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•A novel, hybrid 3,5-diiodo-L-tyrosinato copper(II) complex was synthesized.•The structure is stabilized by π···π, metal···π, π···I non-covalent interactions.•The structural, ...spectroscopic, thermal and magnetic properties were investigated.•The exchange pathway occurs in the zig - zag chain.
The ternary Cu(II)/amino-acid/diamine systems have large positive logK values than binary Cu/amino systems, suggesting stabilization due to the effective stacking interaction between aromatic diamine and the aromatic side group of the amino acid. Thus, a hybrid 3,5-diiodo-L−tyrosinato copper(II) complex with an aromatic diamine, of formula Cu(L−I2TyrO-)(H2O)(phen)∙2H2O (1) was characterized in depth by using X-ray, TG/DTG, DSC, FT-IR, Raman, Q-band EPR, NIR-Vis-UV, magnetic methods and the theoretical calculations. The crystal structure is stabilized by weak π···π stacking, metal···π and intra- and intermolecular π···I non-covalent interactions. The computed interaction energies of Cg(1)∙∙∙Cg(2), Cg(3)∙∙∙I and Cg(1)∙∙∙Cu ranging from 0.69 kcal/mol− -2.20 kcal/mol. The weak interactions shift the bands assigned as ν(C-I) to higher frequency in the FT-IR spectrum. The g tensor is axial with g|| (2.239) > g⊥ (2.057) indicating that the unpaired electron residues in the dx2–y2 orbital. The exchange pathway occurs in the zig-zag chain with d(Cu···Cu) = 9.429 Å.
In this work, the gold nanoparticles (AuNPs) were synthesized using pulse-modulated radio-frequency atmospheric pressure glow discharge (pm-rf-APGD). By tailoring selected operating parameters of the ...pm-rf-APGD reaction-discharge system, the experimental conditions for the synthesis of raw-AuNPs with controlled optical and structural properties were found. The colloidal suspension of the size-controlled raw-AuNPs was mixed with an aqueous solution of gelatine and turmeric oil to produce an oil-in-water (O/W) nanoemulsion. AuNPs loaded into the nanoemulsion were characterized using ultraviolet–visible absorption spectrophotometry, dynamic light scattering, scanning electron microscopy supported by energy dispersive X-ray spectroscopy, and transmission electron microscopy equipped with selected area X-ray diffraction. Additionally, attenuated total reflectance Fourier-transform infrared spectroscopy was used to confirm the efficient functionalization of the AuNPs by nanoemulsion component. It was revealed that AuNPs were mostly spherical with an average size of 4.6 ± 1.0 nm and a face-centered cubic crystal system. The developed O/W nanoemulsion carrying AuNPs was applied towards the human breast cancer cell lines MCF7 and MDA-MB-231. It was found that it exhibited the cytotoxicity towards the breast cancer cells while were non-cytotoxic towards the non-tumour breast cells MCF10A. Moreover, it also inhibited the migration of the invasive cancer breast cells (line MDA-MB-231) and hence, could prevent the breast cancer metastasis.
In the present work seven new complexes of Pd(II) containing halogeno-derivatives of 7-azaindole (7AIH), PdCl2(L)2, where L = 3-chloro-7-azaindole (3Cl7AIH) or 3-bromo-7-azaindole (3Br7AIH) or ...4-chloro-7-azaindole (4Cl7AIH) or 4-bromo-7-azaindole (4Br7AIH) or 5-bromo-7-azaindole (5Br7AIH) or 3-bromo-4-chloro-7-azaindole (3Br4Cl7AIH) or 5-bromo-3-chloro-7-azaindole (5Br3Cl7AIH) were prepared and studied by infrared and Raman spectroscopy accompanied by the DFT calculations. Full geometry optimizations and vibrational frequency calculations were performed for the two possible isomers cis and trans of PdCl2(L)2 using the B3LYP method with the 6–311++G(d,p)/LanL2DZ basis sets. According to the theoretical results, the trans isomers are more stable than cis. As shown by the combined experimental and theoretical vibrational spectroscopic studies, only trans isomers with Ci symmetry are present, in the solid state. The combined experimental and theoretical studies have revealed that in PdCl2(L)2 complexes, palladium(II) is bound to two pyridine nitrogen atoms of L ligands and to two chloride ions, in a square-planar trans arrangement. Detailed vibrational assignments of the experimental infrared and Raman spectra of these complexes have been made on the basis of the calculated potential energy distributions (PEDs). The antiproliferative activity of selected trans-PdCl2(L)2 have been tested against human cancer cell lines (T47D, MCF7, A549 and A2780). The obtained IC50 values indicate that the title complexes possess lower cytotoxicity, in comparison to cisplatin.
