Csaba Várhelyi jr.1, Roland Szalay2, György Pokol3,4, Firuţa Goga1, Péter Huszthy3, János Madarász3, Melinda Simon-Várhelyi1, Róbert Tötös1, Alexandra Avram1
1 Faculty of Chemistry and Chemical Engineering, “Babeş-Bolyai” University, RO-400 028 Cluj-N., Arany János str. 11, Romania
2 Institute of Chemistry, “Eötvös Loránd” University, H-1117 Budapest, Pázmány Péter str.
1/a, Hungary
3 Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, H-1111 Budapest, Műegyetem rkp. 3, Hungary
4 Research Centre for Natural Sciences, H-1117 Budapest, Magyar tudósok körútja 2, Hungary
e-mail: ifj.varhelyi.cs@gmail.com Abstract
Azomethine derivatives have several applications, especially as reagents for the determination of transition metal ions. Furthermore these ligands and their cobalt complexes were also reported to possess biological activities, such as antimicrobial, anti-tubercular, anticonvulsant, anti-inflammatory, anti-proliferative activities as well as antifungal inhibition potential [1].
Another reason for using metal-containing compounds as structural scaffolds is related to the kinetic stability of their coordination spheres in the biological environment. Metallic ions have been shown to play important role in the biological activity of different compounds in such away that, in some cases, activity is enhanced or only takes place in the presence of these ions [2].
In our research new cobalt(III) complexes were synthesized with -glyoximes, azides, amines, thiocyanate and halogens, such as [Co(Me-propyl-GlyoxH)2(N3)(amine)], [Co(Me-pentyl-GlyoxH)2(N3)(amine)], [Co(Et-propyl-GlyoxH)2(N3)(amine)], [Co(Et-propyl-GlyoxH)2(Br)(amine)], [Co(Et-propyl-GlyoxH)2(SCN)(amine)], H[Co(Et-propyl-GlyoxH)2(SCN)2], [Co(phenyl-Me-GlyoxH)2(amine)2]I, [Co(Et-propyl-GlyoxH)2(amine)2]I, [Co(Et-Bu-GlyoxH)2(amine)2]I, where GlyoxH = mono deprotonated glyoxime, and the used amines: imidazole, 3-hydroxy-aniline, lepidine, 3,5-dimethyl-pyridine, di(n-butyl)-amine, diisopropyl-amine, 2-amino-pyrimidine, diphenyl-amine, 2-picoline, 3-picoline. The Co(II)-acetate salt dissolved in water and mixed with the glyoxime alcoholic solution was oxidized by air bubbling, then the corresponding diamines and the other complexing agents were added.
The molecular structure of our products was investigated by IR, UV–VIS spectroscopy, mass spectrometry (MS), thermoanalytical measurements (TG-DTG-DTA), and powder XRD.
The biological activity, like antimicrobial effect, was studied for a few bacteria.
Introduction
The importance of metal compounds in medicine dates back to the 16th century, with reports on the therapeutic use of metals or metal-containing compounds in the treatment of cancer. Metal ions are often electron deficient species whereas most biological molecules (proteins and DNA) are electron rich molecules, consequently, there is a general tendency for metal ions to bind to and interact with many important biological molecules. Several metal ions also have high affinity towards small molecules, e.g. O2, that are crucial to life. These considerations alone have fueled much of the past and current interest in developing novel means to use metals or metal-containing agents to modulate biological systems [3].
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Some Co-glyoximato complexes show antibacterial activity. The B12-vitamine molecule, which is used in the treatment of pernicious anemia, is also regarded as a Co(III)-glyoxime coordiantion compound. Some other cobalt complexes are also used in analytical chemistry and moreover, they act as catalysts in water-splitting reaction for hydrogen generation [4].
In this paper we report the synthesis, characterization and biological evaluation of some Co(III) complexes with glyoximes, amines and other ligands.
Experimental
Used materials: Co(OAc)2, Me-propyl-GlyoxH2, Me-pentyl-GlyoxH2, Et-propyl-GlyoxH2, phenyl-Me-GlyoxH2, Et-Bu-GlyoxH2, imidazole, 3-hydroxy-aniline, lepidine, 3,5-dimethyl-pyridine, (n-Bu)2NH, diisopropyl-amine, 2-amino-pyrimidine, diphenyl-amine, 2-picoline, 3-picoline, sodium azide, potassium thiocyanate, potassium bromide, potassium iodide, EtOH.
