DNA condensation and its thermal stability influenced by phospholipid bilayer and divalent cations

We studied the effect of divalent alkaline earth metal cations Ca2?, Mg2? and transition metals Co2?, Ni2?, Cu2? and Zn2? on DNA condensation and its protection against thermal denaturation in presence of dioleoylphosphatidylcholine liposomes (DOPC). Experimental results have shown that Ca2? and Mg2? as well as Zn2? mediate DNA condensation. Cu2? causes DNA double helix destabilization, and does not mediate binding between DNA and DOPC liposomes. Co2? and Ni2? can interact with DNA on both ways mentioned above. Static light scattering was use to follow the size of aggregates in DNA condensation process. Phospholipid bilayer and divalent cations protect condensed DNA against thermal destabilization. The highest stabilization effect was found in aggregates with Ca2? and Zn2?, whereas in presence of either Co2? or Ni2? some volume fraction of DNA is denatured.     

Construction and DNA Condensation of Cyclodextrin‐Coated Gold Nanoparticles with Anthryl Grafts

The condensation of DNA in a controlled manner is one of the key steps in gene delivery and gene therapy. For this purpose, a water‐soluble supramolecular nanostructure is constructed by coating 14 β‐cyclodextrins onto the surface of a gold nanoparticle, followed by the noncovalent association of different amounts of anthryl‐modified adamantanes with coated β‐cyclodextrins. The strong binding of β‐cyclodextrins with anthryl adamantanes (K_S=8.61×10⁴ M ^?1) efficiently stabilizes the supramolecular nanostructure. Spectrophotometric fluorescence spectra and microscopic studies demonstrated that, with many anthryl grafts that can intercalate in the outer space of the DNA double helix, this supramolecular nanostructure showed good condensation abilities to calf thymus DNA. Significantly, the condensation efficiency of supramolecular nanostructure towards DNA could be conveniently controlled by adjusting the ratio between gold nanoparticles and anthryl adamantane grafts, leading to the formation of DNA condensates of a size that are suitable for the endocytosis of hepatoma cells, which will make it potentially applicable in many fields of medicinal science and biotechnology.     

DNA体外缩合的研究进展

DNA缩合不仅是自然界常见的生理现象,也是非病毒载体介导基因转染的关键步骤。了解DNA体外缩合的性质与特征,将有助于设计出高效的非病毒转基因载体。本文综述了近十几年来以多价阳离子为缩合剂诱发的DNA体外缩合的研究进展,着重介绍了缩合的机理、过程、影响缩合的因素以及应用于转基因的最新成果。     

Thermodynamics of Nucleation on the Particles of Salts-Strong Electrolytes: The Allowance for Ion Adsorption in the Droplet Surface Layer

The contributions dependent on ionic specificity (including those related to the differences in polarizabilities of cations and anions) to the surface tension and ion adsorption on the boundary between an aqueous strong electrolyte solution and the vapor-gas phase are taken into account. The role of these contributions in the thermodynamics of vapor condensation on salt particles completely dissolved in droplets that are emerged on these particles from the vapor is studied. Consistent domains of the applicability of the analytical theory suggesting the complete dissolution of a salt particle and the dissociation of substance comprising this particle into ions, as well as the ideal behavior of solution in a droplet and the linearization with respect to excess electric potentials near the droplet surface, are established in the approximation of a quasi-planar interface. Formulas are derived for the threshold values of the chemical potential of vapor molecules upon the barrierless condensation and for critical vapor supersaturations upon the barrier condensation on salt particles. In the explicit form, these formulas express the dependence of these values on the initial size of salt particles, physicochemical parameters of solution in droplets, and the charge of formed ions. Calculations for water condensation on NaCl, Na₂SO₄, and MgCl₂ particles are performed using these formulas.     

Construction and control of plasmid DNA network

The influences of different cations on plasmid DNA network structures on a mica substrate were investigated by atomic force microscopy (AFM). Interactions between the DNA strands and mica substrate, and between the DNA strands themselves were more strongly influenced by the complex cations (Fe(phen)3(2+), Ni(phen)3(2+), and Co(phen)3(3+)) than by the simple cations (Mg2+, Mn2+, Ni2+, Ca2+, Co3+). The mesh height of the plasmid DNA network was higher when the complex cations were added to DNA samples. The mesh size decreased with increasing DNA concentration and increased with decreasing DNA concentration in the same cation solution sample. Hence, plasmid DNA network height can be controlled by selecting different cations, and the mesh size can be controlled by adjusting plasmid DNA concentration.     

