Temperature effect on thin lipid film elasticity and phase separation: insights from Langmuir monolayer and fluorescence microscopy techniques

Langmuir monolayer pressure isotherms and compressibility modulus measurements of phospholipid mixtures in several Langmuir monolayer systems at the air/water interface were investigated in this study. The ultimate aim was to carry out a comparison of the elasticity modulus for monolayers with different mixtures of l,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), l,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and chicken egg yolk sphingomyelin (eSM), in the presence/absence of cholesterol (Chol). In particular, we were able to propose that the leading force beyond the phase separation into liquid expanded (LE-) and liquid condensed (LC-) phases emerges from the increasing barrier to incorporate DOPC molecules into a highly ordered LC-phase. In addition, our findings suggest that DOPC lipid molecules have a priority to incorporate in a disordered LE-phase, while DPPC and eSM prefer the ordered one. Also, Chol seems to split almost equally into both phases, indicating that Chol has no priority for either phase and there are no particular interactions between Chol and saturated lipid molecules.     

Effect of interaction between loop bases and ions on stability of G-quadruplex DNA

G-quadruplexes(GQs) are guanine-rich, non-canonical nucleic acid structures that play fundamental roles in biological processes. The topology of GQs is associated with the sequences and lengths of DNA, the types of linking loops, and the associated metal cations. However, our understanding on the basic physical properties of the formation process and the stability of GQs is rather limited. In this work, we employed ab initio, molecular dynamics(MD), and steered MD(SMD)simulations to study the interaction between loop bases and ions, and the effect on the stability of G-quadruplex DNA, the Drude oscillator model was used in MD and SMD simulations as a computationally efficient manner method for modeling electronic polarization in DNA ion solutions. We observed that the binding energy between DNA bases and ions(K⁺/Na⁺)is about the base stacking free energies indicates that there will be a competition among the binding of M⁺-base, H-bonds between bases, and the base-stacking while ions were bound in loop of GQs. Our SMD simulations indicated that the side loop inclined to form the base stacking while the loop sequence was Thy or Ade, and the cross-link loop upon the G-tetrads was not easy to form the base stacking. The base stacking side loop complex K+was found to have a good stabilization synergy. Although a stronger interaction was observed to exist between Cyt and K+, such an interaction was unable to promote the stability of the loop with the sequence Cyt.     

环糊精锌(Ⅱ)荧光试剂在水分析中的应用研究

合成高水溶性的锌()荧光试剂-修饰环糊精的N-(8-对氨基苯磺酰)胺基喹啉(HQAS-1-CD)。该试剂在水溶液中与Zn2+形成2:1配合物而使荧光增强,并且碱金属或碱土金属离子几乎不干扰Zn2+的荧光。利用此配位反应建立了一个荧光测定痕量锌的新方法,测定锌的线性范围为0—13μg/L,检出限0.57μg/L,方法成功的应用于矿泉水中痕量锌的测定。     

Effects of charge compensation on red emission in CaYAl3O7:Eu3+ phosphor

Monovalent ions Li+, Na+, and K+, as charge compensators, are introduced into CaYAl3O7: M(M =Eu3+, Ce3+) in this letter. Their crystal phases and photoluminescence properties of different alkali metal ions doped in CaYAl3O7 are investigated. In addition, the influence of charge compensation ion Li+which has a more obvious role in improving luminescence intensity on CaYAl3O7: Eu3+phosphor is intentionally discussed in detail and a possible mechanism of charge compensation is given. The enhancement of red emission centered at 618 nm belonging to Eu3+is achieved by adding alkali metal ion Li+under 393-nm excitation.     

不同价金属离子介导的蓝膜到紫膜转换的光谱分析

研究了Na+,Mg2+和Tb3+三种不同价金属离子介导的的蓝膜到紫膜转换的可见差光谱,M412产率和Mt412衰减寿命.结果表明,他们的转换能力有很大差别,三种不同离子介导的吸收变化的中间点的浓度比Na+:Mg2+:Tb3+为1:2.5:650,同时,在蓝膜到紫膜转换中,其540nm的吸收变化的曲线与M412产率变化的...     

