Tuning the adsorption behaviour of β-structure chitosan by metal binding

2018 ◽  
Vol 15 (5) ◽  
pp. 267 ◽  
Author(s):  
Chunyan Ma ◽  
Fang Li ◽  
Caihua Wang ◽  
Miao He ◽  
Chensi Shen ◽  
...  

Environmental contextChitosan is an abundant natural component of marine life with potential applications as an adsorbant material for pollutants. We investigate the binding behaviour of chitosan, and show that the β-type structure readily chelates metal ions leading to enhanced adsorption of anionic pollutants in the chitosan-metal complex. The results are highly relevant to the removal of anionic organic pollutants from water. AbstractChitosan, which is commonly extracted from squid pens of the Loligo genus, has a β-type structure. Chitosan has potential application to the adsorption of pollutants but has received little study. We investigate the adsorption ability of β-structure chitosan as well as FeIII and AlIII chitosan-metal complexes. Pristine β-chitosan shows lower adsorption abilities for dye, CrVI and fluoride ions compared with those for α-chitosan, mainly owing to having fewer –NH3+ groups on its surface. However, the anionic pollutant adsorption efficiency of β-chitosan is clearly enhanced when chelated with metal ions. A β-structure chitosan-Fe-Al complex displayed adsorption capacities of 621.45 mg g−1 and 144.53 mg g−1 for Acid Red 73 dye and fluoride ions, respectively, according to the fitted Langmuir–Freundlich model; and of more than 173.03 mg g−1 for CrVI, according to the Freundlich model. These values are much higher than those observed for α-structure chitosan-metal complexes. This enhancement effect on the sorptive behaviour of β-chitosan can be attributed to its loose structure. The polymer chains of β-chitosan are arranged in parallel with relatively weak intermolecular forces, which allows them to easily chelate metal ions. Anionic pollutants can then be efficiently adsorbed by the chelated metal ions in the chitosan-metal complex if the electrostatic attraction of the –NH3+ groups is weak. This investigation provides a better understanding of β-chitosan-based adsorbents for application to anionic pollutant adsorption and removal.

2018 ◽  
Vol 25 (1) ◽  
pp. 22-48 ◽  
Author(s):  
Joanna Watly ◽  
Aleksandra Hecel ◽  
Paulina Kolkowska ◽  
Henryk Kozlowski ◽  
Magdalena Rowinska-Zyrek

Background: The understanding of the bioinorganic and coordination chemistry of metalloproteins containing unusual poly-Xaa sequences, in which a single amino acid is repeated consecutively, is crucial for describing their metal binding-structure-function relationship, and therefore also crucial for understanding their medicinal potential. To the best of our knowledge, this is the first systematic review on metal complexes with polyXaa sequences. Methods: We performed a thorough search of high quality peer reviewed literature on poly-Xaa type of sequences in proteins, focusing on their biological importance and on their interactions with metal ions. Results: 228 papers were included in the review. More than 70% of them discussed the role of metal complexes with the studied types of sequences. In this work, we showed numerous medically important and chemically fascinating examples of possible ‘poly-Xaa' metal binding sequences. Conclusion: Poly-Xaa sequences, in which a single amino acid is repeated consecutively, are often not only tempting binding sites for metal ions, but very often, together with the bound metal, serve as structure determinants for entire proteins. This, in turn, can have consequences for the whole organism. Such sequences in bacterial metal chaperones can be a possible target for novel, antimicrobial therapeutics.