Preparation of silver nanoparticles on cellulose nanocrystals and the application in electrochemical detection of DNA hybridization

Synthesis of Ag nanopaticles was carried out with carboxylated cellulose nanocrystals as the scaffolds by reducing metallic cations using NaBH₄. Ag particles with a size less than 10 nm were readily prepared and dispersed well. The carboxyl and hydroxyl groups of carboxylated cellulose nanocrystals supplied a coordination effect to adsorb metallic cations and Ag nanoparticles, which prevent the aggregation of nanoparticles. The carboxylated cellulose nanocrystals carrying Ag nanoparticles were used as labels for electrical detection of DNA hybridization.     

On the break-in and passivation phenomena in polypyrrole/sulfate films

The influence of different divalent cations (M²⁺) on the electrochemical charging/discharging process of polypyrrole/sulfate (PPy/SO₄) films has been investigated. In principle, two different types of M²⁺ were found: (a) cations that cause the break-in phenomenon in the PPy film during electrochemical cycling with a gradual increase of film electroactivity and (b) cations in whose solutions the PPy film remains mainly electroinactive. Certain correlations have been drawn between several physico-chemical properties of the investigated cations and the break-in and passivation phenomena. The break-in and passivation phenomena were found to be influenced by the size and deformability of the cation hydration shell, ion covalent index and softness, as well as by the pH value of the test solution.     

A Cationic Metal Glue Strategy for Expanding Paramagnetic Hetero-Multinuclear Metal-Oxo Clusters within Polyoxometalate Ligands

Precise structural design of large hetero-multinuclear metal-oxo clusters is crucial for controlling their large spin ground states and multielectron redox properties for application as a single-molecule magnet (SMM), molecular magnetic refrigeration, and efficient redox catalyst. However, it is difficult to synthesize large hetero-multinuclear metal oxo clusters as designed because the final structures are unpredictable when employing conventional one-step condensation reaction of metal cations and ligands. Herein, we report a “cationic metal glue strategy” for increasing the size and nuclearity of hetero-multinuclear metal-oxo clusters by using lacunary-type anionic molecular metal oxides (polyoxometalates, POMs) as rigid multidentate ligands. The employed method enabled the synthesis of {(FeMn₄)Mn₂Ln₂(FeMn₄)} oxo clusters (Ln=Gd, Tb, Dy, and Lu), which are the largest among previously reported paramagnetic hetero-multinuclear metal-oxo clusters in POMs and showed unique SMM properties. These clusters were synthesized by conjugating {FeMn₄} oxo clusters with Mn and Ln cations as glues in a predictable way, indicating that the “cationic metal glue strategy” would be a powerful tool to construct desired large hetero-multinuclear metal clusters precisely and effectively.     

La交换NaY分子筛中的离子定位和迁移规律

以NaY分子筛为原料,采用二次交换二次焙烧工艺,制得了LaNH₄Y-1,LaY-1,LaNH₄Y-2和LaY-2四种分子筛样品.采用粉末X射线衍射结合Rietveld结构精修确定了La离子在分子筛中的分布.结果表明,在离子交换过程中,La离子首先定位于分子筛超笼里;经焙烧脱水后,La离子迁移到分子筛方钠石笼并定位在SI′位置.T-O-T键角的变化表明,LaNH₄Y-1表现出最大的骨架扭曲性和结构不稳定性.La离子定位在SI′位置与O3配位,增加了T-O3的键长,表明稀土离子不仅通过控制骨架脱铝抑制晶胞收缩,还可能通过影响T-O3键长使晶胞增大.在REY分子筛中,稀土的主要作用是稳定分子筛结构,从而调节其酸性和催化活性.采用红外光谱和NH₃程序升温脱附考察了La离子和NH₄⁺对分子筛酸性的影响,并总结了稀土离子稳定Y型分子筛的机理.     

Gas phase ion molecule chemistry of tetracarbonyl (η5-cyclopentadienyl) vanadium by Fourier transform ion cyclotron resonance

The kinetics of the reactions between the CpV(CO)₄ molecule and its fragment cations and anions have been examined using Fourier transform ion cyclotron resonance (FTICR) techniques. With 25 eV electron impact ionization the fragment cations V⁺ and CpV(CO)_n=0–4⁺ react principally by charge exchange or by condensation with the parent neutral molecule. Rate constants for these pathways have been determined along with kinetic evidence for the existence of excited state cations. Some of the product cations show unexpected stability despite their large formal electron deficiency. Exchange of carbonyl ligands was also observed. Under 2.5 eV electron impact, only two anions are produced: CpV(CO)_n=2,3⁻, both of which are unreactive with the parent neutral.     

