Nanomaterials based upon silylated layered double hydroxides

A class of nanomaterials based upon the surface modification of layered double hydroxides (LDHs) have been synthesized by grafting silanes onto the surfaces of the LDH. By in situ coprecipitation, the surfaces of a LDH have been modified through grafting of 3-aminopropyltriethoxysilane (APTS) using the anionic surfactant Na-dodecylsulfonate (SDS). The synthesized nanomaterials were characterized by X-ray diffraction (XRD), attenuated total reflection Fourier-transform infrared spectroscopy (ATR FTIR), thermogravimetry (TG) and transmission electron microscopy (TEM). The grafted LDH (LDH-G) displays distinct XRD patterns proving the obtained materials are a new and different phase. The FTIR spectra of the silylated hydrotalcite show bands attributed to Si-O-M (M = Mg and Al) vibration at 996 cm⁻¹, suggesting that APTS has successfully been grafted onto the LDH layers. The TG curves prove the grafted sample has less M-OH concentration and less interlayer water molecules, as indicated by the M-OH consumption during the condensation reaction between Si-OH and M-OH on the LDH surface. The grafted sample displays a ribbon-like thin sheet in the TEM images, with the lateral thickness estimated as 2.5 nm.     

层状复合氢氧化物对乙酰苯甲酸的负载与体外释放

共沉淀-微波晶化法合成层状复合氢氧化物(LDH)后, 用不同方式将乙酰苯甲酸(ASP)组装到LDH层间制成载药体LDH-ASP, 通过对合成及药物释放前后的液相分析与固相表征数据研究了LDH对ASP的负载及载药体LDH-ASP在磷酸盐介质的溶释现象. 结果表明: LDH层间通道是负载、贮存及控制药物释放的微观基础; 载体选择、药物配比、反应能量供给方式及搅拌强度是决定并影响LDH-ASP载药效率的基本因素, LDH-ASP结构参数可以反映药物负载情况、并与其释放性能明确相关; LDH对ASP的负载与释放均致晶胞参数改变、结晶度下降; 载药体与前体的晶态属性、热力学行为及表面特性相似, 而释放药物后固相的晶态性征减弱、无定形性增强、通道吸附活性降低, 有利于使命后载体在体内降解消除.     

Protective effect of melatonin on photo-damage to lysozyme

The behavior of melatonin in the riboflavin-sensitized photo-oxidation of lysozyme was monitored. Melatonin was found to prevent aggregation of protein and the decrease of enzyme activity induced by photo-oxidation. Electron spin resonance experiments showed that photo-oxidation of lysozyme in the presence of riboflavin resulted in formation of protein radicals, and melatonin was highly effective in reducing the formation of protein radicals. Direct evidence of melatonin’s ability for quenching the triplet state of riboflavin and singlet oxygen was presented. A mechanism of the protective effect of melatonin on photo-oxidation of protein was proposed and the physiological relevance was discussed.     

Aluminacyclopropene: syntheses, characterization, and reactivity toward terminal alkynes

Reactions of LAl with ethyne, mono- and disubstituted alkynes, and diyne to aluminacyclopropene LAl[eta2-C2(R1)(R2)] ((L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3); R1 = R2 = H, (1); R1 = H, R2 = Ph, (2); R1 = R2 = Me, (3); R1 = SiMe3, R2 = C[triple bond]CSiMe3, (4)) are reported. Compounds 1 and 2 were obtained in equimolar quantities of the starting materials at low temperature. The amount of C2H2 was controlled by removing an excess of C2H2 in the range from -78 to -50 degrees C. Compound 4 can be alternatively prepared by the substitution reaction of LAl[eta2-C2(SiMe3)2] with Me3SiC[triple bond]CC[triple bond]CSiMe3 or by the reductive coupling reaction of LAlI2 with potassium in the presence of Me3SiC[triple bond]CC[triple bond]CSiMe3. The reaction of LAl with excess C2H2 and PhC[triple bond]CH (<1:2) afforded the respective alkenylalkynylaluminum compounds LAl(CH=CH2)(C[triple bond]CH) (5) and LAl(CH=CHPh)(C[triple bond]CPh) (6). The reaction of LAl(eta2-C2Ph2) with C2H2 and PhC[triple bond]CH yielded LAl(CPh=CHPh)(C[triple bond]CH) (7) and LAl(CPh=CHPh)(C[triple bond]CPh) (8), respectively. Rationally, the formation of 5 (or 6) may proceed through the corresponding precursor 1 (or 2). The theoretical studies based on DFT calculations show that an interaction between the Al(I) center and the C[triple bond]C unit needs almost no activation energy. Within the AlC2 ring the computational Al-C bond order of ca. 1 suggests an Al-C sigma bond and therefore less pi electron delocalization over the AlC2 ring. The computed Al-eta2-C2 bond dissociation energies (155-82.6 kJ/mol) indicate a remarkable reactivity of aluminacyclopropene species. Finally, the 1H NMR spectroscopy monitored reaction of LAl(eta2-C2Ph2) and PhC[triple bond]CH in toluene-d8 may reveal an acetylenic hydrogen migration process.     