Probing membrane surfaces and the location of membrane-embedded peptides by (13)C MAS NMR using lanthanide ions

A simple but efficient (13)C MAS NMR method is presented for the determination of the location of embedded molecules such as peptides relative to biological membrane surfaces by exploiting the interaction with paramagnetic lanthanide ions. Using various aqueous Dy(3+) concentrations a distance-dependent differential paramagnetic quenching of NMR lipid resonance intensities for specific carbon sites was observed, with residues at the bilayer surface quenched effectively and hydrophobic sites unaffected by Dy(3+). Tested on the membrane-embedded 50 residue long M13 coat protein, (13)C labeled at its Val-29 and Val-31 residues, no paramagnetic quenching was observed for the peptide resonances by Dy(3+), suggesting that Val-29 and Val-31 are not in close proximity to the bilayer interface, but buried deeply inside the hydrophobic region of the lipid bilayer.     

Precision measurements of strangeness photoproduction at threshold energies with the Crystal Ball at MAMI-C

The photoproduction of K~+ mesons from the nucleon provides important constraints on the nucleon excitation spectrum and at threshold energies challenges effective field theories based on chiral perturbation in the strange quark sector. Preliminary cross-section measurements for γ(p, K~+)A are presented at an unprece-dented beam energy resolution. The data was collected at the MAMI-C facility in Mainz using the Crystal Ball Detector. A new method of K~+ detection was used in which the K~+ is tagged from its weak decay products in the detector crystals. This technique has application with other calorimeters at present and future hadron facilities.     

Probing Membrane Surfaces and the Location of Membrane-Embedded Peptides by C MAS NMR Using Lanthanide Ions

A simple but efficient ¹³C MAS NMR method is presented for the determination of the location of embedded molecules such as peptides relative to biological membrane surfaces by exploiting the interaction with paramagnetic lanthanide ions. Using various aqueous Dy³⁺ concentrations a distance-dependent differential paramagnetic quenching of NMR lipid resonance intensities for specific carbon sites was observed, with residues at the bilayer surface quenched effectively and hydrophobic sites unaffected by Dy³⁺. Tested on the membrane-embedded 50 residue long M13 coat protein, ¹³C labeled at its Val-29 and Val-31 residues, no paramagnetic quenching was observed for the peptide resonances by Dy³⁺, suggesting that Val-29 and Val-31 are not in close proximity to the bilayer interface, but buried deeply inside the hydrophobic region of the lipid bilayer.     

Miscibility phase diagrams of giant vesicles containing sphingomyelin

Saturated sphingomyelin (SM) lipids are implicated in lipid rafts in cell plasma membranes. Here we use fluorescence microscopy to observe coexisting liquid domains in vesicles containing SM, an unsaturated phosphatidylcholine lipid (either DOPC or POPC), and cholesterol. We note similar phase behavior in a model membrane mixture without SM (DOPC/DPPC/Chol), but find no micron-scale liquid domains in membranes of POPC/PSM/Chol. We delineate the onset of solid phases below the miscibility transition temperature, and detail indirect evidence for a three-phase coexistence of one solid and two liquid phases.     

阳离子对硅酸盐玻璃激光拉曼光谱影响的研究

运用拉曼光谱技术研究了Na2O(K2O)—CaO(MgO)—SiO2,Na2O(K2O)—Al2O3—SiO2,Na2O(K2O)—B2O3—SiO2,Na2O(K2O)—PbO—SiO2和PbO—BaO—SiO2五个系统的玻璃。结果表明,阳离子对玻璃近程结构的改造会引起拉曼特征的变化。部分样品是根据古玻璃平均成分在实验室烧制的,这项研究对于运用激光拉曼光谱区分不同系统的古代硅酸盐玻璃有重要意义。     

Characterization of porous structure through the dynamical properties of ions confined in sulfonated polyimide ionomers films

The structure of sulfonated PolyImide (sPI) ionomer membrane has been investigated via the transport properties of ions confined inside. Transport coefficients of N(CH(3))(4)(+) and Na(+) ions have been determined by several techniques in order to get a range of time/space scale as wide as possible: a method using radiotracers, conductivity, pulsed field gradient NMR and NMR quadrupolar relaxation rates determination. For N(CH(3))(4)(+), the self-diffusion has been measured in the direction of membrane plan (parallel) and in the perpendicular direction (transverse), whereas for Na(+) only transverse self-diffusion has been measured. The conductivity of both ions has been measured in the transverse direction. The results show a anisotropic and multiscale structure with a separation phase between hydrophilic and hydrophobic domains that is not well-defined.     