2012 ◽  
Vol 12 (1) ◽  
pp. 49-56 ◽  
Author(s):  
Suryadi Budi Utomo ◽  
Jumina Jumina ◽  
Dwi Siswanta ◽  
Mustofa Mustofa

The ability of tetrakis-thiomethyl-C-4-methoxyphenylcalix[4]resorcinarene for trapping Pb(II) and Cd(II) from aqueous solution at different pH, contact times, and initial metal concentration was investigated. Concentration of metal ions before and after interaction was analyzed by Atomic Absorption Spectrophotometer (AAS). The result indicated that tetrakis-thiomethyl-C-4-methoxyphenylcalix[4]resorcinarene is a good host for metal ions, where Cd(II) sorption capacity was higher than that of Pb(II). Effect of pH on batch experiments for the mentioned ions indicated that the optimum pH for metal binding were 5 for both of lead(II) and cadmium(II). In order to investigate the mechanism of adsorption, the 1st-order, pseudo 1st-order, and pseudo 2nd-order kinetic models were used. The adsorption model of metal ions on the resorcinarene followed pseudo second order of Ho & McKay expression. The equilibrium adsorption isotherm has been analyzed by Langmuir and Freundlich equations. Langmuir model had the higher correlation coefficient than that of Freundlich model.


2020 ◽  
pp. 15-20
Author(s):  
Ersin Yucel ◽  
Mine Yucel

In this study, the usage of the peppermint (Mentha piperita) for extracting the metal ions [Mg (II), Cr (II), Ni (II), Cu (II), Zn (II), Cd (II), Pb (II)] that exist at water was investigated. In order to analyze the stability properties, Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms were used at removing the metal ions and the highest correlation coefficients (R2) were obtained at Langmuir isotherm. Therefore, it is seen that the Langmuir model is more proper than the Freundlich model. However, it was found that the correlation coefficients of removing Ni and Cd is higher at Freundlich model than Langmuir and low at Dubinin-Radushkevich isotherm. It is established that the biosorption amount increase depends on the increase of biosorbent and it can be achieved high efficiency (95%) even with small amount (0.6 mg, peppermint extract) at lead ions. It is also determined that the peppermint extracted that is used at this study shows high biosorption capacity for metal ions and can be used for immobilization of metals from polluted areas.


2018 ◽  
Vol 69 (7) ◽  
pp. 1678-1681
Author(s):  
Amina Mumtaz ◽  
Tariq Mahmud ◽  
M. R. J. Elsegood ◽  
G. W. Weaver

New series of copper (II), cobalt (II), zinc (II), nickel (II), manganese (II), iron (II) complexes of a novel Schiff base were prepared by the condensation of sulphadizine and pyridoxal hydrochloride. The ligand and metal complexes were characterized by utilizing different instrumental procedures like microanalysis, thermogravimetric examination and spectroscopy. The integrated ligand and transition metal complexes were screened against various bacteria and fungus. The studies demonstrated the enhanced activity of metal complexes against reported microbes when compared with free ligand.


Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3255
Author(s):  
Denise Bellotti ◽  
Maurizio Remelli

Deferoxamine B is an outstanding molecule which has been widely studied in the past decade for its ability to bind iron and many other metal ions. The versatility of this metal chelator makes it suitable for a number of medicinal and analytical applications, from the well-known iron chelation therapy to the most recent use in sensor devices. The three bidentate hydroxamic functional groups of deferoxamine B are the centerpiece of its metal binding ability, which allows the formation of stable complexes with many transition, lanthanoid and actinoid metal ions. In addition to the ferric ion, in fact, more than 20 different metal complexes of deferoxamine b have been characterized in terms of their chemical speciation in solution. In addition, the availability of a terminal amino group, most often not involved in complexation, opens the way to deferoxamine B modification and functionalization. This review aims to collect and summarize the available data concerning the complex-formation equilibria in solutions of deferoxamine B with different metal ions. A general overview of the progress of its applications over the past decade is also discussed, including the treatment of iron overload-associated diseases, its clinical use against cancer and neurodegenerative disorders and its role as a diagnostic tool.


