Zeta potential of Z-DNA: A new signature to study B-Z transition in linear and branched DNA.

Zeta potential is commonly referred as surface charge density and is a key factor in modulating the structural and functional properties of nucleic acids. Although the negative charge density of B-DNA is well understood, there is no prior description of the zeta potential measurement of Z-DNA. In this study, for the first time we discover the zeta potential difference between B-DNA and lanthanum chloride-induced Z-DNA. A series of linear repeat i.e. (CG)n and (GC)n DNA as well as branched DNA (bDNA) structures was used for the B-to-Z DNA transition. Herein, the positive zeta potential of Z-DNA has been demonstrated as a powerful tool to discriminate between B-form and Z-form of DNA. The generality of the approach has been validated both in linear and bDNA nanostructures. Thus, we suggest zeta potential can be used as an ideal signature for the left-handed Z-DNA.

Light rare earth elements stabilize G-quadruplex structure in variants of human telomeric sequences.

Recently, light rare earth elements (LREEs) are gaining importance in modern-day technologies. Thus, the entry of LREEs into biochemical pathways cannot be ignored, which might affect the conformation of biomacromolecules. Herein, for the first time, we discover the G-quadruplex formation in the human telomeric variants in presence of micromolar concentrations of LREEs. Thermal melting show that the LREE-induced unimolecular G-quadruplex structure. Isothermal titration calorimetry, UV-vis, and CD spectroscopy results suggest the binding stoichiometry of lanthanide ions to telomeric variants is 2:1. The data confirms that the LREE ions coordinate between adjacent G-quartets. The excess LREE ions are most likely binding to quadruplex loops. The CD spectra revealed that the LREE-induced quadruplex in human telomere and its variant have antiparallel orientation. The binding equilibria of LREEs have been studied both in the presence and absence of competing metal cations. Addition of LREEs to the Na+ or K+-induced G-quadruplexes led to conformational change, which may be ascribed to the displacement of K+ or Na+ ions by LREE ions and formation of a more compact LREE-induced G-quadruplex structure in human telomeric variant. Moreover, the thymine in the central loop of the human telomeric sequence stabilizes LREE induced G-quadruplex.

Enhanced enzymatic activity and conformational stability of catalase in presence of tetrahedral DNA nanostructures: A biophysical and kinetic study.

The emergence of DNA nanotechnology has shown enormous potential in a vast array of applications, particularly in the medicinal and theranostics fields. Nevertheless, the knowledge on the biocompatibility between DNA nanostructures and cellular proteins is largely unknown. Herein, we report the biophysical interaction between proteins (circulatory protein bovine serum albumin, BSA, and the cellular enzyme bovine liver catalase, BLC) and tetrahedral DNA (tDNA), which are well-known nanocarriers for therapeutics. Interestingly, the secondary conformation of BSA or BLC was unaltered in the presence of tDNAs which supports the biocompatible property of tDNA. In addition, thermodynamic studies showed that the binding of tDNAs with BLC has a stable non-covalent interaction via hydrogen bond and van der Waals contact, which is indicative of a spontaneous reaction. Furthermore, the catalytic activity of BLC was increased in the presence of tDNAs after 24 h of incubation. These findings indicate that the presence of tDNA nanostructures not only ensures a steady secondary conformation of proteins, but also stabilize the intracellular proteins like BLC. Surprisingly, our investigation discovered that tDNAs have no effect on albumin proteins, either by interfering or by adhering to the extracellular proteins. These findings will aid in the design of future DNA nanostructures for biomedical applications by increasing the knowledge on the biocompatible interaction of tDNAs with biomacromolecules.

Thermal plasma processing of Moringa oleifera biochars: adsorbents for fluoride removal from water.

