Insight on Structural Change in Sol–Gel-Derived Silica Gel with Aging under Basic Conditions for Mesopore Control

Structural rearrangement of sol–gel-derived silica gel by aging under basic conditions was investigated using small angle X-ray scattering (SAXS) and ²⁹Si nuclear magnetic resonance (NMR). A wet silica gel prepared under acidic conditions had a fractal nature, and many unreacted silanols remained on the surface. During aging of the gel in ammonia solution, additional Si—O—Si bonds rapidly formed, whereas the change in mesoscale structure gradually proceeded. This result was compared with that of simulation modeling the Ostwald ripening, i.e. dissolution from positive curvature and reprecipitation on negative curvature. In the simulation, structural change in a cluster from fractal nature to particle aggregates was well visualized in 2-dimmensional square lattice. Both scattering profiles calculated from the model clusters and the change in average coordination number of monomers in the cluster well agreed with the experimental SAXS and NMR results, respectively. This agreement strongly ensures us that structural change by aging under basic conditions proceeds through the Ostwald ripening. The mesopore size as well as mesopore volume in calcined silica gel is determined by the shrinkage degree during drying and calcination. The sample aged in basic solution restrains the shrinkage because of the growth of particulate structure, and retains large size and volume of pores.     

Development of a novel nucleoside analogue with S-type sugar conformation: 2′-deoxy-trans-3′,4′-bridged nucleic acids

Two novel trans-3′,4′-bridged nucleic acid (trans-3′,4′-BNA) monomers, one with a 3,5,8-trioxabicyclo[5.3.0]decane structure and the other with a 4,7-dioxabicyclo[4.3.0]nonane structure, were successfully synthesized from thymidine. The locked trans-fused ring structures of the nucleoside analogues were confirmed by X-ray crystallography, which also indicated that their furanose rings had a typical S-type conformation involving C_2′-endo or C_3′-exo sugar puckering, respectively, and the same ring conformation as that observed in the B-type helical structure of the DNA duplex.     

Investigation of Voids in Polyacrylonitrile Fibers by USAXS and SAXS

The void structure of polyacrylonitrile(PAN) fibers was investigated using ultra-small angle X-ray scattering(USAXS) and small angle X-ray scattering(SAXS). A quantitative method was developed to analyze connected USAXS/SAXS data and thus determine the void parameters of PAN fibers. The results showed that voids affected the mechanical performance of PAN fibers and were present throughout the entire wet-spinning process. When the absolute quantity and size of voids decreased, the tensile strength and modulus of PAN fibers increased. The void parameters were optimized by controlling the production process, and thus the tensile strength and modulus of PAN fibers were increased. The method for analyzing the void structure developed in this study is useful for analyzing voids over with larger size range, as well as the effect of the void structure on the mechanical performance of fibers.     

应用弦长度分布函数研究中孔分子筛的精细结构

弦长度分布(chord length distribution, 简称CLD)可以用来描述几何对象(球形颗粒、柱状孔、薄片等)的大小、形状和空间排布等特点. 原理上, 弦长度分布正比于由小角散射所得的相关函数的二次微分, 因此可以由相对散射强度进行计算. 在结构研究中, 将实验所得弦长度分布与理论计算某种确定几何体所得高度准确的弦长度分布进行比较, 可以获知对象的特征几何结构. 本文以中孔氧化硅分子筛为研究对象, 介绍了弦长度分布的计算方法, 以此精确计算了中孔分子筛的孔径分布, 得到了分子筛表面有机官能化对孔径的影响规律.     

Surface layer protein characterization by small angle x-ray scattering and a fractal mean force concept: from protein structure to nanodisk assemblies

Surface layers (S-layers) are the most commonly observed cell surface structure of prokaryotic organisms. They are made up of proteins that spontaneously self-assemble into functional crystalline lattices in solution, on various solid surfaces, and interfaces. While classical experimental techniques failed to recover a complete structural model of an unmodified S-layer protein, small angle x-ray scattering (SAXS) provides an opportunity to study the structure of S-layer monomers in solution and of self-assembled two-dimensional sheets. For the protein under investigation we recently suggested an atomistic structural model by the use of molecular dynamics simulations. This structural model is now refined on the basis of SAXS data together with a fractal assembly approach. Here we show that a nondiluted critical system of proteins, which crystallize into monomolecular structures, might be analyzed by SAXS if protein-protein interactions are taken into account by relating a fractal local density distribution to a fractal local mean potential, which has to fulfill the Poisson equation. The present work demonstrates an important step into the elucidation of the structure of S-layers and offers a tool to analyze the structure of self-assembling systems in solution by means of SAXS and computer simulations.     