Interaction studies of cysteine with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ metal cation complexes

The coordination geometries, electronic features, metal ion affinities, entropies, and the energetics of Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ metal cations with different possible conformations of cysteine complexes were studied. The complexes were optimized using density functional theory (B3LYP) and second order Moller–Plesset Perturbation (MP2) theory methods using 6‐311 + +G** basis set. The interactions of the metal cations at different nucleophilic sites of cysteine conformations were considered after a careful selection among several binding sites. All the metal cations coordinate with cysteine in a tridentate manner and also the most preferred position for the interaction. It is found that, the overall structural parameters of cysteine are not altered by metal ion substitution, but, the metal ion‐binding site has undergone a noticeable change. All the complexes were characterized by an electrostatic interaction between ligand and metal ions that appears slightly more pronounced for lithium and beryllium metal complexes. The metal ion affinity (MIA) and basis set superposition error (BSSE) corrected interaction energy were also computed for all the complexes. The effect of metal cations on the infrared (IR) stretching vibrational modes of amino N? H bond, side chain thiol group S? H bond, hydroxyl O? H bond, and Carbonyl C?O bond in cysteine molecules have also been studied. The nature of the metal ion‐ligand bond and the coordination properties were examined using natural bond order (NBO) at bond critical point (electron density and their Laplacian of electron density) through Atoms in Molecules (AIM) analyses. Copyright © 2010 John Wiley & Sons, Ltd.     

A virtual instrumentation based protocol for the automated implementation of the inner field compensation method

One influential parameter which mediates interactions between many types of molecules and biological membranes stems from the lumped contributions of the transmembrane potential, dipole potential and the difference in the surface potentials on both sides of a membrane. With relevance to cell physiology, such electrical features of a biomembrane are prone to undergoing changes as a result of interactions with the aqueous surrounding. Among the most useful tools devoted to exploring changes of electrical parameters of a lipid membrane induced by certain extracellular ions, lipid composition, and embedded membrane peptides and proteins, are spectroscopic imaging and the inner field compensation (IFC) method. In this work we layout the principles of a fully computerized version of the IFC method, which makes it more readily available to users. As a direct application, we deployed this improved version of the IFC method to time-resolve changes induced by alamethicin monomers upon membrane dipole potential, following their aggregation within an artificial lipid membrane. Intriguingly, even prior crossing the membrane core, the membrane-bound alamethicin monomers are shown to significantly increase the dipole potential of the monolayer they reside in. Such data further emphasize the yet less-explored interplay between membrane-based protein and peptides, and the membrane dipole potential.     

A spectral-kinetic investigation of the negative photochromism of systems based on complexes of spiropyrans with metal ions

A comparative spectral-kinetic study of the negative photochromism of complexes of molecules of nitrosubstituted indoline spiropyrans with metal ions in solutions and polymer matrices is carried out. The possibility of creating polymer coatings with negative photochromism, based on the complexes of spiropyran molecules with metal ions is shown for the first time. It is determined that the efficiency of photochromic transformations of complexes depends on the nature of the polymer binder, the component composition of the polymer film, and the properties of metal cations. During the storage of photochromic polymer films in the dark, a spectral manifestation of the transformation of metal complexes into putative protonated complexes is revealed. It is found that the stability of the complexes is determined by the nature of the polymer binder and the affinity of the metal cations to an electron.     

Gas Phase Emitter Effect of Thulium within Ceramic Metal Halide Lamps in Dependence on Frequency

The gas phase emitter effect within ceramic metal halide (CMH) lamps reduces the effective work function of the electrode material and, therewith, the electrode temperature. An investigation of the gas phase emitter effect of thulium (Tm) within CMH lamps seeded with Tm iodide (TmI3) is carried out. For this purpose, phase resolved images of the arc attachment and measurements of the electrode temperature, Tm atom and ion densities are performed in dependence on operating frequency by pyrometry and optical emission spectroscopy. Additionally, the influence of a sodium iodide (NaI) admixture is studied. The emitter effect is generated by means of a monolayer of Tm atoms on the electrode surface generated by a Tm ion current within the cathodic phase. It overlaps onto the anodic phase at higher frequencies of some hundreds of hertz. The reason is the finite life time of the monolayer, which is determined by the adsorption energy of Tm on the tungsten surface. Due to the low electric field strength in front of the anode and the mass inertia, the emitter ions and atoms remain in front of the anode. They retard the decay of the monolayer and with it the increase of the work function. Moreover, a comparison of a lamp seeded with TmI3 and sodium iodide (NaI) with a lamp seeded only with TmI3 illustrates a slight reduction of the electrode tip temperature caused by a higher Tm saturation vapour pressure and a higher Tm amount within the lamp filling. The influence of Na appears to be quite low. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Substitution priority of Eu~(2+) in multi-cation compound Sr_(0.8)Ca_(0.2)Al_2Si_2O_8 and energy transfer