Methods:
- Synthesis of [Co(GlyoxH)2(N3)(amine)] type complexes
0.005 mol Me-propyl-GlyoxH2 or Me-pentyl-GlyoxH2 or Et-propyl-GlyoxH2 was dissolved in 20 ml EtOH then added to an aqueous solution of 0.0025 mol Co(OAc)2 with 5 ml water. To oxidize Co(II) to Co(III) air was bubbled into the mixture for 2–3 hours, then 0.0025 mol NaN3
dissolved in 5 ml water and 0.0025 mol amine (imidazole, 3-hydroxy-aniline, lepidine, 3,5-dimethyl-pyridine, di(n-butyl)-amine or diisopropylamine) dissolved in 5 ml EtOH were added.
The obtained solutions were heated for 2–3 hours on water bath. After cooling the crystalline complexes were filtered out, washed with EtOH–water mixture (1:1), and then dried on air. One example is shown below:
- Synthesis of [Co(GlyoxH)2(SCN)(amine)] and [Co(GlyoxH)2Br(amine) type complexes The syntheses are similar to the procedure above, however, KSCN or KBr was used instead of NaN3. Examples for the reactions are shown below:
[O], 2 AcOK, ½ H2O
0.005 mol phenyl-Me-GlyoxH2 or Et-propyl-GlyoxH2 was dissolved in 20 ml EtOH was added to the aqueous solution of 0.0025 mol Co(OAc)2 with 5 ml water. Air was bubbled into the
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mixture for 2–3 hours, then 0.005 mol amine (3-hydroxy-aniline, di(n-butyl)-amine, 2-amino-pyrimidine, diphenyl-amine, 2-picoline or 3-picoline) dissolved in 5 ml EtOH was added. The obtained solutions were heated for 2–3 hours on water bath. In the final step 0.0025 mol KI solved in 10 ml water was added. After cooling the crystalline complexes were filtered out, washed with EtOH–water mixture (1:1), and then dried on air. One example is shown
Microscopic characterization and the yield of prepared complexes are presented in Table 1.
Table 1. Microscopic characterization, calculated molecular weight and the yield of prepared complexes.
Nr. Compound Calc. mol.
weight Yield (%) Microscopic characterization 1. [Co(Me-Pr-GlyoxH)2(N3)
(imidazole)] 455.36 53 Dark brown triangle-based
prisms 2. [Co(Me-Pr-GlyoxH)2(N3)
(3-hydroxy-aniline)] 496.41 95 Dark brown triangle-based prisms (microcrystals) 3. [Co(Me-Pr-GlyoxH)2(N3)
(lepidine)] 530.47 60 Dark brown triangle-based
prisms 4. [Co(Me-Pr-GlyoxH)2(N3)
(3,5-dimethyl-pyridine)] 494.43 34 Brown triangle-based prisms
5. [Co(Me-pentyl-GlyoxH)2(N3)
((n-Bu)2NH)] 572.63 16 Dark brown triangle-based
prisms 6. [Co(Me-pentyl-GlyoxH)2(N3)
(diisopropyl-amine)] 544.58 29 Brown triangle-based prisms (microcrystals) 7. [Co(Et-Pr-GlyoxH)2Br
(diisopropyl-amine)] 554.41 86 Brown triangle-based prisms (microcrystals) 8. [Co(Et-Pr-GlyoxH)2Br
((n-Bu)2NH)] 582.46 14 Dark brown triangle-based
prisms (microcrystals) 9. [Co(Et-Pr-GlyoxH)2(SCN)
(diphenyl-amine)] 600.62 20 Black needle-like triangle-based prisms
(3-hydroxy-aniline)2]I 758.45 3 Dark brown triangle-based prisms (microcrystals) 13. [Co(phenyl-Me-GlyoxH)2
(3-picoline)2]I 726.45 50 Dark brown triangle-based prisms
65 14. [Co(phenyl-Me-GlyoxH)2
(2-amino-pyrimidine)2]I 730.40 12 Dark brown triangle-based prisms (microcrystals) 15. [Co(Et-Pr-GlyoxH)2
(2-amino-pyrimidine)2]I 690.42 26 Dark brown triangle-based prisms
16. [Co(Et-Pr-GlyoxH)2
(2-picoline)2]I 686.47 15 Dark brown triangle-based prisms (microcrystals) 17. [Co(Et-Bu-GlyoxH)2
(t-Bu-amine)2]I 674,54 15 Dark brown triangle-based prisms (microcrystals) 18. [Co(Et-Bu-GlyoxH)2
(3-amino-1-propanol)2]I 678.49 1 Black triangle-based prisms (microcrystals) 19. [Co(Et-Bu-GlyoxH)2
(3-amino-pyrimidine)2]I 716.50 28 Brown laminar crystals 20. [Co(Et-Bu-GlyoxH)2
(3-picoline)2]I 714.52 1 Dark brown triangle-based
prisms Infrared spectroscopic study
The mid-IR spectra were recorded with a Bruker Alpha FTIR spectrometer (Platinum single reflection diamond ATR), at room temperature, in the wavenumber range of 4000–400 cm−1, and the far-IR range of 650–150 cm−1, respectively, on a Perkin–Elmer System 2000 FTIR spectrometer, with a resolution of 4 cm−1. The samples were measured in solid state (in powder form) and in polyethylene pellets, respectively. The data of the most characteristic IR bands for the selected complexes are presented in Table 2.
