Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by mercerized cellulose and mercerized sugarcane bagasse chemically modified with EDTA dianhydride (EDTAD)

This work describes the preparation of new chelating materials derived from cellulose and sugarcane bagasse for adsorption of Cu²⁺, Cd²⁺, and Pb²⁺ ions from aqueous solutions. The first part involved the mercerization treatment of cellulose and sugarcane bagasse with NaOH 5 mol/L. Non- and mercerized cellulose and sugarcane bagasse were then reacted with ethylenediaminetetraacetic dianhydride (EDTAD) in order to prepare different chelating materials. These materials were characterized by mass percent gain, X-ray diffraction, FTIR, and elemental analysis. The second part consisted of evaluating the adsorption capacity of these modified materials for Cu²⁺, Cd²⁺, and Pb²⁺ ions from aqueous single metal solutions, whose concentration was determined by atomic absorption spectroscopy. These materials showed maximum adsorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ ions ranging from 38.8 to 92.6 mg/g, 87.7 to 149.0 mg/g, and 192.0 to 333.0 mg/g, respectively. The modified mercerized materials showed larger maximum adsorption capacities than modified non-mercerized materials.     

Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by succinylated mercerized cellulose modified with triethylenetetramine

This study describes the preparation of two new chelating materials derived from succinylated mercerized cellulose (cell 1). Cell 1 was activated through two different methods by using diisopropylcarbodiimide and acetic anhydride (to form an internal anhydride) and reacted with triethylenetetramine in order to obtain cell 2 and 4. New modified celluloses were characterized by mass percent gain, concentration of amine functions, elemental analysis, and infrared spectroscopy. Cell 2 and 4 showed degrees of amination of 2.8 and 2.3 mmol/g and nitrogen content of 6.07% and 4.61%, respectively. The capacity of cell 2 and 4 to adsorb Cu²⁺, Cd²⁺, and Pb²⁺ ions from single aqueous solutions were examined. The effect of contact time, pH, and initial concentration of metal ions on the metal ions uptake was also investigated. Adsorption isotherms were well fitted by the Langmuir model. The maximum adsorption capacity of cell 2 and 4 were found to be 56.8 and 69.4 mg/g for Cu²⁺; 68.0 and 87.0 mg/g for Cd²⁺; and 147.1 and 192.3 mg/g for Pb²⁺, respectively.     

Activated carbon-containing alginate adsorbent for the simultaneous removal of heavy metals and toxic organics

By combining two functions of alginate gel and activated carbon, an activated carbon-containing alginate bead (AC-AB) adsorbent was developed and successfully used to simultaneously remove heavy metal ions and toxic organics. Quantitative analysis showed that almost all of the adsorption of toxic organics, such as p-toluic acid, is caused by the activated carbon in the AC-AB adsorbent, whereas the alginate component has a major role in the removal of heavy metals. A 50-L solution containing eight heavy metals (Pb²⁺, Mn²⁺, Cd²⁺, Cu²⁺, Zn²⁺, Fe²⁺, Al³⁺ and Hg²⁺) and four mineral ions was run continuously through a filter cartridge packed with 160 g of the AC-AB adsorbent. The adsorbent showed a high capacity to remove heavy metals completely from the water, while allowing essential minerals, such as K⁺, Na⁺, Mg²⁺ and Ca²⁺, to pass through the filter. The adsorbent could be regenerated using eluents, such as HNO₃, and reused repeatedly without considerable loss of its metal uptake capacity through 10 subsequent cycles of adsorption and desorption. With its high capacity and high selectivity for toxic heavy metals, the AC-AB adsorbent has enormous potential for application in drinking water treatment technologies.     