鄂尔多斯盆地奥陶纪中央古隆起水平迁移规律——来自于同沉积记录的证据

鄂尔多斯盆地奥陶纪中央古隆起是盆地内的重要油气聚集区,其成因一直是大家关注的热点.利用丰富的钻井资料对古隆起中东部地区中奥陶统马五段地层的沉积特征进行详细的分析,编制出了马五段各层段的厚度等值线图,圈出了各时期的沉降中心位置,发现在马五₈~马五₅时期,沉降中心基本以向南迁移为主,伴随着一定程度的向西迁移;在马五₄³到马五₄¹时期,沉降中心以向西的迁移为主,伴随微弱的向南迁移.这种迁移过程支持鄂尔多斯盆地西、南缘在奥陶纪时发育双前陆盆地,“L”型中央古隆起是在早-中奥陶世时受该双前陆盆地前缘隆起相互叠加的影响.     

磁驱动准等熵平面压缩和超高速飞片发射实验技术原理、装置及应用

利用脉冲大电流产生随时间平滑上升的磁压,实现对样品的准等熵平面压缩和超高速飞片发射,是近十年来发展和完善起来的一种新型的强动态斜波加载技术(ramp wave loading).本文简述了其原理、加载装置及数据处理方法等方面的研究进展,同时着重评述利用该技术和方法开展高压物态方程、材料动力学响应方面的研究进展,并对该技术在冲击动力学、天体物理和高能量密度物理等方面的应用前景进行了展望.      

Characterization of automorphism groups of sporadic simple groups

It is proved that all automorphism groups of the sporadic simple groups are characterized by their element orders and the group orders.     

一种新型比色荧光双通道水相检测氰根离子的化学传感器

合成了一种新型的,能在含水介质中比色荧光双通道单一选择性识别CN^-的传感器分子1-羟基萘甲叉酰肼乙基-3-羟基萘甲叉酰肼甲基苯并咪唑溴鎓盐(J1)。 在J1的DMSO/H₂O (体积比3:2)HEPES 的缓冲体系(pH=7.2)中分别加入F^-、Cl^-、Br^-、I^-、AcO^-、HSO₄^-、ClO₄^-、H₂PO₄^-、SCN^-和CN^-等阴离子后,只有CN^-的加入会使得溶液颜色发生明显的变化,由无色变为深黄色。 相应地在J1的DMSO/H₂O (体积比4:1)HEPES的缓冲体系(pH=7.2)中加入CN^-,溶液发出明亮的黄色荧光。 这一识别过程,不会受到其它阴离子的干扰。 紫外-可见光谱的最低检测限为1.57×10^-7 mol/L,检测线性范围为3.875×10^-4~2.15×10^-2 mol/L。 荧光光谱的最低检测限为4.63×10^-6 mol/L,检测线性范围为0.8×10^-4~1.60×10^-3 mol/L。 此结果表明,J1是一种良好的用于识别 CN^-的化学传感器,在含水介质中对CN^-具有选择性好、灵敏度高以及抗干扰性强的识别性能。 与此同时,基于J1对于CN^-的高选择性识别我们制备了CN^-的检测试纸,该试纸能够方便、快捷、准确地检测水中的CN^-。     

非均相催化臭氧氧化反应机制

臭氧催化氧化作为高级氧化技术是目前水处理领域研究的热点,其中非均相臭氧催化氧化技术因其氧化能力强、降低臭氧投加量特别是能显著提高有机物矿化率等优点而备受关注。非均相催化臭氧氧化领域不断研究新的催化剂,但是其反应过程及机制更加复杂。催化臭氧氧化的性能很大程度上取决于催化剂及其表面性质。污染物在催化剂表面形成络合物,或者臭氧在催化剂表面分解产生不同的含氧物种如表面氧原子、过氧化物和羟基自由基等。本文评述了非均相臭氧催化氧化反应中存在的多种机理,主要是自由基理论、氧空位理论、表面原子氧理论、表面络合物理论和臭氧直接氧化理论。催化剂表面的羟基基团是主要的催化活性中心,本文探讨了表面羟基基团催化反应机制,得出催化剂表面性质决定其表面活性位点的特性及含量,对诱导臭氧分解产生含氧活性物种起了关键作用;概述了催化剂改性后的结构形态、比表面积及其性能和作用机制;并讨论了非均相臭氧催化氧化反应催化剂未来的发展趋势,为催化臭氧氧化污水处理技术提供了理论参考。     

Infrared study of HDTMA+ intercalated montmorillonite

In this paper, FTIR spectroscopy using attenuated total reflection (ATR) and KBr pressed disk techniques has been used to characterize sorbed water and HDTMA+ in organo-clay. Sorbed water content decreases with the intercalation of HDTMA+. With the decrease of the sorbed water content, the position of the nu2 mode shifts to higher frequency dramatically while the stretching vibration shifts to lower frequency slightly, indicating that H2O is less strongly hydrogen bonded. This might be resulted from the polarization of H2O molecules by the changeable cations and HDTMA+. FTIR spectra show that both antisymmetric and symmetric CH2 stretching absorption bands shift to low frequencies with increase of amine concentration within the galleries of montmorillonite, elucidating the increase of ordered conformation. Furthermore, the present study demonstrates that the antisymmetric CH2 stretching mode is more sensitive to the conformational ordering than the symmetric stretching mode. When KBr pressed disk technique used, two well resolved absorption bands at 730 and 720 cm(-1), and at 1473 and 1463 cm(-1), corresponding to the methylene scissoring and rocking modes, respectively, could be observed in FTIR spectra of organo-clays with relative higher concentration of surfactant. However, the FTIR spectra using ATR technique only display singlets and they are independent of amine concentration and chain conformation. Our present study demonstrates that FTIR spectroscopy using KBr pressed disk technique is more suitable to probe the conformational ordering of surfactant in organo-clays than that suing ATR technique does.