Table 2. IR data of the selected complexes.
Comp.
Mass spectra of the samples were recorded using electrospray ionization (ESI). In the spectra we could detect the molecular ions and some decomposition fragments.
66 leaving amine group, then the azide group is lost. Subsequently, the decomposition of glyoxime groups takes place which is accompanied by big exothermic peaks. This behavior can be explained with the presence of oxygen in the molecule. In the case of [Co(GlyoxH)2Br(amine)]
type complexes the decomposition mechanism is similar, unlike azide, here bromine leaves. In the case of [Co(GlyoxH)2(amine)2]+I- type complexes the iodide ion leaves at 30–190 °C, then
The crystal structure of the complexes was studied with powder XRD measurements, carried out on a PANalytical X’pert Pro MPD X-ray diffractometer. As being novel compounds their diffractograms can not found in the Cambridge database.
UV–VIS spectroscopy
The electronic spectra were recorded with Jasco V-670 Spectrophotometer in 10% EtOH/water solutions containing substrate in 10–4 mol/dm3 concentration. Using Sörensen buffer solutions the electronic spectra were also recorded as a function of pH, and then the acidity constants were calculated too. The obtained values were between 1.2·1011 – 1.1·1010.
Biological study
The antimicrobial effects of complexes were studied for Serratia Marcescens Gram-negative bacteria. The observation was made with the disk method. The complexes were dissolved in DMSO in 100 mmol/l concentration. In the case of [Co(Me-Pr-GlyoxH)2(N3)(lepidine)]
antibacterial effect was observed with 30 l solution. The inhibition zone was 46.66 mm.
Conclusion
In this work new cobalt complexes were synthesized and characterized with physico-chemical methods. Thermal decomposition mechanism was monitored with thermoanalytical measurements. Antibacterial activity was also investigated.
Acknowledgement
The authors wish to express their thankfulness to the “Domus Hungarica Foundation” of Hungary for the several fellowships provided to Csaba Várhelyi jr.
References
[1] A. Barakata, S.M. Solimanb, M. Alia, A. Elmarghanya, A.M. Al-Majida, S. Yousufd, Z.
Ul-Haqe, M.I. Choudharyd, A. El-Faham, Inorganica Chimica Acta 503 (2020) 119405 [2] N.A. Mathews, A. Jose, M.R.P. Kurup, Journal of Molecular Structure 1178 (2019) 544 [3] R. Huang, A. Wallqvist, D.G. Covell, Biochemical Pharmacology 69 (2005) 1009
[4] A.K. Renfrew, E.S. O’Neill, T.W. Hambley, E.J. New, Coordination Chemistry Reviews 375 (2018) 221
67
APPLICATION OF HIGH POWER UV LEDs IN HETEROGENEOUS PHOTOCATALYSIS
Máté Náfrádi, Tamás Hlogyik, Luca Farkas, Tünde Alapi
Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7, Hungary
e-mail: nafradim@chem.u-szeged.hu Abstract
In our work, we designed and built a photochemical reactor with High Power LED light sources, and then tested its operation by heterogeneous photocatalytic decomposition of coumarin. The UV-LEDs emitting at a wavelength of 367(±10) nm were built into a frame with air-cooling elements. A well-controlled electrical power source was used to control and regulate the light output of the LEDs. The photon flux was measured at different electric power inputs, and was found to be linearly dependent on electrical power. Coumarin was used to test the new photoreactor during heterogeneous photocatalysis using TiO2 and ZnO as photocatalysts. At low photon flux the UV-LEDs outperformed a fluorescent mercury-vapor lamp in terms of efficiency and power consumption, but their usage at high electric input is not favorable.