Encyclopedia ◽  
2021 ◽  
Vol 1 (1) ◽  
pp. 261-292
Author(s):  
Eugene A. Permyakov

Metal ions play several major roles in proteins: structural, regulatory, and enzymatic. The binding of some metal ions increase stability of proteins or protein domains. Some metal ions can regulate various cell processes being first, second, or third messengers. Some metal ions, especially transition metal ions, take part in catalysis in many enzymes. From ten to twelve metals are vitally important for activity of living organisms: sodium, potassium, magnesium, calcium, manganese, iron, cobalt, zinc, nickel, vanadium, molybdenum, and tungsten. This short review is devoted to structural, physical, chemical, and physiological properties of proteins, which specifically bind these metal cations.


RSC Advances ◽  
2021 ◽  
Vol 11 (21) ◽  
pp. 12815-12825
Author(s):  
Yajie Wang ◽  
Feihong Meng ◽  
Tong Lu ◽  
Chunyun Wang ◽  
Fei Li

Their is a counteraction between a decrease in the disruptive ability of metal-associated oligomer species and an increase in the quantity of oligomers promoted by the metal binding in the activity of hIAPP induced membrane damage.


Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 182-198
Author(s):  
Dalila Rocco ◽  
Samantha Novak ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft

We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (1), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (2), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (3), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (4), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (5), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu2(μ-OAc)4L]n 1D-coordination polymers with L = 1–5 have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in 1 by an F substituent in 2 has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for 1 or H...F for 2) are only secondary packing interactions. Upon going from [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n to [Cu2(μ-OAc)4(3)]n, [Cu2(μ-OAc)4(4)]n, and [Cu2(μ-OAc)4(5)]n·nMeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility.


Inorganics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 54
Author(s):  
Giacomo Manfroni ◽  
Simona S. Capomolla ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft

The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n.2nC6H5Me, [Cu2(hfacac)4(3)2]n.nC6H4Cl2, [Cu2(hfacac)4(3)2]n.nC6H5Cl, and [Cu(hfacac)2(4)]n.nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2].H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 and [Cu(hfacac)2(2)]n.2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n.nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4.


2021 ◽  
Vol 22 (9) ◽  
pp. 4551
Author(s):  
Julie-Anne Fenger ◽  
Gregory T. Sigurdson ◽  
Rebecca J. Robbins ◽  
Thomas M. Collins ◽  
M. Mónica Giusti ◽  
...  

Red cabbage (RC) and purple sweet potato (PSP) are naturally rich in acylated cyanidin glycosides that can bind metal ions and develop intramolecular π-stacking interactions between the cyanidin chromophore and the phenolic acyl residues. In this work, a large set of RC and PSP anthocyanins was investigated for its coloring properties in the presence of iron and aluminum ions. Although relatively modest, the structural differences between RC and PSP anthocyanins, i.e., the acylation site at the external glucose of the sophorosyl moiety (C2-OH for RC vs. C6-OH for PSP) and the presence of coordinating acyl groups (caffeoyl) in PSP anthocyanins only, made a large difference in the color expressed by their metal complexes. For instance, the Al3+-induced bathochromic shifts for RC anthocyanins reached ca. 50 nm at pH 6 and pH 7, vs. at best ca. 20 nm for PSP anthocyanins. With Fe2+ (quickly oxidized to Fe3+ in the complexes), the bathochromic shifts for RC anthocyanins were higher, i.e., up to ca. 90 nm at pH 7 and 110 nm at pH 5.7. A kinetic analysis at different metal/ligand molar ratios combined with an investigation by high-resolution mass spectrometry suggested the formation of metal–anthocyanin complexes of 1:1, 1:2, and 1:3 stoichiometries. Contrary to predictions based on steric hindrance, acylation by noncoordinating acyl residues favored metal binding and resulted in complexes having much higher molar absorption coefficients. Moreover, the competition between metal binding and water addition to the free ligands (leading to colorless forms) was less severe, although very dependent on the acylation site(s). Overall, anthocyanins from purple sweet potato, and even more from red cabbage, have a strong potential for development as food colorants expressing red to blue hues depending on pH and metal ion.


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