Hypophosphite oxidase fromBacillus caldolyticus

Bacillus caldolyticus can utilize phosphorus either as phosphate, phosphite, or hypophosphite. When cultures are supplied with PO₂ as the sole source of phosphorus, the hypophosphite is oxidized to phosphate, which accumulates in the medium prior to the beginning of the log phase, and is then metabolised during growth. Resting cell suspensions also have the ability to oxidise PO₂ to PO₄. The reaction is specific for hypophosphite: PO₃ is not oxidised to PO₄, regardless of whether the cells are grown in PO₃- or PO₂-medium. The hypophosphite oxidase works optimally between pH 7.0 to 7.5, with a temperature optimum at 75°C; theK _m for NaH₂PO₂ is 320 μM. Sonication of cells, followed by high-speed centrifugation and ammonium sulfate fractionation of the cell-free extract showed that the PO₂ oxidation, which is accompanied by the formation of NADH, requires at least three components: An ammonium sulfate fraction of the cell-free extract, the residue fraction containing the respiratory chain, and NAD as cofactor. Most probably a second cofactor, so far not characterized, is required to accomplish full activity.     

Shoot specific fungal endophytes alter soil phosphorus (P) fractions and potential acid phosphatase activity but do not increase P uptake in tall fescue

Aims

An experiment was performed to test how different fungal endophyte strains influenced tall fescue’s ability to access P from four P sources varying in solubility.

Methods

Novel endophyte infected (AR542E+ or AR584E+), common toxic endophyte infected (CTE+), or endophyte-free (E-) tall fescues were grown for 90 days in acidic soils amended with 30 mg kg^?1 P of potassium dihydrogen phosphate (KH₂PO₄), iron phosphate (FePO₄), aluminum phosphate (AlPO₄), or tricalcium phosphate ((Ca₃(PO₄)₂), respectively.

Results

Phosphorus form strongly influenced plant biomass, P acquisition, agronomic P use efficiency, microbial communities, P fractions. P uptake and vegetative biomass were similar for plants grown with AlPO₄, Ca₃(PO₄)₂, and KH₂PO₄ but greater than in control and FePO₄ soils. Infection with AR542E+ resulted in significantly less shoot biomass than CTE+ and E- varieties; there was no influence of endophyte on root biomass. The biomarker for arbuscular mycorrhizal fungi (AM fungi, 16:1ω5c) was selected as an effective predictor of variations in P uptake and tall fescue biomass. Potential acid phosphatase activity was strongly influenced by endophyte x P form interaction.

Conclusions

Endophyte infection in tall fescue significantly affected the NaOH-extractable inorganic P fraction, but had little detectable influence on soil microbial community structure, root biomass, or P uptake.

     

Lead toxicity and phosphate deficiency in chlamydomonas

The addition of lead salts to phosphate-containing Chlamydomonas reinhardtii media caused precipitation of Pb₃(PO₄)₂, effectively removing phosphate from solution. The effect of Pb²⁺ on growth of Chlamydomonas in liquid cultures depended strictly on the ratio of the equivalents of Pb²⁺ to phosphate present. When the amount of Pb²⁺ approached equivalency with phosphate, cell growth was initially slow as cells adhered to the surface of the precipitated Pb₃(PO₄)₂. Later, cells grew at a normal rate, spread throughout the solution, and reached the same densities obtained in the absence of Pb²⁺. Cells did not survive when the amount of Pb²⁺ in the culture exceeded the equivalents of phosphate.

Elemental analysis showed that in the presence of equivalent Pb²⁺ and phosphate, considerable Pb²⁺ remained in solution. The concentration of dissolved Pb²⁺ did not vary significantly when the amount of Pb²⁺ added to the culture was increased slightly, from an amount which permitted growth to an amount which completely prevented growth. The concentration of phosphate was decreased to an undetectable level when the amount of Pb²⁺ approached equivalency with phosphate.

In the presence of the chelating agent nitrilotriacetic acid, higher concentrations of Pb²⁺ remained in phosphate-containing media. The chelated Pb²⁺ did not retard the growth of Chlamydomonas.

It appears that Pb²⁺ is not toxic to Chlamydomonas, but kills cells by depriving them of phosphate.

