Structural model of silica nanowire assembled from a highly stable (SiO2)8 unit

The ground-state structures of silica clusters (SiO2)n for n = 1-8 were studied by performing calculations at the B3LYP/6-311+G(d) level of density functional theory. The results indicate that the growth mode of a silica nanowire based on small silica clusters may change at different wire lengths. A linear chain might be assembled from the smallest clusters of rhombic two-membered ring (2MR) with n < or = 5, while the growth motif changes at n = 6 into a more compact form composed of three-membered-rings (3MRs). The 3MR-containing structures become energetically favorable configurations for even longer silica clusters. In particular, the closed molecular ring consisting of 3MRs at n = 8 (i.e., (SiO2)8) with a high symmetry shows extreme energetic stability and relatively high chemical reactivity and thus is considered to be an important building block to assemble into silica nanowires. The relative stability of so-assembled silica nanowires were evaluated and compared with the models of silica nanowires in the literature.     

Atom cell for use in hydride-generation atomic fluorescence spectrometry

An electrically-heated silica tube atom cell is described for the determination of selenium in blood serum. The detection limit was 1.4 ng in 10 ml of aqueous solution. The r.s.d. at 10, 50 and 200 ng of selenium was 6.8% (n = 5), 4.3% (n = 6) and 4.7% (n = 10) respectively. Calibration was linear up to 600 ng.     

Immobilisation and evaluation of a vancomycin chiral stationary phase for capillary electrochromatography

The macrocyclic antibiotic, vancomycin, is covalently bonded to LiChrospher diol silica packed columns and evaluated in capillary electrochromatography (CEC) both in the reversed-phase and polar organic mode. Initially, capillaries were packed with 5 microm LiChrospher 100 A diol silica and evaluated in CEC with a reversed-phase biphenyl-pyrene achiral test resulting in resolution and efficiency values of ca. 2.5 and 100000 plates meter(-1), respectively. Repeatability for this test (resolution and efficiency) was also examined and found to be acceptable for both run-to-run (n=5, 0.74% and 1.5%) and column-to-column (n=5, 3.4% and 9.0%), respectively. Similar results were obtained when the 10 microm LiChrospher 1000 A diol silica was examined with the exception of efficiency, where a reduced plate height value of four times lower was obtained compared to the 100 A material. A simple three step in-situ vancomycin immobilisation procedure was subsequently carried out on these packed diol columns. Selectivity was obtained for thalidomide enantiomers on this vancomycin chiral stationary phase in reversed-phase CEC with resolution and efficiency values of ca. 2.5 and 80000 plates meter(-1), with acceptable repeatability (n=8) 0.9% and 3.0%, respectively. Selectivity was also obtained for thalidomide enantiomers on this phase in the polar organic mode with resolution and efficiency values of ca. 2.5 and 120000 plates meter(-1), with acceptable repeatability (n=7) 0.9% and 2.0%, respectively. It was possible to deduce from a chemometric design carried out for evaluating the mobile phase component effects that organic modifier ratio, MeOH/MeCN, played a significant role in controlling both resolution and efficiency. It was also possible to separate a number of basic analytes including four beta-adrenergic blocking agents in the polar organic mode albeit with lower resolution and efficiency values, ca. 1.5 and 45000 plates meter(-1), respectively.     

Inverse opal photonic crystal of chalcogenide glass by solution processing

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.     

Adsorbability and photocatalytic degradability of humic substances in water on Ti-modified silica

From the viewpoint of development of a removal agent for humic substances, we prepared Ti-modified silica gel, SiO2-Ti, from titanium alkoxide and microsized silica gel. The prepared silica agent was investigated in adsorption and photocatalytic degradation of humic substances in water. In these experiments, four humic substances, commercially available Wako humic acid (Wako-HA), Nordic aquatic humic acid (Nordic-HA), Nordic aquatic fulvic acid (Nordic-FA), and Suwannee river fulvic acid (Suwannee-FA), were used, and Freundlich constants (KF and 1/n) and photodegradation rates were evaluated. Wako-HA, which has the highest aromaticity ratio [Ar-OH]/[COOH] and molecular weight, had the highest adsorbability (KF=17.5 (mg/g)(L/mg)(1/n), 1/n=0.67) but the lowest photodegradability (<80%). On the other hand, Suwannee-FA, which has the lowest aromaticity, [Ar-OH]/[COOH] ratio, and molecular weight, afforded lesser adsorbability (KF=7.1 (mg/g)(L/mg)(1/n), 1/n=0.39) but the highest photodegradability (>99%). Nordic-HA and Nordic-FA afforded adsorbabilities similar to that for Suwannee-FA, and medium photodegradabilities between those for Wako-HA and Suwannee-FA. Adsorption and photodegradation capacities of SiO2-Ti were improved with increased Ti content and phosphorescence emission amount, respectively. From XRD analysis, we found that the structure of anatase-type TiO2 features the Ti modifiers of SiO2-Ti. Therefore, humic substance molecules effectively interact with the Ti modifiers and are decomposed by OH radicals generated in situ. We hope that SiO2-Ti will be used as a photodegradation catalyst in water purification plants.     