Influence of ion size on the stability of chloroplumbates containing PbCl<Stack><Subscript>5</Subscript><Superscript>−</Superscript></Stack> or PbCl<Stack><Subscript>6</Subscript><Superscript>2−</Superscript></Stack>

The enthalpies of formation of PbCl₄, PbCl₅⁻ and PbCl₆²⁻, originating from quantum mechanics, have enabled the thermodynamic behaviour of these ions with respect to Cl-detachment to be assessed. The stability of salts containing PbCl₅⁻ and PbCl₆²⁻ as a function of the dimensions of these anions and complementary cations was studied using an approach combining the Kapustinskii-Yatsimirskii equation with basic thermochemical relationships. It was found that hexachloroplumbates of monovalent metal cations will not dissociate into metal chlorides and PbCl₄, provided the complementary cations are suitably large in size. Hexachloroplumbates of divalent metal cations have not yet been synthesised since no known metal cations attain the requisite large size. Such salts will not dissociate if the divalent metal cations are able to complex suitably large electron-donating ligands. The pentachloroplumbates of both monovalent and divalent metal cations are unstable, since no known metal cations have appropriately large ionic radii. The approach adopted appears to be useful for the examination of the thermal behaviour, stability and reactivity of chloroplumbates.     

Explicit ions condensation around strongly charged polyelectrolytes and spherical macroions: the influence of salt concentration and chain linear charge density. Monte Carlo simulations

The condensation of monovalent counterions and trivalent salt particles around strong rigid and flexible polyelectrolyte chains as well as spherical macroions is investigated by Monte Carlo simulations. The results are compared with the condensation theory proposed by Manning. Considering flexible polyelectrolyte chains, the presence of trivalent salt is found to play an important role by promoting chain collapse. The attraction of counterions and salt particles near the polyelectrolyte chains is found to be strongly dependent on the chain linear charge density with a more important condensation at high values. When trivalent salt is added in a solution containing monovalent salt, the trivalent cations progressively replace the monovalent counterions. Ion condensation around flexible chains is also found to be more efficient compared with rigid rods due to monomer rearrangement around counterions and salt cations. In the case of spherical macroions, it is found that a fraction of their bare charge is neutralized by counterions and salt cations. The decrease of the Debye length, and thus the increase of salt concentration, promotes the attraction of counterions and salt particles at the macroion surface. Excluded volume effects are also found to significantly influence the condensation process, which is found to be more important by decreasing the ion size.     

Syntheses of bifunctional molecules containing [12]aneN3 and carbazol moieties as effective DNA condensation agents

Bifunctional molecules containing macrocyclic polyamine[12]aneN3 and carbazol units,1 4,have been efficiently synthesized and fully characterized.Through gel electrophoresis,atomic force microscopy,and dynamic light scattering experiments,compounds 3 and 4b bearing both[12]aneN3and carbazol moieties showed effective DNA condensation ability at the concentration of 80μM.Investigations from EB displacement fluorescence spectra,viscosity titration,and ionic strength effects revealed that the effective DNA condensation comes from the appropriate combination of carbazol and[12]aneN3units in the bifunctional molecules,and the DNA condensation process is reversible.The incorporation of triazole units in the molecules clearly reduced the cytotoxicity.     

Azolium and acetate ions in DMF: Formation of free N-heterocyclic carbene. A voltammetric analysis

In order to reveal the possible formation of free N-heterocyclic carbene (NHC) in DMF-azolium and acetate solutions, the proton exchange equilibrium between azolium cations and CH₃COO⁻ was investigated (by cyclic voltammetry) by adding CH₃COOH or tetrabutylammonium acetate to DMF solutions of imidazolium or thiazolium salts of different acidity.The voltammetric analysis confirms that the deprotonation of the azolium cation by CH₃COO⁻ (with the formation of free NHC) is significant in the case of the more acidic thiazolium cations, while it is not effective with the less acidic imidazolium ones.Accordingly, the NHC-catalyzed benzoin condensation was carried out in DMF solutions of azolium salts, tetrabutylammonium acetate, and benzaldehyde. Benzoin was isolated only starting from the more acidic thiazolium salts.     

Salt effect on polymer solutions

The salt effect was investigated by measurements of viscosity, cloud point, and solubility of aqueous solutions of poly(vinyl alcohol—acetate) copolymers, as these copolymers in water are sensitive in various ways to addition of various electrolytes. The major role in the salt effect is played by the anions, and water-structure breaking anions produce salting-in of the copolymers. Tetraalkylammonium halides (bromides and iodides) cause salting-in of the copolymers more effectively with increase of size of the hydrophobic cations. The Setschenow equation does not hold for the polymers except for very dilute polymer concentration. In salts of monoalkyl-substituted anions (R? COONa and R? SO₄Na) and cations (R? NH₃Cl and Br), so long as the alkyl chain is short, the salt effect is also dominated by the anions. With increase of the alkyl chain length, sodium salts of the monoalkyl-substituted anions exert a stronger salting-in effect upon the polymers than chlorides of similar long-chain cations. The significance of the counteranions is suggested for the interaction of nonionic polymers and the long-chain cations. The action of the salts on the copolymers is discussed in terms of medium effects (change of the water structure) and of the binding effect of the single ions to the polymers.     