     

PHOSPHOLTPID METABOLISM IN ISOLATED NEURONAL AND GLIAL CELLS FROM BRAINS OF 17-DAY OLD RATS1

Neuronal and glial cells were isolated from the brains of 17-day old rats and incubated for 5 h with either radioactive inorganic phosphate, palmitate, serine, choline or ethanolamine in a tissue culture medium. A comparison of the results suggests that both neuronal and glial cells exhibit effective de novo, phospholipid synthesis and that the observed differences in the uptake are due more to quantitative rather than qualitative differences in phospholipid metabolism of both cell types. Incubations of the combined neuronal and glial fractions with ³²PO₄ and [³H]palmitate result in incorporations up to 100% higher than calculated from incubations of the separate fractions, suggesting that phospholipid metabolism of neuronal and glial cells may exhibit cooperativity.     

Alterations of alkaline phosphatase activity during adaptation of Escherichia coli to phosphite and hypophosphite

When Escherichia coli cells were grown in media containing either phosphite or hypophosphite as the sole source of phosphorus, they responded to this situation primarily in the same way as phosphatelimited cultures: The activity of alkaline phosphatase increased drastically, which under natural conditions would enable the cells to compklensatae for the shortage increased drastically, which under natural conditions would enable the cells to compensate for the shortage of phosphate. Subsequent transfers, however, resulted in a quite different response: While the phosphatase activity of phosphate-limited cells stays at a high derepressed level, its increase was followed by a gradual decline in organisms grown on phosphite or hypophosphite. After eight to ten transfers on these P-compounds, phosphatase activity was back to its initial, repressed, low level, indicating that the cells were fully adapted to these substrates. Adaptation to either PO ₃ ^3- or PO ₂ ^3- was completely abolished if the cells were again grown with PO ₄ ^3- as P-source, whereafter the entire process of adaptation had to be repeated. The observed adaptation pattern, reflected by the alterations of phosphatase activity, was qualitatively equal with PO ₃ ^3- and PO ₂ ^3- , but quantitatively different, because the response to hypophosphite gave much higher values than the increase obtained with phosphite.Phosphite-adapted cells are not simultaneously adapted to hypophosphite, but their response to the latter was less intense than observed after direct transfers from PO ₄ ^3- to PO ₂ ^3- . Adaptation to hypophosphite, however, led simultaneously to phosphite adaptation, so that these cells can utilize both P-compounds as a substitute for phosphate.     

Determination of molecular groups involved in the interaction of annexin A5 with lipid membrane models at the air-water interface

Annexin A5 (AnxA5) is a member of a family of homologous proteins sharing the ability to bind to negatively charged phospholipid membranes in a Ca²⁺-dependent manner. In this paper, we used polarization-modulated infrared reflection absorption spectroscopy (PMIRRAS), Brewster angle microscopy (BAM), and ellipsometry to investigate changes both in the structure of AnxA5 and phospholipid head groups associated with membrane binding. We found that the secondary structure of AnxA5 in the AnxA5/Ca²⁺/lipid ternary complex is conserved, mainly in α-helices and the average orientation of the α-helices of the protein is slightly tilted with respect to the normal to the phospholipid monolayer. Upon interaction between AnxA5 and phospholipids, a shift of the ν_as PO₂⁻ band is observed by PMIRRAS. This reveals that the phosphate group is the main group involved in the binding of AnxA5 to phospholipids via Ca²⁺ ions, even when some carboxylate groups are accessible (PS). PMIRRAS spectra also indicate a change of carboxylate orientation in the aspartate and glutamate residues implicated in the association of the AnxA5, which could be linked to the 2D crystallization of protein under the phospholipid monolayer. Finally, we demonstrated that the interaction of AnxA5 with pure carboxylate groups of an oleic acid monolayer is possible, but the orientation of the protein under the lipid is completely different.     

Cytotoxic Effect of Photoluminescent RE3+ Doped Ca3(PO4)2 Nanorods on Breast Cancer Cell Lines