Electron microscopy of oriented high-density polyethylene: Comparison with small-angle X-ray scattering

The morphology of cold-drawn, rolled and annealed high-density polyethylene was investigated by transmission electron microscopy of stained sections. From the electron micrographs, a model of the structure was developed and the scattering pattern calculated. This was then compared with the corresponding small-angle X-ray scattering (SAXS) pattern, in order both to aid in the interpretation of SAXS patterns of oriented polymers, and to assess the effects of staining with chlorosulphonic acid on the morphology.     

Structure and properties of gel-spun ultra-high molecular weight polyethylene fibers with high gel solution concentration

The gel-spun ultra-high molecular weight polyethylene(UHMWPE) fibers were prepared at the industrial production line with different gel solution concentrations of 15 wt%, 18 wt% and 24 wt%. The difference in ultimate structure and mechanical properties of UHMWPE fibers for different gel solution concentrations were analyzed by tensile testing, differential scanning calorimetry(DSC), wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS). With the increase of gel solution concentration, the ultimate mechanical properties of UHMWPE fibers were decreased and the crystallization and orientation of UHMWPE fibers became inferior. Besides, both the average shish length(〈L _(shish)〉) and shish misorientation(B_φ) of UHMWPE fibers were decreased with the increase of gel solution concentration. In addition, the appropriate increase of spinning temperature led to the further optimization of the ultimate structure and mechanical properties of UHMWPE fibers.     

Preparation of the recombinant НU-proteins from <Emphasis Type="Italic">S. melliferum</Emphasis> and <Emphasis Type="Italic">M. gallisepticum</Emphasis> and of their complexes with DS-DNA for structural NMR experiments

We created a high-performance system for expression of ¹³C, ¹⁵N-double-labeled recombinant НU-proteins from mycoplasms S. melliferum (HUSpm) and M. gallisepticum (HUMgal), and a purification protocol that yields protein samples suitable for structure studies by high-resolution NMR. Using these proteins we optimized the conditions of NMR experiments and obtained two-dimensional heteronuclear ¹H/¹⁵N-HSQC and ¹H/¹³С-HSQC-CT NMR spectra of free НU-proteins (HUSpm and HUMGal), and 1H/15N-HSQC spectrum of a complex between HUSpm and a double-stranded DNA (ds-DNA). The techniques we created are applicable in the studies of НU-proteins from other organisms. They allow analyzing structure and dynamics of free proteins and of their conformational changes induced by binding of various ds-DNAs or of DNA binding inhibitors.     

Refinement of multidomain protein structures by combination of solution small-angle X-ray scattering and NMR data

Determination of the 3D structures of multidomain proteins by solution NMR methods presents a number of unique challenges related to their larger molecular size and the usual scarcity of constraints at the interdomain interface, often resulting in a decrease in structural accuracy. In this respect, experimental information from small-angle scattering of X-ray radiation in solution (SAXS) presents a suitable complement to the NMR data, as it provides an independent constraint on the overall molecular shape. A computational procedure is described that allows incorporation of such SAXS data into the mainstream high-resolution macromolecular structure refinement. The method is illustrated for a two-domain 177-amino-acid protein, gammaS crystallin, using an experimental SAXS data set fitted at resolutions from approximately 200 A to approximately 30 A. Inclusion of these data during structure refinement decreases the backbone coordinate root-mean-square difference between the derived model and the high-resolution crystal structure of a 54% homologous gammaB crystallin from 1.96 +/- 0.07 A to 1.31 +/- 0.04 A. Combining SAXS data with NMR restraints can be accomplished at a moderate computational expense and is expected to become useful for multidomain proteins, multimeric assemblies, and tight macromolecular complexes.     

