Gelatine/silicate interactions: from nanoparticles to composite gels

The possibility to design new composites associating biopolymers with mineral phases relies on the understanding and control of their mutual interactions. In this work, aqueous solutions of gelatine and sodium silicate were mixed at pH 5, 37 degrees C and left to stand at 20 degrees C for 1 day. At low gelatine and high silicate contents, precipitates were obtained, containing a fixed silicon/polymer molar ratio. Scanning electron microscopy (SEM) reveals that they are formed of large aggregates of platelets, constituted of closely-packed nanoparticles. For high gelatine contents, composite gels were formed consisting of silica particles dispersed in the biopolymer matrix. Swelling studies indicate that the addition of silica decreases the stability of the gels by inducing gelatine depletion in solution. Similar experiments conducted at pH 7 show that at this pH, silicates are more effective at precipitating gelatine. A model is proposed for the formation of the composites, based on the electrostatic interactions arising between silicates and polymer chains. These results are discussed in the context of hybrid biomaterials design and biosilicification processes.     

High-temperature reaction of a Co2(CO)6-complexed propargyl cation

The novel high-temperature reaction of Co₂(CO)₆-complexed propargyl cations, occurring in the spontaneous and stereoselective (90-97% d,l-) manner and yielding the radical dimers, d,l-3,4-diaryl-1,5-hexadiynes (2, 11, 14), is described. Despite the alleged thermal lability and delicate nature of the requisite Co₂(CO)₆-complexed propargyl cations, the reaction temperature can be elevated from 20 °C to 147 °C, shortening the reaction time from 660 min to less than 1 min. Isotopic enrichment experiments detected (MS TOF/ESI/APCI) an incorporation of upto, eight ¹³CO ligands into the metal core, suggesting a single electron, cluster-to-cluster reduction along the reaction coordinate. The reaction kinetics is found to be sensitive toward the electronic nature of the substituents (H, OMe) and to the substitution pattern (0-, 4-, 3,4,5-) on the periphery of the aromatic ring. Calculation data suggest that the spontaneous transfer of a single electron from the metal cluster, onto a π-bonded propargyl moiety, is dependent upon the negative charge on aromatic C_1^′ carbon atom, located alpha to the cationic center. The spontaneous conversion of diamagnetic species (propargyl cation) to paramagnetic counterparts (propargyl radical) indicates that the π-bonded organometallic cations can act as the prototypes for transition metal-based thermal sensors. Their application in photochemical research, electronic devices, molecular electronics, and biomedical fields can also be envisioned.     

Existence and regularity of solutions for some partial functional integrodifferential equations in Banach spaces

In this work, we study the existence and regularity of solutions for some partial functional integrodifferential equations in Banach spaces. We suppose that the undelayed part admits a resolvent operator in the sense given by Grimmer in [R. Grimmer, Resolvent operators for integral equations in a Banach space, Transaction of American Mathematical Society 273 (1982) 333–349]. The delayed part is assumed to be locally Lipschitz. Firstly, we show the existence of the mild solutions. Secondly, we give sufficient conditions ensuring the existence of the strict solutions.     

Organotellurium-bridged cyclodextrin dimers as artificial glutathione peroxidase models

To elucidate the importance of the goodness of fit in complexes between substrates and glutathione peroxidise (GPX) mimics, we examined the decomposition of a variety of structurally distinct hydroperoxides at the expense of glutathione (GSH) catalyzed by 2,2′-ditellurobis(2-deoxy-γ-cyclodextrin) (2-Te-γ-CD), and by the corresponding derivatives of β-cyclodextrin (β-CD) and α-cyclodextrin. The good fit of the cumene group into the γ-CD binding cavity reflected the result of well-defined reaction geometry, leading to the most excellent peroxidase activity with high substrate specificity. Furthermore, the catalytic constant and the combination with the best binding also exhibited the highest regioselectivity in the substrate decomposition. Saturation kinetics were observed and the catalytic reaction agreed with a ping-pong mechanism, in analogy with natural GPX, and might exert its thiol peroxidase activity via tellurol, tellurenic acid, and tellurosulfide. The stoichiometry of the inclusion complex was determined to be of 2:1 host-to-guest. The value of stability constant K _c for (2-Te-γ-CD)₂/GSH at room temperature was calculated to be 3.815?×?10⁴?M^?2, which suggested that 2-Te-γ-CD had a moderate ability to bind GSH. Importantly, the proposed mode of the (2-TeCD)₂/GSH complex was the possible important noncovalent interactions between enzymes and substrates in influencing catalysis and binding.     

Local existence and regularity of solutions for some partial functional integrodifferential equations with infinite delay in Banach spaces

In this work, we study the existence and regularity of solutions for some partial functional integrodifferential equations with infinite delay in Banach spaces. We suppose that the undelayed part admits a resolvent operator in the sense of Grimmer [R. Grimmer, Resolvent operators for integral equations in a Banach space, Transactions of the American Mathematical Society 273 (1982) 333–349]. The delayed part is assumed to be locally Lipschitz. Firstly, we show the existence of the mild solutions. Secondly, we give sufficient conditions ensuring the existence of strict solutions.     

Beyond 90-km Reach of a 16 × 2.5 Gb/s C/L-band Dense Wavelength-Division Multiplexing Metropolitan Network Based on Self-Seeded Reflective Semiconductor Optical Amplifiers

Abstract

This article reports the operation of a cost-effective, colorless, dense wavelength-division multiplexing metropolitan network based on self-seeded reflective semiconductor optical amplifiers. All reflective semiconductor optical amplifiers used in the experiments are packaged in commercial small form-factor pluggable modules. The proposal architecture is simple and symmetric thanks to utilization of two cyclic array waveguide gratings. Downstream link functions in the C-band wavelength range and the upstream link functions in the L-band wavelength range. By using erbium-doped fiber amplifiers to extend the reach, an error-free transmission over 90 km for 16 channels at 2.5 Gb/s was experimentally demonstrated for both directions, and an optical budget over 35 dB was obtained.     

时序控制预裂爆破参数优化及应用

针对白鹤滩水电站地下厂房的爆破开挖,为降低爆破对岩体的损伤,采用数值模拟与现场试验研究小孔径时序控制预裂爆破中,后爆孔孔间延期时间及后爆孔孔距对时序控制预裂爆破成缝的影响,从而获取合理的延期时间和最佳的后爆孔孔距。研究结果表明,孔径为42mm的时序控制预裂爆破,先爆孔孔距为35cm时,合理的起爆延期时间为75~100μs;综合考虑炸药爆炸能量利用率和成缝效果,最佳的后爆孔孔距为70cm。科学地采用时序控制预裂爆破不仅可以减小钻孔工作量与炸药用量,还能降低对岩体的损伤,可为地下厂房爆破开挖安全、高效的进行提供一条有效的途径。