BackgroundBreast cancer reported in the young women exhibits high local and distant recurrence and a poor prognosis. Rare earth doped calcium phosphate phosphors have been extensively investigated due to their unique applications in biomedicine.MethodsIn the current study, Tb³⁺, Ce³⁺ doped Ca₃(PO₄)₂ phosphor were prepared by hydrothermal method at 150 °C using citric acid as additive and characterized by PXRD, FT-IR, TG-DTA, EDX, TEM and PL techniques. The photoluminescence properties of Tb³⁺, Ce³⁺ doped Ca₃(PO₄)₂ phosphor was investigated upon photo excitation at 240 nm. Antiproliferative activity was evaluated by MTT, BrdU proliferation, ELISA, Methylene blue and caspase-3 assays.ResultsCa₃(PO₄)₂:Tb³⁺, Ce³⁺ phosphor exhibited needle like morphology with length and width ∼100-500 nm and ∼40-50 nm, respectively. It exhibited green emission at 550 nm corresponding to ⁵D₄→⁷F₅ transition with the CIE coordinates (x, y) as (0.284, 0.614). It also showed remarkable concentration dependent cytotoxicity against MCF-7 as well as MDA-MB 231 cells with negligible cytotoxicity compared to MCF-12A, a human epithelial healthy cell line. It reduced the proliferative index of both cell lines in a concentration dependent manner by inhibiting DNA synthesis and Ki67 protein. It also induced distinct apoptotic changes in the morphology of cell and nucleus and also activated the caspase-3 activity in breast cancer cell lines.ConclusionThe results suggest that Ca₃(PO₄)₂:Tb³⁺, Ce³⁺ phosphor may be useful for therapeutic application in clinical settings.     

Preservation of dried liposomes in the presence of sugar and phosphate

It has been well established that sugars can be used to stabilize liposomes during drying by a mechanism that involves the formation of a glassy state by the sugars as well as by a direct interaction between the sugar and the phospholipid head groups. We have investigated the protective effect of phosphate on solute retention and storage stability of egg phosphatidylcholine (egg PC) liposomes that were dried (air-dried and freeze-dried) in the presence of sugars and phosphate. The protective effect of phosphate was tested using both glucose (low T_g) and sucrose (high T_g) by measuring leakage of carboxyfluorescein (CF), which was incorporated inside the vesicles. Liposomes that were dried with glucose or phosphate alone showed complete leakage after rehydration. However, approximately 30% CF-retention was obtained using mixtures of phosphate and glucose. Approximately 75% CF-retention was observed with liposomes that were dried with sucrose. The solute retention further increased to 85% using mixtures of phosphate and sucrose. The pH of the phosphate buffer prior to drying was found to have a strong effect on the solute retention. Fourier transform infrared spectroscopy studies showed that phosphate and sugars form a strong hydrogen bonding network, which dramatically increased the T_g. The HPO₄²⁻ form of phosphate was found to interact stronger with sugars than the H₂PO₄⁻ form. The increased solute retention of liposomes dried in the sugar phosphate mixtures did not coincide with improved storage stability. At temperatures below 60 °C the rate of solute-leakage was found to be strikingly higher in the presence of phosphate, indicating that phosphate impairs storage stability of dried liposomes.     

Interaction of Doxorubicin and Dipalmitoylphosphatidylcholine Liposomes

The interaction between doxorubicin (DOX), an anthracycline antibiotic frequently used in chemotherapy, and zwitterionic dipalmitoylphosphatidylcholine (DPPC) was investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and rheological measurements. FTIR results showed that DOX shifted the wavenumber of the PO₂ ⁻ band for pure DPPC to a higher wavenumber. This may have been because of the strong interactions between the NH₃ ⁺ group in DOX and the phosphate (PO₂ ⁻) group in the polar head of DPPC. The main transition temperature of DPPC liposomes was slightly shifted to a lower temperature for DPPC liposome-encapsulated DOX. This suggested that DOX had a significant effect on the acyl chains in the DPPC bilayers, and that its presence decreased the transition cooperativity of lipid acyl chains. There was also the appearance of an additional transition peak at nearly 136°C for the DPPC/DOX sample. These interactions between DOX and DPPC phospholipid would cause a decrease in the DPPC liposomes plastic viscosity and increase membrane fluidity. A better understanding of the interactions between DOX and lipid bilayers could help in the design and development of improved liposomal drug delivery systems.     

Factors influencing phosphate exchange across the sediment-water interface of eutrophic reservoirs