Introduction
Advanced Oxidation Processes (AOPs) are a possible solution to some emerging environmental problem, such as the elimination of organic pollutants from waters. Several AOPs include the use of UV light, like O3/UV, UV/Cl2, photo-Fenton reactions, or heterogeneous photocatalysis. Generally the used light sources are mercury-vapor lamps, but these have some drawbacks, like fragility and hazardous waste production. In the last few years, with the advances in optoelectronics the application of Light Emitting Diodes (LEDs) emitting in the UV region gained more and more popularity. With the application of High Power LEDs the mercury vapor lamps emitting in the 300-400 nm region can be replaced with other UV light sources. UV-LEDs emitting in the UV-C region (260-290 nm) are already available, but their power-efficiency is still relatively low (1-5 %). Due to the further improvements they might also provide a good alternative for mercury vapor lamps emitting UV-C photons (254 nm) [1,2].
UV LEDs that emit at 300-400 nm are especially useful for heterogeneous photocatalysis, since the most frequently used catalysts, TiO2 and ZnO can be excited with light having wavelength shorter than 390 nm. Due to the absorption of photons having appropriate energy (~3.2 eV), excited conduction band electrons (ecb-) and valence band holes (hvb+) form, and they initiate the transformation of organic compounds via charge transfer or hydroxyl radicals (HO•) based reactions. UV-LEDs have already been used in the last few years with good efficiency to transform various pollutants in aqueous media [3-5].
The goal of this current study was to plan, and build a new photoreactor equipped with high power UV-LEDs, and test it for use in the field of heterogeneous photocatalysis. The effect of electric input, and the distance between the reactor wall and light sources were investigated. The photon flux absorbed by the treated solution was determined with actinometry. To test the light sources during heterogeneous photocatalysis, TiO2 and ZnO as photocatalysts, and coumarin (COU) as a model compound were used. The formation of the hydroxylated product of COU, 7-hydroxy-coumarin (7-HO-COU) allows the estimation of HO• formation rates [6].
68 Experimental
The Vishay (VLMU3510-365-130) high power UV-LEDs emitting at 367 nm wavelength were supplied by Distrelec Hungary. The LEDs use InGaN die, and are equipped with a high purity silicone lens. Their typical opening voltage is 4.0 V, and they have a radiant power of 690 mW (with a typical 2000 mW power consumption). They have been soldered to star shaped metal core printed circuit boards (MCPCB) supplied by Meodex. Due to the high amount of heat generated by the LEDs, 0.70 K/W aluminum heat sinks were used to convey the heat. An AX-3005DBL-3 laboratory power supply (maximum output is 5.0 A / 30.0 V) was used to provide and precisely control the electrical power needed to operate the light sources.
The irradiated solution was held in a 200 cm3 cylindrical glass reactor that can be bubbled with gas from a porous glass filter at the bottom. Depending on the measurements, N2 (99.995 %) or synthetic air was used.
The photon flux of the light sources were measured using ferrioxalate actinometry, as described by Hatchard and Parker [7]. 1.0×10-2 M Fe(III)-Oxalate solutions were irradiated, the released Fe(II) was measured using 0.2 % phenanthroline. The absorbance of Fe(II)-phenanthroline complex was measured at 510 nm using UV-Vis spectrophotometry (Agilent 8453) in a quartz cuvette with 0.20 cm optical path length. The solutions were bubbled during the measurements with N2 (99.995 % purity).
The photocatalytic measurements were performed in the previously described UV-LED system, or in a 500 cm3 glass reactor irradiated using a 15 W mercury vapor lamp emitting between 300-400 nm (GCL303T5/UVA, LightTech) as a reference. Before the measurements, the suspensions were saturated with synthetic air, and they were stirred in the dark for 30 minutes. The samples taken were centrifuged at 15000 RPM, and filtered through a 0.22 µm syringe filter. The experiments were started with turning on the light sources. During the photocatalytic experiments suspensions of TiO2 (Aeroxide P25) and ZnO (Sigma Aldrich) were irradiated. COU concentration was 5.0×10-4 M, its concentration was determined via UV-Vis spectrophotometry at 277 nm. The formation of 7-HO-COU was measured using fluorescence spectroscopy (Hitachi F-4500), the excitation wavelength was 345 nm, while the detection was performed at 455 nm wavelength. Reaction rates were determined from the initial linear part of the kinetic curves (up to 15 % transformation of COU).
Results and discussion
As the first part of the current work, the new LED reactor was planned, and built. The 12 pieces of UV-LEDs were soldered according to their manual to the MCPCB stars. Two LEDs were fastened to each heat sinks, the adequate heat conductivity was provided by thermal paste.