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•Pd(II) complexes of seven halogeno-7-azaindole were synthesized.•The trans structures were confirmed by FT-IR, FT-Raman and DFT studies.•In trans-PdCl2(L)2, palladium is bonded to two Cl and two pyridine N atoms.•A detailed interpretation of the IR and Raman spectra is reported.•The trans-PdCl2(L)2 possess low cytotoxicity against the human cancer cell lines.
•The efficiency of pollution removal in one-stage and hybrid constructed wetland (CWs) was analyzed.•One-stage CWs provide 80–89% efficiency of BOD5, COD and TSS removal as well as 59–66% of TN and ...TP removal.•Hybrid CWs provide above 92% efficiency of BOD5, COD and TSS removal as well as 65 and 89% of TN and TP removal.•Hybrid constructed wetland can be used on a larger scale in Polish conditions.
This paper is a review of research and experiences related to the application of constructed wetland systems (CWs) insoutheastern Poland in 1992–2016. On the basis of literature data, a comparison between pollutant removal efficiencies of one-stage and hybrid CWs was made. Some problems regarding the operation of these treatment plants were also presented. Data from various facilities indicate that one-stage CWs with horizontal or vertical flow were characterised by a quite high (80–89%) efficiency of removal of BOD5, COD and total suspended solids, but were less efficient in removing of biogenic compounds nitrogen and phosphorus – respectively 59 and 66%. Significantly higher removal efficiencies for the basic pollutants (above 92%) were observed in hybrid CWs with a VF–HF bed configuration. Those facilities removed ca. 65% of total nitrogen and 89% of total phosphorus. A statistical analysis revealed that hybrid VF–HF type CWs were characterised by a very high, about 99%, operation reliability. Lower reliabilities were achieved by one-stage CWs, especially those with a VF bed. Twenty five years of research on and experiences in the application of CWs in southeastern Poland indicate that one-stage CWs can be used on a larger scale in Polish conditions in rural areas with a scattered housing structure. Hybrid systems, on the other hand, can be applied successfully in recreational centres or in protected areas, especially in national parks, where a high pollutant removal efficiency is required. It has been shown that the use of hybrid CWs is consistent with the idea of sustainable development.
Two Pd(II) complexes of 7-azaindole-3-carboxaldehyde (7AI3CAH) were synthesized. Structure of Pd2(7AI3CA)4 was confirmed by XRD, IR, Raman and DFT studies. In trans-PdCl2(7AI3CAH)2, palladium is ...bonded to two Cl and two pyridine N atoms. A detailed interpretation of the IR and Raman spectra is reported. trans-PdCl2(7AI3CAH)2 revealed remarkable cytotoxicity against T47D cancer cell lines.