A blue phosphor was obtained by doping Eu~(2+)into a multi-cation host Sr_(0.8)Ca_(0.2)Al_2Si_2O_8 through high temperature solid state reaction.The emission spectra show a continuous red-shift behavior from 413 nm to 435 nm with Eu~(2+)concentration increasing.The substitution priority of Eu~(2+)in Sr_(0.8)Ca_(0.2)Al_2Si_2O_8 was investigated via x-ray diffraction(XRD)and temperature properties in detail:the Ca~(2+)ions are preferentially substituted by Eu~(2+)at lower doping,and with the Eu~(2+)concentration increasing,the probability of substitution for Sr~(2+)is greater than that of replacing Ca~(2+).Accordingly,we propose the underlying method of thermal property to determine the substitution of Eu~(2+)in the multi-cation hosts.Moreover,the abnormal increase of emission intensity with increasing temperature was studied by the thermoluminescence spectra.The energy transfer mechanism between the Eu~(2+)ions occupying different cation sites was studied by the lifetime decay curves.A series of warm white light emitting diodes were successfully fabricated using the blue phosphors Sr~+_(0.8)Ca_(0.2)Al_2Si_2O_8:Eu~2 with commercial red phosphor (CaSr)SiAlN_3:Eu~(2+)and green phosphor(Y Lu)_3Al_5O_(12):Ce~(3+),and the luminescent efficiency can reach 45 lm/W.     

金属离子掺杂对TiO2/白云母纳米复合材料中TiO2的颗粒形态及相组成的影响

采用化学液相沉积法制备了系列未掺杂和掺杂不同金属离子的TiO2白云母纳米复合材料.利用扫描电子显微镜(SEM),x射线衍射(XRD)对其TiO2薄膜的TiO2颗粒形态和相组成进行了详细研究.结果表明,TiO2颗粒在15—50nm之间;除球形颗粒外,掺杂Mn2+,Zn2+的样品中还出现有金红石柱状颗粒.TiO2薄膜中相组成以锐钛矿、金红石共存为特征;掺杂金属离子对TiO2相组成的影响取决于金属离子的离子半径、电荷及配位体特征. 关键词： 金属离子掺杂 TiO2 颗粒形态 相组成     

Eu3+在硼酸盐玻璃中的发光以及Bi3+对Eu3+的敏化作用

本文研究了单掺和双掺(Eu3+,Bi3+,Fu3++Bi3+)约二十余种不同成份的硼酸盐玻璃,探讨了玻璃成份对Eu3+发光性质的影响和Bi3+对Eu3+的敏化作用.     

SrBPO_5:Dy~(3+)荧光粉的制备及光谱性能研究

通过高温固相法制备了用于紫外激发的系列SrBPO_5:Dy~(3+)荧光粉,并对样品进行了XRD分析和发光性能测试。结果表明,合成样品为单一相的SrBPO_5材料;在388 nm紫外光激发下,样品的发射光谱包括485和575 nm两个发射峰。研究了Dy~(3+)浓度,Mg~(2+)加入量,烧结温度以及电荷补偿剂对发射光谱的影响。当Dy~(3+)掺杂摩尔浓度为4 mol%时发光强度最强;随着Mg~(2+)的加入量的增加B/Y峰的强度比不断增加;最佳烧结温度为1 100℃;Na~+作为电荷补偿剂效果最佳。该荧光粉有较强的黄色发射峰,可以增强UV激发的白光LED的黄光成分从而提高其穿透雾霾的能力。     

荧光显微镜研究极端pH值诱导磷脂支撑膜的侧向再组织

利用荧光显微镜研究了极端pH值诱导支撑磷脂双层膜的侧向再组织.结果表明,在强酸/强碱性溶液中,流动性较好的二油酰磷脂酰胆碱支撑膜出现破裂、分离、出芽或生出微管等与细胞内吞和外排相似的现象.基于极性分子与H+/H3O+或OH-的相互作用,以电中性的磷脂首基为核吸附溶液中的H+/H3O+或OH-.当磷脂膜上下叶吸附的电荷量不同时,引起两叶有效面积差,即磷脂膜曲率不对称,从而诱发磷脂膜出现各种结构和动力学的响应.本研究有助于理解极端环境对生物膜的影响,为研究生物膜的形变过程提供了参考.