The results of a survey of the sediment chemistry of 7 East Anglian reservoirs are presented as part of a regional study on the assessment and control of eutrophication. The influence of water quality (dissolved oxygen, pH, temperature) on phosphate (PO₄) adsorption by sediment from hypertrophic Ardleigh Reservoir is also examined. Extractable phosphate-P (extr.-P) varied between 92 and 383 mg kg^–1 dry matter. Extractable P varied between 5.3 and 16.6% of the total phosphate-P (Tot. P) content and increased with the concentration of dissolved reactive phosphate-P (DRP) in the overlying water column. Organically complexed iron (organic Fe) was the determinand which correlated most closely with phosphate adsorption capacity, PAC (r = 0.8). Organic Fe was also related inversely to Extr. P. The rate and extent of PO₄ adsorption by Ardleigh Reservoir sediment increased with the initial concentration of DRP and adsorption equilibria were reached after 24 h. The equilibrium DRP concentration, [DRP], was 0.7 mg P 1^–1 under aerobic conditions indicative of a high potential for PO₄ exchange. The rate and extent of PO₄ adsorption was greater at 7 °C than at 22 °C PO₄ adsorption increased markedly with dissolved oxygen status. Ardleigh sediment exhibited a marked buffering capacity to a change in pH; however, PO₄ adsorption was greatest at an equilibrium pH of 5.6 and decreased progressively either side of this pH value.Options for the artificial control of sediment PO₄ release are discussed in relation to the seasonal variation in sediment PO₄ exchange observed for Ardleigh Reservoir.     

Hydrothermal synthesis and characterization of a novel 3D open framework structure of mixed valence ethylenediamine-vanadium phosphate: [C2H10N2][(HVO3)(HVO2) (PO4)]

A new three-dimensional open framework structure of mixed valence ethylenediamine-vanadium phosphate [C₂H₁₀N₂][(HV^IVO₃)(HV^VO₂)(PO₄)] (1), has been synthesized under mild hydrothermal conditions and characterized by elemental analyses, IR, fluorescent spectrum, TG-DTA and single crystal X-ray diffraction. Compound 1 exhibits a novel three-dimensional (3D) vanadium phosphate anion framework composed of vanadium, phosphate, and oxygen atoms through covalent bonds, with the diprotonated ethylenediamine [NH₃CH₂CH₂NH₃]²⁺ cations residing in the channels along c-axis. The organic diprotonated ethylenediamine cations interact with the O atoms in the inorganic network through hydrogen bonds. The electrochemical behavior of 1 has also been studied in detail by cyclic voltammograms, which is very important for practical applications in electrode modification. Furthermore, the strong photoluminescence property of compound 1 is also measured at room temperature.     

Vibrational analysis of nucleic acids. IV. normal modes of the DNA phosphodiester structure modeled by diethyl phosphate

Raman and ir spectra are reported for diethyl phosphate [(CH₃CH₂O)₂PO^-₂] and diethyl phosphate isotopomers incorporating carbon-13 at methylene group sites [(CH¹³₃CH₂O)₂PO^-₂] and deuterium substituents on methyl and methylene carbons [(CH₃CD₂O)₂PO^-₂, (CD₃CH₂O)₂PO^-₂ (CD₃CD₂O)₂PO^-₂]. The vibrational spectra are analyzed to develop a consistent set of assignments for the C-C-O-P(O^-₂)-O-C-C network, which serves as a model for the nucleic acid phosphodiester backbone. The present study resolves previously conflicting vibrational assignments for the phosphodiester skeleton and provides a firm empirical basis for interpreting conformationally sensitive modes of DNA and RNA. Ab initio vibrational analyses have also been conducted on the above isotopomers of diethyl phosphate in the trans-gauche-gauche-trans conformation, optimized using the 3-21+G^* basis set at the restricted Hartree-Fock level. The ab initio calculations are in good agreement with the empirical results, thus strengthening the proposed assignment scheme for Raman and infrared spectra. The present study provides a basis for improvement of empirical force fields utilized in previous normal coordinate analyses of the nucleic acid phosphodiester group. © 1996 John Wiley & Sons, Inc.     

Phosphate Solubility and the Cyanate-Mediated Synthesis of Pyrophosphate

The justification for a less alkaline primordial ocean (than present) is briefly reviewed, along with constraints on aqueous phosphate under such conditions. Based on the assumption that CaHPO₄ dihydrate determined the availability of phosphorus species, we have carried out laboratory simulations to determine equilibrium concentrations as a function of pH (in PIPES buffer) with added NaCl and CaCl₂. Consistent with expectations, solubility declines with higher pH and [CaCl₂], but increases only slightly with [NaCl]. Significantly, PIPES shows no specific effect on the dissolution beyond its influence on pH and ionic strength. Data are also presented on the synthesis of pyrophosphate from the NaOCN/CaHPO₄·2H₂O system, which could have provided a source of this phosphate anhydride on the early Earth.     