Metal ion dependence of DNA cleavage by SepMI and EhoI restriction endonucleases

Most of type II restriction endonucleases show an absolute requirement for divalent metal ions as cofactors for DNA cleavage. While Mg²⁺ is the natural cofactor other metal ions can substitute it and mediate the catalysis, however Ca²⁺ (alone) only supports DNA binding. To investigate the role of Mg²⁺ in DNA cleavage by restriction endonucleases, we have studied the Mg²⁺ and Mn²⁺ concentration dependence of DNA cleavage by SepMI and EhoI. Digestion reactions were carried out at different Mg²⁺ and Mn²⁺ concentrations at constant ionic strength. These enzymes showed different behavior regarding the ions requirement, SepMI reached near maximal level of activity between 10 and 20 mM while no activity was detected in the presence of Mn²⁺ and in the presence of Ca²⁺ cleavage activity was significantly decreased. However, EhoI was more highly active in the presence of Mn²⁺ than in the presence of Mg²⁺ and can be activated by Ca²⁺. Our results propose the two-metal ion mechanism for EhoI and the one-metal ion mechanism for SepMI restriction endonuclease. The analysis of the kinetic parameters under steady state conditions showed that SepMI had a K_m value for pTrcHisB DNA of 6.15 nM and a V_max of 1.79 × 10^?2 nM min^?1, while EhoI had a K_m for pUC19 plasmid of 8.66 nM and a V_max of 2 × 10^?2 nM min^?1.     

An amperometric biosensor based on horseradish peroxidase immobilized onto maize tassel-multi-walled carbon nanotubes modified glassy carbon electrode for determination of heavy metal ions in aqueous solution

A biosensor for trace metal ions based on horseradish peroxidase (HRP) immobilized on maize tassel-multiwalled carbon nanotube (MT-MWCNT) through electrostatic interactions is described herein. The biosensor was characterized using Fourier transform infrared (FTIR), UV–vis spectrometry, voltammetric and amperometric methods. The FTIR and UV–vis results inferred that HRP was not denatured during its immobilization on MT-MWCNT composite. The biosensing principle was based on the determination of the cathodic responses of the immobilized HRP to H₂O₂, before and after incubation in trace metal standard solutions. Under optimum conditions, the inhibition rates of trace metals were proportional to their concentrations in the range of 0.092–0.55 mg L⁻¹, 0.068–2 mg L⁻¹ for Pb²⁺ and Cu²⁺ respectively. The limits of detection were 2.5 μg L⁻¹ for Pb²⁺ and 4.2 μg L⁻¹ for Cu²⁺. Representative Dixon and Cornish-Bowden plots were used to deduce the mode of inhibition induced by the trace metal ions. The inhibition was reversible and mixed for both metal ions. Furthermore, the biosensor showed good stability, selectivity, repeatability and reproducibility.     

Studies of adsorption for heavy metal ions and degradation of methyl orange based on the surface of ion-imprinted adsorbent

In order to prepare a novel adsorbent which can not only degrade organic compound, but also adsorb the heavy metal ions, immobilization of nanometer titanium dioxide on ion-imprinted chitosan carries was investigated. The amount of TiO₂, different kinds and amounts of dispersants, adding methods of TiO₂, different kinds of cross-linking agents and target metal ions are important factors influencing the degradation of Methyl Orange (MO) and the adsorption for Ni²⁺. When 15% amount of TiO₂ was added in preparation, the removal of MO was highly increased to nearly 90%, which was about eight times higher than that without TiO₂, at the same time, the effect of TiO₂ on the adsorption capacity was not obvious. The results show that in the presence of Ni²⁺ and MO, the MO could be removed effectively and the removal of MO reached 95.4%. At the initial concentration of Ni²⁺ of 200 mg/L, the adsorption capacity of Ni²⁺ reached 33 mg/g in the presence of MO.     

Alkaline phosphatase conductometric biosensor for heavy-metal ions determination

Alkaline phosphatase conductometric biosensors consisting of interdigitated gold electrodes and enzyme membranes have been used for assessment of heavy-metal ions in water. These analytes act as enzyme inhibitors. Enzyme residual activity has been measured in Tris-nitrate buffer without metal preincubation in the presence of Mg²⁺ ions as activator. The results indicate that the toxicity of the various metals tested toward immobilized phosphatase is ranged as follows: Cd²⁺ > Co²⁺ > Zn²⁺ > Ni²⁺ > Pb²⁺. Detection limits were about 0.5 ppm for Cd²⁺, 2 ppm for both Zn²⁺ and Co²⁺, 5 ppm for Ni²⁺ and 40 ppm for lead ions. In addition, the responses during 10 h were stable (RSD 4%) and a drift of about 7% per day was observed. The storage stability in buffer solution at 4 °C remained stable for more than one month.     