Anthropogenic activities accelerate fluoride contamination in groundwater, which largely affects public health. Though biochars have been explored for defluoridation, the plasma technology-based production of biochars has not received as considerable attention as other methods and it is also important that biochars be tested on groundwater samples. In the present study, for the first time, we report the preparation of biochars from different parts of Moringa oleifera using thermal plasma processing and demonstrate fluoride adsorption in both synthetic and contaminated groundwater. Water samples were collected from different locations in Nuapada district of Odisha such as Kotamal-Makardampada (20°24'46''N 82°37'19''E), Pandrapathar (20°34'41''N 82°39'25''E), Karlakot-Kadobhata (20°22'52''N 82°37'24''E), Kotamal-Jhakarpada (20°24'35''N 82°37'20''E), and Dohelpada (20°33'50''N 82°38'57''E). The Moringa leaf samples are processed at 1600 °C for 3 min in an inert atmosphere under a continuous flow of argon to get suitable biochars. The plasma-synthesized biochars contain larger exposed surfaces, which are efficient for the adsorption of fluoride. The prepared biochars were highly porous, amorphous, and contain > 72% carbon, which increases the efficiency of defluoridation due to the surface adsorbate site exposed. XRD of the samples showed the presence of calcium hydroxide, magnesium oxide, and calcium oxide, and large peaks of carbon. Raman data showed the double bond of carbon with oxygen in the form of carbonyl bonds, thioether, and sulfhydryl bonds, which contribute to the protonated site for the adsorption of fluoride, and assist in water penetration and swelling of biochars. The biochar of Moringa oleifera is very efficient for the adsorption of fluoride from standard samples as well as groundwater samples up to a concentration of 6 ppm. Conclusively, the present investigation shows that Moringa oleifera leaves are a good alternative adsorbent that could be used for the removal of fluoride from groundwater samples with > 85% removal in 18 h using 1 g biochar for 100 mL or 10 g biochar for 1 L water containing 4 ppm fluoride. To our knowledge, this is the first report on the thermal plasma-based production of Moringa biochars for the removal of fluoride from drinking water.

Biophysical interaction between lanthanum chloride and (CG)n or (GC)n repeats: A reversible B-to-Z DNA transition.

The transition from right-handed to left-handed DNA is not only acts as the controlling factor for switching gene expression but also has equal importance in designing nanomechanical devices. The (CG)n and (GC)n repeat sequences are well known model molecules to study B-Z transition in the presence of higher concentration of monovalent cations. In this communication, we report a cyclic transition in (CG)6 DNA using millimolar concentration of trivalent lanthanide salt LaCl3. The controlled and reversible transition was seen in (CG)12, and (GC)12 DNA employing CD spectroscopy. While LaCl3 failed to induce B-Z transition in shorter oligonucleotides such as (CG)3 and (GC)3, a smooth B-Z transition was recorded for (CG)6, (CG)12 and (GC)12 sequences. Interestingly, the phenomenon was reversible (Z-B transition) with addition of EDTA. Particularly, two rounds of cyclic transition (B-Z-B-Z-B) have been noticed in (CG)6 DNA in presence of LaCl3 and EDTA which strongly suggest that B-Z transition is reversible in short repeat sequences. Thermal melting and annealing behaviour of B-DNA are reversible while the thermal melting of LaCl3-induced Z-DNA is irreversible which suggest a stronger binding of LaCl3 to the phosphate backbone of Z-DNA. This was further supported by isothermal titration calorimetric study. Molecular dynamics (MD) simulation indicates that the mode of binding of La3+ (of LaCl3) with d(CG)8.d(CG)8 is through the minor groove, wherein, 3 out of 11 La3+ bridge the anionic oxygens of the complementary strands. Such a tight coordination of La3+ with the anionic oxygens at the minor groove surface may be the reason for the experimentally observed irreversibility of LaCl3-induced Z-DNA seen in longer DNA fragments. Thus, these results indicate LaCl3 can easily be adopted as an inducer of left-handed DNA in other short oligonucleotides sequences to facilitate the understanding of the molecular mechanism of B-Z transition.