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New Pd(II) complex, trans-PdCl2(7AI3CAH)2, containing 7-azaindole-3-carboxaldehyde (7AI3CAH) and the dinuclear complex Pd2(7AI3CA)4·DMSO with the deprotonated ligand (7AI3CA) have been prepared and characterized by X-ray crystallography, infrared and Raman spectroscopy, DFT calculations and antiproliferative activity studies. A single crystal X-ray analysis of Pd2(7AI3CA)4·DMSO has shown that the complex crystallizes in Cmca space group with the following unit cell dimensions: a = 15.6593(9), b = 17.9444(8), c = 13.8915(7) Å, V = 3903.5(3) Å3, Z = 4. Two ligands and DMSO solvate molecule are disordered. In this complex, the Pd24+ unit is surrounded by four N-deprotonated 7AI3CA− anions with a Pd–Pd distance of 2.7122(12) Å. Vibrational spectroscopic studies have revealed that in trans-PdCl2(7AI3CAH)2 complex, palladium(II) is bound to two pyridine nitrogen atoms of 7AI3CAH and to two chloride ions, in a square-planar trans arrangement. Comprehensive DFT calculations (including geometry optimizations, theoretical vibrational spectra and HOMO/LUMO orbitals) were performed for the four possible isomers of the dinuclear complex Pd2(7AI3CA)4 and for two isomers of PdCl2(7AI3CAH)2 using the B3LYP method with the 6–311++G(d,p)/LanL2DZ basis sets. The results have shown that the most stable isomers are: cis-(2,2)-Pd2(7AI3CA)4 for the dinuclear complex and trans-PdCl2(7AI3CAH)2 for the mononuclear complex. Detailed vibrational assignments of the experimental infrared and Raman spectra of both the palladium(II) complexes have been made on the basis of the calculated potential energy distributions (PEDs). The antiproliferative activity of trans-PdCl2(7AI3CAH)2 has been tested against the following human cancer cell lines: T47D and MCF7 (breast cancer), A549 (lung carcinoma), A2780 (ovarian cancer) and one normal cell line BALB/3T3 (mouse fibroblast). The trans-PdCl2(7AI3CAH)2 has revealed a remarkable cytotoxicity against the T47D tumour cell line (IC50 = 4.77 ± 1.61 μM), which is over three-times higher than the clinically used cisplatin (IC50 = 16.3 ± 3.9 μM). A study on stability of trans-PdCl2(7AI3CAH)2 in DMSO solution has been performed by FT-IR (ATR) spectroscopy.
The crystal and molecular structure of 7-azaindole-3-carboxylic acid (7AI3CAH2) has been determined by a single-crystal X-ray diffraction analysis (space group Pca21, a = 14.247(3), b = 5.1983(10), ...c = 9.871(2) Å, V = 731.0(2) Å3, Z = 4). The crystal structure consists of chains of the 7AI3CAH2 molecules, arranged into ribbons and connected via intermolecular O–H⋯N and N–H⋯O hydrogen bonds. The IR and Raman spectra of 7AI3CAH2 and its deuterated derivative were recorded in the solid state. The DFT calculations at the B3LYP/6–311++G(d,p) level were performed for four conformers of the 7AI3CAH2 monomer as well as for the dimer and trimer, which included intermolecular H-bonding motifs. The analogous calculations were carried out for the deuterated derivative (7AI3CAD2). The optimized structural parameters and the calculated vibrational spectra of trimer reproduce the experiment very well. In addition, new complexes of 7AI3CAH2 with Pt(II) and Pd(II) were prepared and studied by infrared and Raman spectroscopy. The geometry optimizations and vibrational frequency calculations were conducted for two possible (cis and trans) isomers of MCl2(7AI3CAH2)2 (where M = Pt(II) or Pd(II)) using the B3LYP method with the 6–311++G(d,p)/LanL2DZ basis sets. The combined experimental and theoretical vibrational spectroscopic studies have shown that in the solid state the platinum(II) complex exists as the cis isomer (cis-PtCl2(7AI3CAH2)2), whereas the palladium(II) complex has the trans conformation (trans-PdCl2(7AI3CAH2)2). In both isomers, two pyridine nitrogen atoms of the 7AI3CAH2 ligands and two chloride ligands are coordinated to the central Pt(II) or Pd(II) atoms in a square-planar arrangement. The carboxylic and NH groups of 7AI3CAH2 are not bonded by metal ions. Detailed vibrational assignments for 7AI3CAH2 and its Pt(II) and Pd(II) complexes have been made on the basis of the calculated potential energy distributions (PEDs). The in vitro antiproliferative activities of cis-PtCl2(7AI3CAH2)2 and trans-PdCl2(7AI3CAH2)2 were studied on two human cancer cell lines (T47D and A549). As follows from the obtained IC50 values, the trans-PdCl2(7AI3CAH2)2 complex exhibits cytotoxicity against T47D cell line, which is comparable to that of cisplatin.
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•7AI3CAH2 molecules are linked by O–H⋯N and N–H⋯O hydrogen bonds, in crystal.•cis-PtCl2(7AI3CAH2)2 and trans-PdCl2(7AI3CAH2)2 are formed in the solid state.•Pt(II) and Pd(II) ions are bound by pyridine N atoms of 7AI3CAH2.•Carboxylic and NH groups of 7AI3CAH2 are not bonded by metal ions.•Cytotoxicity of Pd(II) complex against T47D cell line is similar to cisplatin.
Crystal structures of new one-dimensional coordination polymers of 1H-indazole-3-carboxylic acid with Na+ (1) and Li+ (2) have revealed that in 1 both the neutral and deprotonated forms of the acid ...act as the tridentate ligand making a distorted octahedral environment around the Na+ ion (NaO4N2), whereas in 2, the Li+ ion is penta-coordinated (LiO4N) by the deprotonated bidentate acid ligands and the bridging water molecules, which lead to the formation of polymeric ribbons of edge-sharing distorted pyramids. The Li-ligand and Na-ligand stretching and bending vibrations are observed below 400 cm−1.
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•Single crystal structures of Na(I) and Li(I) one-dimensional coordination polymers were determined.•1H-indazole-3-carboxylic acid (IND3CAH2) acts as tridentate and bidentate ligand.•In 1, both the deprotonated and neutral forms of tridentate ligand coordinate to Na(I).•The coordination spheres around Na(I) in 1 and Li(I) in 2 are different.
Sodium(I) and lithium(I) one-dimensional coordination polymers, Na(IND3CAH)(IND3CAH2)n (1) and Li(IND3CAH)(H2O)n (2), with 1H-indazole-3-carboxylic acid (IND3CAH2) have been synthesized and investigated by a single crystal X-ray diffraction and vibrational spectroscopy. In compound 1, both the O-deprotonated (IND3CAH−) and neutral (IND3CAH2) forms of the acid act as the tridentate ligands and are bound with Na+ via two oxygen atoms and the 1H-indazole nitrogen atom forming polymeric chains. Each Na+ ion is six-coordinate in a distorted octahedral geometry (NaO4N2). In compound 2, the Li+ ion is five-coordinate (LiO4N) and the coordination sphere is intermediate between square-pyramid and trigonal-bipyramid. The deprotonated IND3CAH− ion acts as the bidentate ligand coordinated to Li+ ion via one carboxylate oxygen atom and the 1H-indazole nitrogen atom. In contrast to 1, the carboxylate group exhibits the monoatomic bridging mode. In addition, the oxygen atom of the water molecule also links two adjacent Li+ ions. The bridging ligands lead to the formation of polymeric ribbons of edge-sharing O4N distorted pyramids. Intermolecular NH⋯O and OH⋯O hydrogen bonds have a distinctive effect on crystal packing of the title compounds. The IR and Raman spectra of 1 and 2 in the solid state confirm the results from X-ray analysis. Vibrational spectra of the ligand IND3CAH2 and its deuterated derivative (IND3CAD2) have been measured and assigned based on DFT calculations.
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•In CuBr2(7AI3CAH)2n, the CuBrBrCu double bridge system is formed.•Trans-PtCl2(7AI3CAH)2 is comparable to cisplatin on LoVo and MCF7 cell lines.•It is much less active than cisplatin ...against A549 cells.•It is 8-fold less toxic against healthy BALB/3T3 cells in comparison to cisplatin.
Pt(II) and Cu(II) complexes, trans-PtCl2(7AI3CAH)2 and CuBr2(7AI3CAH)2n, containing 7-azaindole-3-carboxaldehyde (7AI3CAH) have been synthesized and investigated by a single crystal X-ray diffraction, vibrational spectroscopy and DFT calculations. In the platinum(II) complex two pyridine nitrogen atoms of the 7AI3CAH ligands and two chloride ligands are coordinated to the central metal atom, in a square-planar trans arrangement. In the polymeric copper(II) complex the coordination geometry is a tetragonal bipyramid (4 + 2), where the in-plane ligands are two pyridine nitrogen atoms of two organic ligands and two trans-bromide ligands. The apical positions of bipyramid are occupied by the two Br ligands from the neighboring units. Thus, the CuBrBrCu double bridge system is formed. Detailed vibrational assignments of the IR and Raman spectra of the Pt(II) and Cu(II) complexes have been made on the basis of the calculated potential energy distributions (PEDs) using B3LYP method. The in vitro antiproliferative activity of trans-PtCl2(7AI3CAH)2 was studied against different human cancer cell lines. The results have shown that this complex is comparably cytotoxic with cisplatin at the LoVo (colon cancer) and MCF7 (breast cancer) cells, whilst its cytotoxicity is significantly lower against the A549 cells (lung cancer) as compared to cisplatin. However, it is about 8-fold less toxic than cisplatin against a normal fibroblast cell line (BALB/3T3). A study on stability of trans-PtCl2(7AI3CAH)2 in DMSO solution has been performed by FT-IR (ATR) spectroscopy to predict a possible binding mode of trans-platinum(II) complex with DNA.