Co-remediation of pentachlorophenol and Cr6+ by free and immobilized cells of native Bacillus cereus isolate: Spectrometric characterization of PCP dechlorination products,bioreactor trial and chromate reductase activity

In this study, Bacillus cereus isolate efficiently remediated 57% PCP and 74% Cr⁶⁺ simultaneously with uptake rate of 0.65 mg Cr⁶⁺ g^?1 biomass h^?1 at initial 200 mg Cr⁶⁺ and 500 mg PCP l^?1 concentration under optimized 0.4% glucose, 0.2% NH₄Cl, pH 7.0, 35 °C, 1.0% inoculum during 60 h incubation. Optimization of agitation (100 rpm) and aeration (0.6 vvm) in bioreactor further enhanced PCP dechlorination by ～5.0% and Cr⁶⁺ removal 7.5%. Presence of other heavy metals variedly affected bioremediation of both the toxicants. Maximum and minimum inhibition was exhibited by mercury and lead, respectively. Out of 74% Cr⁶⁺ remediated, 90% reduced to Cr³⁺, of which 52.8% was associated with cell biomass and 37.2% with culture supernatant. Maximum chromate reductase activity was evident in culture supernatant followed by cytosolic fraction and cell debris. A direct correlation existed between chromate reductase activity and reduced Cr³⁺ in different cell fractions. Among matrices, alginate was most suitable for biomass immobilization, which enhanced Cr⁶⁺ removal by 20.2% compared to free cells at 36 h. Gas chromatography and mass spectrometry detected 2,3,4,6-tetrachlorophenol, 2,4,6-trichlorophenol, 2,6-dichlorophenol and 6-chlorohydroxyquinol as PCP dechlorination products. Our promising strain can be efficiently employed for simultaneous bioremediation of PCP and Cr⁶⁺ under wide environmental conditions.     

A simple method to prepare poly(amic acid)-modified biomass for enhancement of lead and cadmium adsorption

A modified biomass of baker's yeast was prepared by grafting poly(amic acid), which was obtained via reaction of pyromellitic dianhydride (PMDA) and thiourea, onto the biomass surface at 50 °C for 4 h. This method was simpler than other reported chemical grafting methods. The presence of poly(amic acid) on the biomass surface was verified by FTIR, X-ray photoelectron spectroscopy (XPS) and microscope analyses, and the amount of carboxylate and amide groups in the biomass surface were found to be 1.36 and 0.7 mmol g⁻¹ through potentiometric titration. Compared with the pristine biomass, the adsorption capacity of the modified biomass increased 15- and 11-fold for Cd²⁺ and Pb²⁺, respectively. According to the Langmuir equation, the maximum uptake capacities (q_m) for lead and cadmium were 210.5 and 95.2 mg g⁻¹, respectively. The kinetics for cadmium and lead adsorption followed the pseudo-second-order kinetics. FTIR and XPS demonstrated that carboxyl, amide, and hydroxyl groups were involved in the adsorption of lead and cadmium, and the adsorption mechanism for the two metal ions included ion exchange, electrostatic interaction and complexation.     