The two LEDs on one heat sink was connected in series, and the six parts were connected in parallel, resulting in 8.0 V maximum applicable voltage and 3.0 A maximum applicable current. The six heat sinks are fastened to an aluminum base, their distance from the glass reactor can be changed from 1.25 to 4.25 cm (Fig. 1).
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Figure 1. Schematic setup of the reactor (top view), with the LEDs
The reactor was tested using ferrioxalate actinometry to determine the photon flux, and compare it to the mercury vapor lamp. The measurements were performed with different electrical parameters, from 3.39 to 20.77 W. The voltages were set to constant 8.0 V (6.8(±0.1) V measured when turned on), and the current was changed from 0.5 to 3.0 A. The absorbance of the Fe(II)-phenanthroline complex was measured at 510 nm according to literature [7], and the photon flux was calculated from the slope of the line fitted (Figure 2/A). The light emission of UV-LEDs showed very good linearity as a function of electrical energy consumption. The photon flux of the mercury-vapor lamp was also determined (Figure 2/B), and we can see the much greater efficiency of the LED light sources, as they provide ~60 % more photons at similar electric power consumption.
Figure 2. The absorbance values measured at 510 nm as a function of irradiation time at different electric power output (A), and the calculated photon flux of the LEDs compared
with the Hg-vapor lamp (B)
The effect of the distance (r) between the LEDs and the glass reactor on the photon flux was also determined at constant power input (13.6 W). The photon flux was reduced with the distance from the light source. Therefore the best option is to use the light sources at the closest position (r = 1.25 cm). The possibility to irradiate a larger volume via changing the distance and using a reactor having a larger diameter is an advantage of this reactor setup.
The LED reactor was tested using TiO2 P25 Aeroxide and ZnO photocatalysts and COU, as model compound. The hydroxylated product of COU, 7-HO-COU only form during reactions with HO•, therefore it can be used to determine the formation rate of HO• [6]. First, the optimal catalyst concentration was determined, since it greatly depends on the reactor size and design, and light intensity. 5.0×10-4 M solutions of COU was irradiated in the presence of
,
70
TiO2 and ZnO. The LEDs were operated at 13.6 W (photon flux = 5.63×10-5 molphoton sec-1 dm
-3). The reaction rate of COU did not change above 0.5 g dm-3 catalyst load (Fig. 3/A), similarly to the formation rates of 7-HO-COU, it even started to lower at high (1.5 g dm-3) ZnO dosage (Fig. 3/B), probably because of the increased light scattering. During further experiments, 1.0 g dm-3 catalyst concentration was used, to exclude the contribution of direct photolysis.
Figure 3. The transformation rate of COU (A), and the formation rate of 7-HO-COU (B) as a function of catalyst concentration
The reaction rates of COU, and the formation rates of 7-HO-COU were determined at different photon fluxes by varying the electric power input (3.07 - 21.14 W) of the LEDs.
Although the photon flux increased linearly with electric power input, in the presence of catalysts the reaction rates of COU increased according to a saturation curve (Fig. 4/A). The formation rate of HO• showed a similar tendency (Fig. 4/B). The apparent photonic efficiencies can be calculated using the photon flux determined via actinometry. With the increase of the photon flux the photonic efficiency of the transformation of COU reduced from 1.5 % to 0.5
%.
In the case of measurements with the Hg-vapor lamp similar photonic efficiencies were measured (1.1 %). The results have been corrected according to the different reactor volumes.
If we take these into account then the difference is negligible, therefore the cost-efficiency of the two light sources is similar (Fig. 4).
Figure 4. The transformation rate of COU (A), and the formation rate of 7-HO-COU (B) in
the case of LEDs and Hg-vapor lamp as a function of electrical power used Conclusions
The constructed high power UV-LED based photoreactor setup was highly efficient, and well customizable for use with either photolytic of photocatalytic applications. Overall, we can conclude, that the use of LED light sources for photochemical applications is highly favorable
0.0E+00
71
due to their power efficiency, and customizability. The operation of the LEDs is especially cost-effective in the case of lower electric energy input.
Acknowledgements
This work was supported by the János Bolyai Research Scholarship of the Hungarian Academy of Sciences, and new national excellence program of the Ministry for Innovation and Technology (ÚNKP-20-3-SZTE 548, and ÚNKP-20-5-SZTE 639). This work was sponsored by the National Research, Development and Innovation Office-NKFI Fund OTKA, project number FK132742.
References
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ULTRAHIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC