, respectively) compared with AgNO3 (IC50 = 6.1 (5.7) µM) and even significantly higher selectivity than cisplatin (cisPt) against MDA-MB-231 cancer cell lines (SI = 3.05 (AgPro); 1.16 (cisPt), SI - selectivity index). The binding constants and the number of binding sites (n) of AgPro and AgHyp complexes with bovine serum albumin (BSA) were determined at four different temperatures, and the zeta potential of BSA in the presence of silver(I) complexes was also measured. The in ovo method shows the safety of the topical and intravenous application of AgPro and AgHyp. Moreover, the complexes' bioavailability was verified by lipophilicity evaluation from the experimental and theoretical points of view.


Asunto(s)
Antibacterianos , Antineoplásicos , Complejos de Coordinación , Hidroxiprolina , Pruebas de Sensibilidad Microbiana , Prolina , Plata , Plata/química , Plata/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Humanos , Hidroxiprolina/química , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Prolina/química , Prolina/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Complejos de Coordinación/síntesis química , Relación Estructura-Actividad , Línea Celular Tumoral , Estructura Molecular , Péptidos/química , Péptidos/farmacología , Péptidos/síntesis química , Ensayos de Selección de Medicamentos Antitumorales , Pseudomonas aeruginosa/efectos de los fármacos , Modelos Moleculares , Supervivencia Celular/efectos de los fármacos , Proliferación Celular/efectos de los fármacos
20.
J Inorg Biochem ; 239: 112067, 2023 02.
Artículo en Inglés | MEDLINE | ID: mdl-36423394

RESUMEN

A series of five decavanadates (V10) using a simple, one-pot synthesis, adhering to the model template: transition metal ion - decavanadate - ligands:(Hnicotinamide)2{[Co(H2O)3(nicotinamide)2]2[µ-V10O28]}.6H2O (1), {[Co(H2O)4(isonicotinamide)2]3}V10O28·4H2O (2), {[Co(H2O)4]2[Co(H2O)2(µ-pyrazinamide)2][µ-V10O28]}·4H2O (3) {[Co(H2O)4(µ-pyrazinamide)]3.V10O28}·4H2O (4), and (NH4)2{[Ni(H2O)4(2-hydroxyethylpyridine)]2}V10O28·2H2O (5) was synthesized. X-ray analysis reveals that 1 and 3 are decavanadato complexes, while 2, 4 and 5 are decavanadate complex salts. Moreover, 3 is the first example of a polymeric decavanadato complex, employing direct coordination with the metal center and the organic ligand, in toto. From the solution studies using 51V NMR spectroscopy, it was decoded that 1 and 3 stay stable in the model buffer solution and aqueous media. Binding to model proteins, cytotoxicity and water oxidation catalysis (WOC) was studied primarily for 1 and 3 and concluded that neither 1 nor 3 have an interaction with the model proteins thaumatin, lysozyme and proteinase K, because of the presence of the organic ligands in the Co(II) center, any further interplay with the proteins was blocked. Cytotoxicity studies reveal that 1 is 40% less toxic (0.05 mM) and 26% less toxic (0.1 mM) than the uncoordinated V10 with human cell lines A549 and HeLa respectively. In WOC, 1 performed superior activity, by evolving 143.37 nmol of O2 which is 700% (9-fold) increase than the uncoordinated V10.


Asunto(s)
Cobalto , Vanadatos , Humanos , Vanadatos/química , Cobalto/química , Agua/química , Ligandos , Pirazinamida , Aniones , Catálisis
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