Population health risk due to dietary intake of toxic heavy metals from Spinacia oleracea harvested from soils collected in and around Tshwane,South Africa

In order to assess the possible health risk associated with the consumption of vegetables harvested from waste dump sites, trace metal levels in Spinacia oleracea planted in soils collected from waste dump sites were investigated. Soil samples from different waste dump sites and mining areas were collected and placed in different pots. Seedlings of S. oleracea were introduced into the pots, harvested after 3 months and analysed for trace metal contents using ICP-MS. From the leaves of the plants, the concentration of Fe was found to be significantly higher than all other trace metals (p < 0.05). The trend in trace metal accumulation from the leaves was in the order Fe > Mn > Zn > Pb > Cu > Cr > Ni > Cd. A significantly different concentration of trace metals in the plant was noticed from different soils in different pots used (p < 0.05). Trace metal concentration from plant parts showed roots > leaves > stem. The risk to human health indicated as Hazard Quotient (HQ) was highest for Zn followed by Cu from all the plant parts. The HQ result showed that humans might be at risk if they consume spinach from these waste dump sites. From the study it was concluded that harvesting/consuming spinach from soil around a waste dump site may be extremely dangerous.     

Application of dye-ligands affinity adsorbent in capturing of rabbit immunoglobulin G

The applicability of dye-ligands attached to an expanded bed chromatography quartz base matrix (Streamline™) for the affinity bioseparation of rabbit immunoglobulin G (IgG) was investigated. Reactive Green 5 (RG-5) immobilized onto adsorbent was selected for capturing of rabbit-IgG due to its higher binding capacity compared to other dye-ligands possessing similar ligand density. Adsorption parameters such as pH, temperature, ionic strength and initial rabbit-IgG concentration were optimized for the adsorption of rabbit-IgG on the RG-5-immobilized adsorbent. The highest rabbit-IgG adsorption was recorded in pH 7.0, while the maximum binding capacity for BSA was achieved at pH 4.0. The adsorption of rabbit-IgG on RG-5-immobilized adsorbent was declined as the increase of ionic strength. There is no significant influence of temperature against adsorption efficiency of RG-5-immobilized adsorbent for rabbit-IgG. The adsorption phenomenon of rabbit-IgG on RG-5-immobilized adsorbent appeared to follow the Langmuir–Freundlich adsorption isotherm model. The theoretically maximum binding capacity (q_m) of RG-5-immobilized adsorbent estimated from this isotherm was 49.3 mg ml⁻¹, which is very close to that obtained experimentally (49.0 mg ml⁻¹). About 50% of bound BSA on RG-5-immobilized adsorbent in binary adsorption system was removed with washing buffer containing 1 M NaCl.     

Hexavalent chromium removal from aqueous solution by adsorption on treated sawdust

The studies on adsorption of hexavalent chromium were conducted by varying various parameters such as contact time, pH, amount of adsorbent, concentration of adsorbate and temperature. The kinetics of adsorption of Cr(VI) ion followed pseudo second order. Langmuir adsorption isotherm was employed in order to evaluate the optimum adsorption capacity of the adsorbent. The adsorption capacity was found to be pH dependant. Sawdust was found to be very effective and reached equilibrium in 3 h (adsorbate concentration 30 mg l⁻¹). The rate constant has been calculated at 303, 308, 313 and 318 K and the activation energy (E_a) was calculated using the Arrhenius equation. Thermodynamic parameters such as standard Gibbs energy (ΔG°) and heat of adsorption (ΔH_r) were calculated. The ΔG° and ΔH_r values for Cr(VI) adsorption on the sawdust showed the process to be exothermic in nature. The percentage of adsorption increased with decrease in pH and showed maximum removal of Cr(VI) in the pH range 4.5–6.5 for an initial concentration of 5 mg l⁻¹.     

Origin of magnetization tunneling in single-molecule magnets as determined by single-crystal high-frequency EPR

