Study on the polymerization of ϵ‐caprolactam in the interlamellar spaces of [TEACOOH]–montmorillonite intercalations complex and its characterization

The polymerization of ?‐caprolactam between the interlamellar spaces of the [TEACOOH]–montmorillonite intercalations complex was attempted using Na–montmorillonite and 10‐carboxy‐n‐decyltriethylammonium bromide to achieve [TEACOOH]–polycaprolactam–montmorillonite, in which montmorillonite (inorganic polymer) is chemically bonded with the polycaprolactam (organic polymer). The results of X‐ray and IR analysis for the samples obtained after polymerization showed that the polymerization reaction has been successfully accomplished. For the purpose of studying the polymeric reaction product more precisely, we have isolated the polymerized product from the silicate layers and analyzed it with X‐ray diffractometer and IR spectrometer. Comparison of the results of X‐ray and IR analysis between the isolated polymer and the polymer that was synthesized by the reaction of ?‐caprolactam only with the organic cation without montmorillonite showed that both obtained polymers are the same compounds. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1904–1910, 2003     

Synthesis and evaluation of an intercalator-polyamide hairpin designed to target the inverted CCAAT box 2 in the topoisomerase IIalpha promoter

The synthesis and DNA-binding properties of a novel naphthalimide-polyamide hairpin (3) designed to target the inverted CCAAT box 2 (ICB2) site on the topoisomerase IIalpha (topoIIalpha) promoter are described. The polyamide component of 3 was derived from the minor-groove binder, 2, and tailored to bind to the 5'-TTGGT sequence found in and flanking ICB2. The propensity of mitonafide 4 to intercalate between G-C base pairs was exploited by the incorporation of a naphthalimide moiety at the N terminus of 2. Hybrid 3 targeted 5'-CGATTGGT and covered eight contiguous base pairs, which included the underlined ICB2 site. DNase I footprinting analysis with the topoIIalpha promoter sequence demonstrated that 3 bound selectively to the ICB2 and ICB3 sites. Thermal-denaturation studies confirmed these results, and the highest degree of stabilization was found for ICB2 and -3 in preference to ICB1 (4.1, 4.6, and 0.6 degrees C, respectively). CD studies confirmed minor-groove binding and suggested a 1:1 binding stoichiometry. Emission-titration experiments established intercalative binding. Surface plasmon resonance results showed strong binding to ICB2 (2.5x10(7) M(-1)) with no observable binding to ICB1. Furthermore, the binding constant of 3 to ICB2 was larger than that of the parent polyamide 2. The increased binding affinity was primarily due to a reduction in the dissociation-rate constant of the polyamide-DNA complex, which can be attributed to the N-terminal naphthalimide moiety. In addition, the binding site of 3 was larger than that of 2, which innately improved sequence selectivity. We conclude that the polyamide-naphthalimide 3 selectively binds to the ICB2 site by simultaneous intercalation and minor-groove binding, and warrants further investigation as a model compound for the regulation of topoIIalpha gene expression.     

循环动荷载下泥化夹层累积变形特性研究

泥化夹层是诱发岩体工程失稳破坏的重要因素之一。为研究循环动荷载下泥化夹层的累积变形特性,深入分析主要影响因素,在黄河中游某大型水利枢纽工程勘探平硐采取试样,开展了不同工况条件下泥化夹层的动三轴试验研究。在考虑主要黏土矿物成分、黏粒含量、含水率、围压和频率等影响因素的基础上,根据试验成果,探求适合描述泥化夹层累积应变发展规律的理论模型,并基于动应力～应变关系研究了泥化夹层的动弹性模量特征。研究结果表明:(1)泥化夹层的累积应变发展规律具有破坏型特征,不符合稳定型累积应变特征,利用Monismith模型进行描述是合理的;(2)泥化夹层的动应力～应变曲线符合Hardin双曲线模型;(3)泥化夹层的累积应变随含水率、黏粒含量和频率的增大而增大,随围压的增大先减小后增大;(4)泥化夹层的动弹性模量随围压增大单调递增,随循环周次、含水率和频率的增大而单调递减;(5)主要黏土矿物成分为蒙伊混层时,泥化夹层的累积应变最大,动弹性模量随循环周次增加而衰减最快。     

小浪底工程中原状泥化夹层的动三轴试验

对黄河小浪底工程左岸山体含泥化夹层的岩芯试样进行了动三轴试验研究。结果表明：当总剪应力比α较小时，试样变形随振次增加而趋向稳定，而当α大于０．４时，变形随振次增加呈破坏性发展趋势；试样的动强度随振次增加而减小，在振次达到千次后趋向稳定。根据试验成果，并结合山体的实际条件，提出了泥化夹层的动力总强度指标     