Multiple small-angle X-ray scattering analyses of the structure of gold nanorods with unique end caps

Small-angle X-ray scattering (SAXS) experiments were carried out on gold nanorods generated by a seed-mediated growth method. Previous transmission electron microscopy observations suggest that the main components of nanoparticles are rod-shaped nanoparticles, but they are contaminated by other different-shaped, large-volume particles. By performing profile fitting of theoretical and experimental scattering curves, we determined and then removed from the obtained SAXS profile, the contribution of the contaminating particles. From the revised SAXS profile, we calculated the distance distribution function by Fourier transform and precisely determined the structural parameters of the nanorods and the structure of the nanorod end caps.     

Nanostructure changes with Krafft transitions of polyelectrolyte-surfactant complexes in aqueous NaCl solutions

Nanostructure changes with the Krafft transition of complexes of poly(acrylicacid) with octadecyltrimethylammonium (PAA-OTA) in the aqueous solutions at various NaCl concentrations (Cs) from 20 to 400 mM, were studied making temperature-scanning small-angle X-ray scattering (SAXS) experiments and differential scanning calorimetric (DSC) measurements. For the PAA-OTA complex in the solution at a higher temperature than 25 degrees C, four SAXS peaks with a spacing ratio of 1:31/2:41/2:71/2, indicating the 2D hexagonal structure, were observed at Cs below 100 mM and two SAXS peaks with a spacing ratio of 1:2, indicating the lamella structure, were observed at Cs above 200 mM. For the complex in the solution at a lower temperature than 22 degrees C, a broad SAXS peak was observed at the scattering vector q = 1.2 nm-1 when the Cs was less than 200 mM but not when Cs was 400 mM. Two peaks with a spacing ratio 1:2, indicating the lamella structure, were also observed for the complex in the solution at 8 degrees C. The DSC data demonstrated that the nanostructure changes were accompanied with the endothermic enthalpy change. On the basis of the experimental results, the salt concentration dependent nanostructures are discussed.     

Structural Characteristics of Xyloglucan – Congo Red Aggregates as Observed by Small Angle X-ray Scattering

Xyloglucan is a type of hemicellulose with a cellulose backbone containing (1→6)-α-xylose or (1→2)-β-galactoxylose as a side chain. It is soluble in water. Its aqueous solution forms a gel or gel-like precipitate by addition of Congo red. Xyloglucan gel structures with various concentrations of Congo red were observed by small angle X-ray scattering (SAXS) at the nano-level. SAXS results indicated that the xyloglucan chains interacted with Congo red, and that an increase of concentration of Congo red induced a characteristic cross-linking domain, which consisted of a flat structure containing stacked xyloglucan chain assemblies. The Congo red molecules are inserted between the xyloglucan chains.     

利用小角/广角X射线散射联用及一维相关函数分析研究聚(ε-己内酯)片晶的形态

用小角/广角X射线散射(SAXS/WAXS)联用的实验方法考察了等温结晶温度(Tc)和等温时间对聚(ε-己内酯)(PCL)片晶形态的影响.根据WAXS数据计算了PCL的重量结晶度,进而求得其体积结晶度Vc(WAXS).在不同Tc下结晶的PCL样品的Vc(WAXS)均略高于50%.对SAXS谱线做一维相关函数(1DCF)分析,得到了PCL的片晶长周期(LP)和无定形层厚度(La).通过比较WAXS及SAXS的数据分析结果,认为PCL晶体需用"三相模型"予以描述,其过渡层厚度(E)约为LP的15%～18%,对片晶形态具有重要影响.随着Tc升高,PCL晶体的Lc、La及E均逐渐增大,但Lc的变化率最大,这使得结晶度上升.在50℃等温结晶不同时间,发现Lc随延长时间显著增加,而La及E则不断减小.等温10天后,PCL晶体的SAXS谱线上可观察到5级散射,表明片晶相当完善.     

液晶态磷脂酰乙醇胺脂质体和LB膜结构的研究

用原子力显微镜、小角X射线散射和³¹PNMR分别对液晶态磷脂酰乙醇胺脂质体和LB膜结构进行了研究.用原子力显微镜观察到了液晶态脂质体的立方相和双层膜共存的结构图像.研究结果表明,两相共存的状态与双亲性分子的结构、浓度以及介质的组分和pH等因素有关.用小角X射线散射和³¹PNMR研究发现,在DEPE液晶态中,钠盐诱导形成Q²²⁹(Im3m)立方相.DEPE液晶态分别在37.5℃出现L_β→L_α可逆相变,在63.5℃出现L_α→H_Ⅱ可逆相变.     