Effect of nitrogen and phosphorus on algal growth in citrus wastes experimental oxidation pond

Summary Concentrations of 50 mg/l nitrate (as NO₃ ^–) and 20 mg/l phosphate (as PO₄---) were found to be optimal for algal growth in experimental citrus waste oxidation ponds.Reliable results were only obtained after three weeks of detention. Nitrogen or phosphorus alone did not suffice for stimulating algal growth but had to be used together. Dilution of the waste resulted in very poor growth.Several inexpensive fertilizers were compared with sodium nitrate and phosphate and were found to give an equivalent algal yield.

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Résumé Pour le développement des algues dans des ponds d'oxidation expímentales du dechet de l'industrie des agrumes les concentrations ci dessous ont été trouvées optimales: 50 mg/1 de nitrate (NO₃ ^–) et 20 mg/1 phosphate (PO₄---). On n'a obtenu des réesultats satisfaisants qu'apres trois semaines de detention.Seulement l'azote or le phosphore ne stimule pas le développement des algues: il faut les utiliser en conjunction.La prolifération des algues dans des eaux résiduaires diluées est très faible.Plusieurs engrais moins chers ont été comparés au nitrate de soude et au phosphate et ont donné des résultats équivalents aux développement des algues.

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This study was sponsored by the Ministry of Agriculture — Water Commission.     

Most probable number quantification of hypophosphite and phosphite oxidizing bacteria in natural aquatic and terrestrial environments

Concentrations of hypophosphite and phosphite oxidizing bacteria were found to be high, relative to bacterial concentrations growing on phosphate, in sediment and soil during winter and summer seasons from 12 common terrestrial and aquatic sites using a most probable number method. The percent of total culturable bacterial concentrations that could use these reduced phosphorus compounds as a sole source of phosphorus were as follows: hypophosphite, 7–100%; phosphite, 10–67%; aminoethylphosphonate, 34–270%. The average MPN/g (±SEM) was as follows: phosphate, 6.19 × 10⁶ (±2.40 × 10⁶); hypophosphite, 2.61 × 10⁶ (±1.35 × 10⁶) phosphite, 1.91 × 10⁶ (±1.02 × 10⁶); aminoethylphosphonate, 3.90 × 10⁶ (± 1.95 × 10⁶). Relatively high concentrations of reduced phosphorus oxidizing bacteria were found in both pristine sites and sites with urban and agricultural disturbance. Concentrations of reduced phosphorus oxidizing bacteria in anoxic sediments and soil were equivalent. Our data indicate that reduced phosphorus oxidizing bacteria are abundant in the environment and provide strong evidence for the importance of bacterial P oxidation in nature.     

Characterization of phosphate absorption in maize root cortex segments

Uptake of phosphate ions by 1 mm segments of isolated maize root cortex layers was studied. Cortex segments (from roots of 8 days old maize plants) absorb phosphate ions from 1 mM KH₂PO₄ in 0.2 mM CaSCO₄ at the average rate of 34.3 ±3.2 μg P_i g^?1 (fr. m.) h^?1,i.e. 0.35± 0.02 μmol P_i g^?1 (fr. m.) h^?1. Phosphate uptake considerably increases after a certain period of “augmentation”,i.e. washing in aerated 0.2 mM CaSO₄. This increase is completely blocked by the presence of 10 μg ml^?1 cycloheximide. The relation of uptake rate to phosphate concentration in the medium was shown to have 3 phases in the concentration range of 0.02 - 40 mM. Transition points were found between 0.8–1 mM and 10–20 mM. Following K_m and V_max values were found: K_m[mM] : 0.37 - 3.82 - 27.67 V_max[μg P_i g^?1 (fr. m.) h^?1] : 3.33 - 39.40 - 66.67 We have found no sharp pH optimum for phosphate uptake. It proceeds at almost constant rate till pH 6.0 and then the uptake rate drops with increasing pH. At low phosphate concentrations (1 mM) the lowest uptake rate was found at 5 and 13 °C, while the uptake is higher at 5 °C than at 13 °C at phosphate concentrations higher than 1 mM. At these concentrations uptake rate at 35 °C is lower than at 25 °C. Phosphate uptake considerably decreased in anaerobic conditions. DNP and iodoacetate (0.1 mM) completely blocked phosphate uptake from 1 mM KH₂PO₄, while uptake from 5 and 10 mM KH₂PO₄ was left unaffected by these substances. The inhibitors of active - SH groups NEM and PCMB inhibited phosphate uptake: 10^?3 M NEM by 81.6%, 10⁴ M NEM by 42% and 10^?4 M PCMB by 42%.     