Flexible Carbon Dots-Intercalated MXene Film Electrode with Outstanding Volumetric Performance for Supercapacitors

2D MXenes have emerged as promising supercapacitor electrode materials due to their metallic conductivity, pseudo-capacitive mechanism, and high density. However, layer-restacking is a bottleneck that restrains their ionic kinetics and active site exposure. Herein, a carbon dots-intercalated strategy is proposed to fabricate flexible MXene film electrodes with both large ion-accessible active surfaces and high density through gelation of calcium alginate (CA) within the MXene nanosheets followed by carbonization. The formation of CA hydrogel within the MXene nanosheets accompanied by evaporative drying endow the MXene/CA film with high density. In the carbonization process, the CA-derived carbon dots can intercalate into the MXene nanosheets, increasing the interlayer spacing and promoting the electrolytic diffusion inside the MXene film. Consequently, the carbon dots-intercalated MXene films exhibit high volumetric capacitance (1244.6 F cm⁻³ at 1 A g⁻¹), superior rate capability (662.5 F cm⁻³ at 1000 A g⁻¹), and excellent cycling stability (93.5% capacitance retention after 30 000 cycles) in 3 m H₂SO₄. Additionally, an all-solid-state symmetric supercapacitor based on the carbon dots-intercalated MXene film achieves a high volumetric energy density of 27.2 Wh L⁻¹. This study provides a simple yet efficient strategy to construct high-volumetric performance MXene film electrodes for advanced supercapacitors.     

冲孔灌注桩在坑口火电厂水泵房地基处理中的应用

本文通过龙岩坑口水泵房地基处理的工程实例,介绍了冲孔灌注桩在软弱夹层、溶洞地基中的应用。通过工程桩,承受及传递泵房上部结构的荷载,解决由于软弱夹层、溶洞等地质条件的不均匀性对水工建筑物的影响。     

Triplex‐Forming Twisted Intercalating Nucleic Acids (TINAs): Design Rules,Stabilization of Antiparallel DNA Triplexes and Inhibition of G‐Quartet‐Dependent Self‐Association

The majority of studies on DNA triple helices have been focused on pH‐sensitive parallel triplexes with Hoogsteen CT‐containing third strands that require protonation of cytosines. Reverse Hoogsteen GT/GA‐containing antiparallel triplex‐forming oligonucleotides (TFOs) do not require an acidic pH but their applicability in triplex technology is limited because of their tendency to form undesired highly stable aggregates such as G‐quadruplexes. In this study, G‐rich oligonucleotides containing 2–4 insertions of twisted intercalating nucleic acid (TINA) monomers are demonstrated to disrupt the formation of G‐quadruplexes and form stable antiparallel triplexes with target DNA duplexes. The structure of TINA‐incorporated oligonucleotides was optimized, the rules of their design were established and the optimal triplex‐forming oligonucleotides were selected. These oligonucleotides show high affinity towards a 16 bp homopurine model sequence from the HIV‐1 genome; dissociation constants as low as 160 nM are observed whereas the unmodified TFO does not show any triplex formation and instead forms an intermolecular G‐quadruplex with T_m exceeding 90 °C in the presence of 50 mM NaCl. Here we present a set of rules that help to reach the full potential of TINA‐TFOs and demonstrate the effect of TINA on the formation and stability of triple helical DNA.     

Zinc Intercalated Lattice Expansion of Ultrafine Platinum–Nickel Oxygen Reduction Catalyst for PEMFC

Platinum (Pt)-based membrane electrode assembly (MEA) catalysts with high performance under operating proton exchange membrane fuel cells (PEMFCs) conditions are a prerequisite for practical applications. As indicated by theoretical calculations, lattice expansion in zinc (Zn)-intercalated Pt alloys can weaken the adsorption of oxygen intermediates, enabling strong electronic interaction for boosting MEA catalysis. To test this hypothesis, herein, a new class of carbon (C)-supported ultrafine Pt alloys with the assistance of Zn is explored. Detailed characterizations indicate that the introduction of Zn can reduce the particle size, and simultaneously intercalates into the Pt alloys, resulting in the lattice expansion for enhancing metallic state of Pt and lowering d-band center. This intercalation strategy can be extended to PtNi, PtCo, as well as Pt. As a result, the optimized Zn-PtNi/C exhibits superior MEA activity (937.6 mW cm⁻² of peak power density), much higher than those of corresponding PtNi/C (771.6 mW cm⁻²) and commercial Pt/C (700.7 mW cm⁻²) under the harsh operating fuel cell conditions. This work opens up a new avenue for creating high-performance PEMFC catalysts in terms of lattice engineering.