Scattering studies of hydrophobic monomers in liposomal bilayers: an expanding shell model of monomer distribution

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.     

Contrast-Matched Small-Angle X-ray Scattering from a Heavy-Atom-Labeled Protein in Structure Determination: Application to a Lead-Substituted Calmodulin-Peptide Complex

The information content in 1-D solution X-ray scattering profiles is generally restricted to low-resolution shape and size information that, on its own, cannot lead to unique 3-D structures of biological macromolecules comparable to all-atom models derived from X-ray crystallography or NMR spectroscopy. Here we show that contrast-matched X-ray scattering data collected on a protein incorporating specific heavy-atom labels in 65% aqueous sucrose buffer can dramatically enhance the power of conventional small- and wide-angle X-ray scattering (SAXS/WAXS) measurements. Under contrast-matching conditions the protein is effectively invisible and the main contribution to the X-ray scattering intensity arises from the heavy atoms, allowing direct extraction of pairwise distances between them. In combination with conventional aqueous SAXS/WAXS data, supplemented by NMR-derived residual dipolar couplings (RDCs) measured in a weakly aligning medium, we show that it is possible to position protein domains relative to one another within a precision of 1 ?. We demonstrate this approach with respect to the determination of domain positions in a complex between calmodulin, in which the four Ca(2+) ions have been substituted by Pb(2+), and a target peptide. The uniqueness of the resulting solution is established by an exhaustive search over all models compatible with the experimental data, and could not have been achieved using aqueous SAXS and RDC data alone. Moreover, we show that the correct structural solution can be recovered using only contrast-matched SAXS and aqueous SAXS/WAXS data.     

利用X射线小角度散射法研究大孔吸附树脂的孔结构——平均孔径的测定

利用小角X射线散射技术研究了吸附剂的孔结构。选择含6％二乙烯基苯和100％汽油作致孔剂制备的干燥及水和甲苯溶胀的聚合物小球为样品,测定了干态及溶胀态样品的平均孔径及孔径分布。得到了随溶剂吸附量增加平均孔径变化的关系。对吸附和溶胀机理作了初步探讨。     

A pyrrole-containing surfactant as a tecton for nanocomposite SiO2 films

A surfactant featuring a polymerizable pyrrole head group (dodecyl-dimethyl-(2-pyrrol-1-yl-ethyl)-ammonium bromide, DDPABr) was synthesized. The thermotropic behavior of the surfactant was investigated by differential scanning calorimetry (DSC) and X-ray scattering techniques, with small-angle X-ray scattering (SAXS) analysis revealing a highly ordered lamellar bilayer structure. After full characterization, DDPABr was used in the preparation of mesostructured SiO2 nanocomposite thin films via evaporation-induced self-assembly (EISA). Resulting thin SiO2-DDPABr films were studied by 1D and 2D small-angle X-ray scattering (SAXS) techniques, indicating a lamellar nanocomposite structure. Suitable theoretical SAXS models were applied to fit the experimental 1D SAXS data. The surfactant could be chemically polymerized within the lamellar domains.     

Growth process for fractal polymer aggregates formed by perfluorooctyltrimethoxysilane. Time-resolved small-angle X-ray scattering study

The acid-catalyzed condensation reaction of perfluorooctyltrimethoxysilane (PFOS) and n-octyltrimethoxysilane (OTMS) in ethanol has been followed by time-resolved synchrotron radiation small-angle X-ray scattering (SAXS) on a short time scale. SAXS curves for PFOS and OTMS have been interpreted as arising from mass fractals with D _f=2 (PFOS) and D _f=1.7 (OTMS). The time dependence of the apparent radius of gyration, obtained from the Guinier plots, showed that the growth of fractal precursors occurs in a two-step process within 2 h for PFOS and within 1.5 h for OTMS, in which small clusters involving monomers, dimers and trimers are formed in the initial step and formation of larger clusters occurs in the second step. Furthermore, it has been suggested that the hydrophobicity and lipophobicity of the bulky alkyl groups may also contribute to the formation of these giant aggregates. Received: 13 July 1999/Accepted in revised form: 6 October 1999