We review an extensive body of single-crystal high-frequency electron paramagnetic resonance (HFEPR) data in order to determine the transverse spin Hamiltonian parameters that control the tunneling of the direction of magnetization in a variety of integer and half-integer-spin single-molecule magnets (SMMs). The SMMs studied are members of the following families: S = 9/2 [Mn₄O₃Cl]⁶⁺; S = 5 [Mn₃NiO₄]⁶⁺; S = 6 [Mn₃ZnO₄]⁶⁺; and S = 4 [Ni₄(OR)₄]⁴⁺. HFEPR spectra for the half-integer S = 9/2 Mn₄ complexes that have C₃ symmetry do not provide measurable evidence for transverse spin Hamiltonian terms. This finding is consistent with the relatively large coercive field seen in the magnetization hysteresis loops for these complexes. On the other hand, a low symmetry S = 9/2 complex exhibits a much faster rate of ground-state magnetization tunneling, in agreement with HFEPR spectra for a powder sample that gives a rhombic zero-field splitting (ZFS) parameter of E = 0.140 cm^?1. The S = 5 Mn₃Ni systems exhibit magnetization tunneling that is much faster than seen for the high-symmetry S = 9/2 Mn₄ complexes. This can be attributed to their integer-spin ground states. Like the C₃ symmetry Mn₄ SMMs, the HFEPR spectra for high-symmetry Mn₃Ni complexes do not provide measurable evidence for transverse ZFS terms. However, the spectra exhibit broad peaks, suggesting distributions in the local molecular environments brought about by disordered solvate molecules. This disorder likely explains the fast tunneling in the high-symmetry S = 5 Mn₃Ni systems, though one cannot rule out fourth- (and higher-) order interactions that cannot be detected by HFEPR due to the broad resonances. The one S = 6 Mn₃Zn complex shows an even faster rate of tunneling compared to the isostructural S = 5 Mn₃Ni complex. Finally, the S = 4 [Ni(hmp)(dmb)Cl]₄ complex provides unique insights into the origin of fourth- (and higher-) order interactions found for many SMMs on the basis of analysis using a giant spin Hamiltonian (GSH) approximation. We conclude that the fourth-order anisotropy found for the S = 4 ground state of [Ni(hmp)(dmb)Cl]₄ originates from the second-order ZFS interactions associated with the individual Ni^II ions, but only as a result of higher-order processes that occur via S-mixing between the ground state and higher-lying (S < 4) spin-multiplets. The S-mixing is relatively strong in this system because of comparable exchange and anisotropy energy scales. The relatively fast tunneling is a direct consequence of this S-mixing, as opposed to any intrinsic fourth-order (spin–orbit) anisotropy associated with Ni^II.     

Characterization of a metal resistant Pseudomonas sp. isolated from uranium mine for its potential in heavy metal (Ni2+, Co2+, Cu2+, and Cd2+) sequestration

Heavy metal sequestration by a multimetal resistant Pseudomonas strain isolated from a uranium mine was characterized for its potential application in metal bioremediation. 16S rRNA gene analysis revealed phylogenetic relatedness of this isolate to Pseudomonas fluorescens. Metal uptake by this bacterium was monophasic, fast saturating, concentration and pH dependent with maximum loading of 1048 nmol Ni²⁺ followed by 845 nmol Co²⁺, 828 nmol Cu²⁺ and 700 nmol Cd²⁺ mg^?1 dry wt. Preferential metal deposition in cell envelope was confirmed by TEM and cell fractionation. FTIR spectroscopy and EDX analysis revealed a major role of carboxyl and phosphoryl groups along with a possible ion exchange mechanism in cation binding. Binary system demonstrated selective metal binding affinity in the order of Cu²⁺ > Ni²⁺ > Co²⁺ > Cd²⁺. A comparison with similar metal uptake reports considering live bacteria strongly indicated the superiority of this strain in metal sequestration, which could be useful for developing efficient metal removal system.     

Diversity and heavy metal tolerance of endophytic fungi from six dominant plant species in a Pb–Zn mine wasteland in China