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•Zn(I3AAH)2)n (1), a 2D polymer of plant hormone (I3AAH2) was synthesized.•The structure of 1 was confirmed by XRD, FT-IR, FT-Raman, 1H and 13C NMR studies.•Zn(II) is bound by four ...oxygen atoms of four O-deprotonated I3AAH− ligands.•For 1, the inhibition zones for bacteria were from 11 mm to 14 mm.
A new 2D coordination polymer of indole‑3‑acetic acid (I3AAH2) with Zn(II), Zn(I3AAH)2n (1) has been synthesized and fully characterized using single-crystal X-ray diffraction, infrared, Raman, 1H and 13C NMR spectroscopy, DFT calculations and microbiological activity tests. The crystal structure is monoclinic, space group P21/n, with a = 6.1948(2), b = 7.4954(3), c = 36.2877(12) Å, β = 94.006(3)°, V = 1680.81(9) Å3 and Z = 4. The Zn atom is bound to four oxygen atoms of four O-deprotonated I3AAH− ligands, in a slightly distorted tetrahedral environment. The carboxylate groups adopt the μ-O,O′ bidentate bridging mode. Non-classical CH⋯O intra- and intermolecular interactions provide ancillary structural stabilization of 1. A theoretical study was carried out at the B3LYP/6–31++G(d,p) level. Detailed vibrational assignment for 1 was based on the calculated PED. The in vitro antibacterial activity against Gram-negative (E. coli, P. aeruginosa) and Gram-positive (B. subtilis, L. monocytogenes and S. aureus) bacteria and in vitro antifungal activity against A. niger and C. albicans of 1 were investigated. For comparison, similar microbiological tests were performed for four other Zn(II) complexes (2–5) with indolecarboxylic acids reported earlier. For 1, the inhibition zones for bacteria were from 11 mm to 14 mm, but for fungi, no inhibition zones were observed. Promising results were obtained for 3, against B. subtilis, L. monocytogenes and A. niger and for 4 against B. subtilis (with inhibition zones >20 mm).
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Eight platinum(II) complexes of the general formula cis-PtCl2(L)2 containing 7-azaindole (L = 7AIH) and its halogeno-derivatives: L = 3-chloro-7-azaindole (3Cl7AIH); ...3-bromo-7-azaindole (3Br7AIH); 4-chloro-7-azaindole (4Cl7AIH); 4-bromo-7-azaindole (4Br7AIH); 5-bromo-7-azaindole (5Br7AIH); 3-bromo-4-chloro-7-azaindole (3Br4Cl7AIH) and 5-bromo-3-chloro-7-azaindole (5Br3Cl7AIH) were prepared. Two complexes, cis-PtCl2(3Br4Cl7AIH)2 (2) and cis-PtCl2(4Br7AIH)2·DMF, are reported for the first time. Crystal structure of the latter compound has been determined with X-ray diffraction analysis (space group P43, with a = 14.775(2), c = 41.640(8) Å, V = 9090(3) Å3 and Z = 16). For all of these complexes, formation of the cis isomers in the solid state was confirmed by experimental vibrational (IR and Raman) spectroscopy combined with DFT calculations. A complete assignment of the IR and Raman spectra was made on the basis of the calculated potential energy distribution (PED). Stability of complex (2) in DMSO solution was investigated by FT-IR (ATR) spectroscopy. The in vitro antiproliferative activity of cis-PtCl2(3Br4Cl7AIH)2, cis-PtCl2(3Cl7AIH)2 and cis-PtCl2(3Br7AIH)2 was evaluated on selected human cancer cell lines and towards normal mouse fibroblast cell line (BALB/3T3). All complexes are more toxic than cisplatin against Es-2 (ovarian cancer), LNCaP (prostate adenocarcinoma) and MCF7 (breast cancer). Moreover, complex (2) is significantly more active than the other complexes on A549 (lung carcinoma, IC50 = 3.9 μM). However, the three investigated Pt(II) complexes with 7-azaindoles have revealed higher cytotoxicity against a normal cell line (BALB/3T3), in comparison to cisplatin.
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