Near-UV induced interstrand cross-links in anthraquinone-DNA duplexes

Anthraquinone (AQ) has been extensively used as a photosensitizer to study charge transfer in DNA. Near-UV photolysis of AQ induces electron abstraction in oligonucleotides leading to AQ radical anions and base radical cations. In general, this reaction is followed by the transport of base radical cations to sites of low oxidation potential, that is, GG, and conversion of G radical cations to DNA breaks. Here, we show that AQ also produces interstrand cross-links in DNA duplexes. About half of the cross-links collapse to single strands in hot piperidine treatment. The structure of stable interstrand cross-links was deduced by MS, NMR, and sequence substitution. The cross-links consist of a covalent link between the methyl group of T on one strand with either C6 or C7 of AQ on the other strand. The formation of interstrand cross-links decreased in O2 compared to deoxygenated solutions. In the presence of O2, the yield of breaks at GG doublets was 10-fold greater than that of cross-links for end tethered AQ, while cross-links exceeded breaks for centrally located AQ. The formation of stable cross-links can be explained by initial charge transfer from T to excited AQ, deprotonation of T radical cations, and condensation of the latter species with AQ radicals. These studies reveal a novel pathway of damage in the photolysis of AQ-DNA duplexes.     

Solid electrolytes with potassium cation conductivity in K1−2x M x AlO2 (M = Ba, Pb) systems

New solid electrolytes with high potassium cationic conductivity based on potassium monoaluminate were synthesized and studied in the K_1?2x Ba _x AlO₂ and K_1?2x Pb _x AlO₂ systems. A partial substitution of potassium cations with double charged positive cations results in a considerable increase in the conductivity of KAlO₂ in the whole studied range of temperatures. The electric characteristics are somewhat higher in the bariumcontaining system, which is in all probability connected with the effect of the size factor: the size of the Ba²⁺ ion is higher than that of Pb²⁺, which must correlate with the increase of the effective dimensions of the migration channels in the electrolyte structure. The main cause of the conductivity increase at the introduction of the studied additives is the formation of potassium vacancies at the substitution of 2K⁺ → Ba²⁺(Pb²⁺) + V′_K.     

Ultrasonic vibration potentials,apparent molal volumes,and apparent molal heat capacities of 1:1 electrolytes in acetonitrile

The ultrasonic vibration potentials and apparent molal volumes for many inorganic and organic electrolytes were measured in acetonitrile at 25°C and combined to obtain ionic contributions to the standard partial molal volumes V°(ion). Monatomic cations and anions of the same size essentially have the same V°(ion). Their size dependence can be interpreted through Hepler's equation. The apparent molal heat capacities were also measured in acetonitrile and used to derive standard values. Various methods of estimating C _p ⁰ (ion) were investigated and an ionic scale is proposed. It is concluded that C _p ⁰ (ion) of large organic ions are very close to the intrinsic heat capacities of the ions, and the solvation contribution to monatomic ions is positive for both cations and anions.     

Reversible DNA condensation induced by a tetranuclear nickel(II) complex

DNA condensing agents play a critical role in gene therapy. A tetranuclear nickel(II) complex, [Ni^II₄(L?2H)(H₂O)₆(CH₃CH₂OH)₂] ? 6NO₃ (L=3,3',5,5'‐tetrakis{[(2‐hydroxyethyl)(pyridin‐2‐ylmethyl)amino]methyl}biphenyl‐4,4'‐diol), has been synthesized as a nonviral vector to induce DNA condensation. X‐ray crystallographic data indicate that the complex crystallizes in the monoclinic system with space group P2₁/n, a=10.291(9), b=24.15(2), c=13.896(11) Å, and β=98.175(13)°. The DNA condensation induced by the complex has been investigated by means of UV/Vis spectroscopy, fluorescence spectroscopy, circular dichroism spectroscopy, dynamic light scattering, atomic force microscopy, gel electrophoresis assay, and zeta potential analysis. The complex interacts strongly with DNA through electrostatic attraction and induces its condensation into globular nanoparticles at low concentration. The release of DNA from its compact state has been achieved using the chelator ethylenediaminetetraacetic acid (EDTA) for the first time. Other essential properties, such as DNA cleavage inactivity and biocompatibility, have also been examined in vitro. In general, the complex satisfies the requirements of a gene vector in all of these respects.