The diversity and metal tolerance of endophytic fungi from six dominant plant species in a Pb–Zn mine wasteland in Yunnan, China were investigated. Four hundred and ninety-five endophytic fungi were isolated from 690 tissue segments. The endophytic fungal colonization extent and isolation extent ranged from 59 % to 75 %, and 0.42–0.93, respectively, and a positive correlation was detected between them. Stems harboured more endophytic fungi than leaves in each plant species, and the average colonization extent of stems was 82 %, being significantly higher than that of leaves (47 %) (P ≤ 0.001, chi-square test). The fungi were identified to 20 taxa in which Phoma, Alternaria and Peyronellaea were the dominant genera and the relative frequencies of them were 39.6 %, 19.0 % and 20.4 %, respectively. Metal tolerance test showed that 3.6 mM Pb²⁺ or 11.5 mM Zn²⁺ exhibited the greatest toxicity to some isolates and they did not grow on the metal-amended media. In contrast, some isolates were growth stimulated in the presence of tested metals. The isolates of Phoma were more sensitive to Zn²⁺ than the isolates of Alternaria and Peyronellaea. However, the sensitivity of isolates to Pb²⁺ was not significantly different among Phoma, Alternaria, Peyronellaea and other taxa (P > 0.05, chi-square test). Our results suggested that fungal endophyte colonization in Pb–Zn polluted plants is moderately abundant and some isolates have a marked adaptation to Pb²⁺ and Zn²⁺ metals, which has a potential application in phytoremediation in this area.     

Response surface analysis for enzymatic decolorization of Congo red by manganese peroxidase

The enzymatic decolorization process of manganese peroxidase (MnP) is a complex system, which is greatly affected by the concentrations of H₂O₂, Mn²⁺, dye and enzyme. This work aimed to study these factors and investigate the combined interactions between them by applying response surface methodology (RSM) for decolorization of Congo red with MnP from Schizophyllum sp. F17, meanwhile conventional one-factor-at-a-time analysis was carried out. Through the one-factor-at-a-time analysis the optimized H₂O₂, Mn²⁺, Congo red and MnP extract was 0.2 mM, 0.5 mM, 50 mg/l and 0.8 ml, respectively, and the maximum decolorization attained under such conditions was 24.2%. Response surface analysis was conducted through Box–Behnken design and a second-order polynomial model (R² = 0.8565) was generated to describe the combined effect and the interactions quantificationally. ANOVA analysis indicated that the interactions between H₂O₂ and MnP, between dye and MnP were significant; the optimum condition through RSM was found to be 0.35 mM H₂O₂, 0.5 mM Mn²⁺, 75 mg/l Congo red and 1.4 ml MnP extract, for maximum decolorization of 30.8%.     

Mn2+ and Mg2+ improved sphingomyelinase production by Lactobacillus rhamnosus FTDC 8313 and binding affinity to sphingomyelin for generation of ceramides

The present research aims to optimize the sphingomyelinase (SMase) activity produced by Lactobacillus rhamnosus FTDC 8313 using divalent metal ions via response surface methodology and to further study the effects of the divalent metal ions on SMase activity using molecular modeling approach. This study also aimed to assess the possibility of increasing ceramide levels in vitro on cultured keratinocytes upon treatment with the extracellular extract of the optimized L. rhamnosus FTDC 8313. Using a central composite design, an optimum point of SMase activity (6.54 mU ml^?1) was produced from a combination of 0.65% (w/v) MnSO₄ and 0.82% (w/v) MgSO₄. 3D response surface indicated that the altered availability of the two ions (Mn²⁺ and Mg²⁺) reduced their effects on SMase activity. In addition, the treatment of the HaCaT cells with optimized extracellular extract of L. rhamnosus FTDC8313 significantly increased (P < 0.05) the conversion of sphingomyelin to ceramide as compared to the control. Molecular docking demonstrated that the addition of Mn²⁺ and Mg²⁺ into the active site of SMase improved the binding affinity between the SMase and sphingomyelin based on its free energy of binding as well as the interaction distances between the important catalytic residues Glu53 and His296.     

Arginase from Bacillus thuringiensis SK 20.001: Purification,characteristics, and implications for l-ornithine biosynthesis