Biological response to lake remediation by phosphate stripping: control of Cladophora

• 1 The North and South Basins of Windermere, Cumbria, have experienced a large increase in concentrations of nutrients, particularly phosphate, since 1945 when detailed measurements began. Over‐winter concentrations have increased from 1 to 3 mg PO₄‐P m^‐3 in the 1940s, up to 30 mg PO₄‐P m^‐3 in the South Basin of Windermere in the early 1990s where nutrient enrichment has been most marked. A visible manifestation of this ‘eutrophication’ in recent years has been the production of a large biomass by the green filamentous macroalga, Cladophora.
• 2 Since April 1992, tertiary chemical stripping of phosphate at the two sewage treatment plants on Windermere has reduced direct sources of phosphate to both basins. In the South Basin, over‐winter concentrations of phosphate have fallen to values similar to those in the early 1970s.
• 3 The biomass of Cladophora has declined markedly in response to the reduced phosphate availability. Significant relationships were found between the annual maximum biomass of Cladophora and two measures of phosphate availability: the over‐winter concentration and, more strongly, the day of year when the concentration fell below 1 mg m^‐3.
• 4 The annual biomass maxima of Cladophora since 1945, estimated from the regressions, showed a gradual increased potential for biomass production after 1965 as phosphate concentrations increased, followed by a striking and rapid biological response to lake remediation by phosphate stripping.

     

THE R?LE OF PHOSPHATE IN BIOLOGICAL OXIDATIONS

1. The effect of phosphate on the oxidation of glyceric aldehyde by methylene blue, 1-naphthol 2-sulfonate indophenol, and phenol-indophenol has been studied. 2. At pH 4.77 in a phthalate-buffered medium phosphate does not catalyze the reaction. 3. At pH 7.9 in solutions buffered with borate, carbonate, or phenylalanine marked catalysis by phosphate is observed. The effect is most pronounced in borate. 4. Phosphate catalysis, within the limits studied, is strictly a linear function of the phosphate concentration. 5. The high concentration of HPO₄ ⁼ and the low concentration of PO₄ ^≡ relative to that of the substrate virtually demand the conclusion that the PO₄ ^≡ ion is the active catalytic species.     

Association of Potassium and Some Other Monovalent Cations with Occurrence of Polyphosphate Bodies in Chlorella pyrenoidosa

Phosphate-starved Chlorella pyrenoidosa cells formed polyphosphate bodies (PB) upon transfer into nutrient solutions containing phosphate and potassium, or another monovalent cation, such as Na⁺, NH₄⁺, Li⁺, or Rb⁺. The phenomenon was studied by chemical analyses, light microscopy, and electron microscopy.

When the P-starved cells were transferred into a complete nutrient solution containing 100 micromolar P, they accumulated large quantities of P and K within several hours. The accumulation was accompanied by a corresponding appearance of PB in the cells. The absence of K from the medium prevented appreciable P accumulation and PB formation, but omitting Ca or Mg did not.

The P-starved cells exposed to a simple solution of at least 20 micromolar H₃PO₄ and 100 micromolar KHCO₃ responded in a similar manner as the cells exposed to the complete nutrient solution. However, the PB appeared structurally different.

It is proposed that monovalent cations are essential for PB formation in C. pyrenoidosa. K is suggested to be a major component of PB formed in K-sufficient media.

     

An FTIR Spectroscopic Study of Calf-thymus DNA Complexation with Al(III) and Ga(III) Cations

Abstract

The interaction of calf-thymus DNA with trivalent Al and Ga cations, in aqueous solution at pH =6–7 with cation/DNA(P) (P=phosphate) molar ratios (r) 1/80, 1/40, 1/20, 1/10, 1/4 and 1/2 was characterized by Fourier Transform infrared (FTIR) difference spectroscopy.

Spectroscopic results show the formation of several types of cation-DNA complexes. At low metal ion concentration (r=l/80, 1/40), both cations bind mainly to the backbone PO₂ group and the guanine N-7 site of the G-C base pairs (chelation). Evidence for cation chelate formation comes from major shifting and intensity increase of the phosphate antisymmetric stretch at 1222 cm-¹ and the mainly guanine band at 1717 cm¹. The perturbations of A-T base pairs occur at high cation concentration with major helix destabilization. Evidence for cation binding to A-T bases comes from major spectral changes of the bands at 1663 and 1609 cm-¹ related mainly to the thymine and adenine in-plane vibrations. A major reduction of the B-DNA structure occurs in favor of A-DNA upon trivalent cation coordination.