An l-ornithine high producing strain Bacillus thuringiensis SK20.001 was screened by our laboratory. An intracellular arginase used to biosynthesize l-ornithine from the strain was purified and characterized. The final specific arginase activity was 589.2 units/mg, with 70.1 fold enrichment and 22.4% recovery. The molecular weight of the enzyme was approximately 33,000 Da as evaluated by SDS-PAGE and 191,000 Da as determined by gel filtration. The enzyme had an optimum pH of 10.0 and an optimum temperature of 40 °C. It was stable from pH 8.0–12.0 and <50 °C without Mn²⁺. The presence of Mn²⁺ and Ni²⁺ had strong effects on the enzyme activity, and Mn²⁺ significantly increased the thermal stability of the enzyme. The arginase was slightly inhibited by Ca²⁺, Fe²⁺ and Zn²⁺. Trp, Asp, Glu, Tyr, and Arg residues were directly involved in the arginase activity evaluated by chemical modifications. The K_m and V_max for l-arginine were estimated to be 15.6 mM and 538.9 μmol/min/mg. The biosynthesis yield of l-ornithine was 72.7 g/L with the enzyme.     

Significant impact of divalent metal ions on the fidelity,sugar selectivity,and drug incorporation efficiency of human PrimPol

Human PrimPol is a recently discovered bifunctional enzyme that displays DNA template-directed primase and polymerase activities. PrimPol has been implicated in nuclear and mitochondrial DNA replication fork progression and restart as well as DNA lesion bypass. Published evidence suggests that PrimPol is a Mn²⁺-dependent enzyme as it shows significantly improved primase and polymerase activities when binding Mn²⁺, rather than Mg²⁺, as a divalent metal ion cofactor. Consistently, our fluorescence anisotropy assays determined that PrimPol binds to a primer/template DNA substrate with affinities of 29 and 979 nM in the presence of Mn²⁺ and Mg²⁺, respectively. Our pre-steady-state kinetic analysis revealed that PrimPol incorporates correct dNTPs with 100-fold higher efficiency with Mn²⁺ than with Mg²⁺. Notably, the substitution fidelity of PrimPol in the presence of Mn²⁺ was determined to be in the range of 3.4 × 10⁻² to 3.8 × 10⁻¹, indicating that PrimPol is an error-prone polymerase. Furthermore, we kinetically determined the sugar selectivity of PrimPol to be 57–1800 with Mn²⁺ and 150–4500 with Mg²⁺, and found that PrimPol was able to incorporate the triphosphates of two anticancer drugs (cytarabine and gemcitabine), but not two antiviral drugs (emtricitabine and lamivudine).     

Toxic metal biosorption by macrocolonies of cyanobacterium <Emphasis Type="Italic">Nostoc sphaeroides</Emphasis> Kützing

The cyanobacterium Nostoc sphaeroides Kützing is expected to be effective in toxic metal adsorption as it produces abundant exopolysaccharides with functional groups. Therefore, the adsorption properties of Cu²⁺, Cd²⁺, Cr³⁺, Pb²⁺, Ni²⁺, and Mn²⁺ on fresh macrocolonies and algal powder of N. sphaeroides were compared at pH 5 and 25 °C. The adsorption capacity of fresh biomass for Pb²⁺ and of algal powder for Pb²⁺ and Cr³⁺ were highest in single metal solutions. Compared to the fresh biomass, the metal adsorption capacities of algal powder were similar for Ni²⁺, Cd²⁺, and Pb²⁺ and slightly greater for Cr³⁺, but they were markedly smaller for Mn²⁺ and Cu²⁺. Coexisting ions (in tap water or in multiple solutions) significantly decreased the metal adsorption capacity, except for Cr³⁺ in tap water. The Pb²⁺ and Cr³⁺ adsorption dynamic process fitted the pseudo-second-order model well, showing fast adsorption at the first stage in 10 and 20 min, respectively. Higher pH in acidic ranges favored the adsorption greatly. The Langmuir isotherm model was suitable for explaining the adsorption, and the maximum adsorption capacities were 116.28 and 22.37 mg g^?1 for Pb²⁺ and Cr³⁺, respectively. The adsorption process was endothermic, confirmed by the significantly higher adsorption capability at higher temperature. Hydroxyl, amino, and carboxyl groups were the main functional groups based on Fourier transform infrared spectroscopy analysis, and they bind to metal ions via ion exchange. The results suggest that fresh macrocolonies of N. sphaeroides can be used as an effective biosorbent for metal ion removal, especially for Pb²⁺ and Cr³⁺.