Solid-phase extraction-gas chromatography and solid-phase extraction-gas chromatography-mass spectrometry determination of corrosion inhibiting long-chain primary alkyl amines in chemical treatment of boiler water in water-steam systems of power plants

Gas chromatography with simultaneous flame-ionization detection (FID) and a nitrogen-phosphorus detection (NPD) as well as gas chromatography-mass spectrometry (GC/MS) has been used to characterize long-chain primary alkyl amines after derivatization with trifluoroacetic anhydride (TFAA). Electron impact ionization- (EI) and negative chemical ionization (NCI) mass spectra of trifluoroacetylated derivatives of the identified tert-octadecylamines are presented for the first time. The corrosion inhibiting alkyl amines were applied in a water-steam circuit of energy systems in the power industry. Solid-phase extraction (SPE) with octadecyl bonded silica (C18) sorbents followed by gas chromatography were used for quantification of the investigated tert-octadecylamines in boiler water, superheated steam and condensate samples from the power plant. The estimated values were: 89 microg l(-1)(n = 5, RSD = 7.8%), 45 microg l(-1) (n = 5, RSD = 5.4%) and 37 microg l(-1)(n = 5, RSD = 2.3%), respectively.     

Tailored core-shell-shell nanostructures: sandwiching gold nanoparticles between silica cores and tunable silica shells

Size tunable and structure tailored core-shell-shell nanospheres containing silica cores, gold nanoparticle shells, and controlled thicknesses of smooth, corrugated, or porous silica shells over the gold nanoparticles have been synthesized. The synthesis involved the deposition of gold nanoparticles on silica cores, followed by sol-gel processing of tetraethoxysilane (TEOS) or sodium silicate to form dense or porous silica shells, respectively, over the gold nanoparticles. The structures and sizes of the resulting core-shell-shell nanospheres were found to heavily depend on the sizes of the core nanoparticles, the relative population of the gold nanoparticles on each core, and the concentration of TEOS. While a higher TEOS concentration resulted in thicker and more uniform silica shells around individual larger silica cores (approximately > or =250 nm in diameter), the same TEOS concentration resulted in aggregated and twin core-shell-shell nanostructures for smaller silica cores (approximately < or =110 nm in diameter). The thinner silica shells were synthesized by using a lower TEOS concentration. By using sodium silicate (Ung et al. J. Phys. Chem. B 1999, 103, 6770), the porous silica shells were synthesized. Controlled chemical etching of the core-shell-shell nanoparticles with an aqueous KCN solution resulted in corrugated silica shells around the gold nanoparticles or corrugated silica nanospheres with few or no gold nanoparticles. This has allowed synthesis of new types of core-shell-shell nanoparticles with tailored corrugated shells. The nanoporous silica shells provided accessible structures to the embedded metal nanoparticles as observed from the electrochemical response of the gold nanoparticles.     

不同硅铝比β沸石的理化性质及烃类催化裂化活性

采用润湿态固相转化方法按照投料硅铝摩尔比(n(SiO2)/n(Al2O3))分别为30、60、150、300、500和纯硅时合成了β沸石, 化学法和X射线荧光(XRF)测定产物的硅铝比和反应初始凝胶基本一致. 利用X射线衍射(XRD)、红外光谱(FT-IR)、扫描电镜(SEM)、氨程序升温脱附(NH3-TPD)和低温N2吸附对系列样品的物相、水热稳定性、晶体形貌、酸性以及表面积和孔体积做了系统的表征. 并将该系列样品作为活性组分添加剂, 以高岭土为基质分别制备烃类裂化催化剂, 对其催化裂化性能进行了评价. 结果表明, 不同硅铝比β沸石添加到裂化催化剂均可以提高其裂化活性, 改善催化剂的抗积炭性能, 硅铝比为150的β沸石催化剂在保持较高裂化活性的前提下, 汽油收率最高, 抗积炭性能也较好, 是优选的裂化催化材料.     

Silica nanoparticles as pseudostationary phase for protein separation

This paper investigated the potential use of silica nanoparticles (SNPs) as pseudostationary phase (PSP) for protein separation. The wall adsorption of SNPs as well as the influences of SNPs and poly(ethylene oxide) (PEO) were studied. The SNPs showed selectivity toward the proteins, and the concentration ratio of SNPs to PEO influenced the separation. The proteins that could not be baseline-resolved under conventional CZE mode were separated in a buffer consisting of 30 mM phosphoric acid, 0.05% PEO, and 0.05% SNPs at pH 2.37, with detection limits ranging from 2 to 45.5 ppm. The intraday and interday RSDs of the migration times were in the ranges of 2.1-2.8% (n = 5) and 2.5-3.4% (three days, n = 3 x 5 = 15), respectively.     

混合超分子液晶模板法合成六方介孔相含钛氧化硅

采用混合十六烷基三甲基溴化铵（CTAB）与不同碳链的脂肪胺（CnNH2n＋3, n=8,10,12,14,16）作模板,在四甲基氢氧化胺为碱源的条件下,合成了具有六方介孔结构的含钛氧化硅Ti MCM 41分子筛材料. XRD和TEM测试表明所合成材料具有高度的长程有序结构,样品的N2吸附/脱附等温线表明,高度有序的Ti MCM 41材料展示了毛细凝聚的陡峭台阶和狭窄的介孔孔径分布.对反应物配比中Ti/Si比、脂肪胺碳链长度n对六方介孔相结构的影响进行了研究,实验发现当Ti/Si< 0.15和n< 16时,均可获得具有六方介孔结构的含钛氧化硅Ti MCM 41;而当Ti/Si≥0.15或n >16时,产物将分别发生从六方向无定形态或从六方向层状介孔相结构的转移,从混合表面活性剂的堆积参数对这种相转移现象进行了分析.     

Fast neutron activation analysis of bulk coal samples for alumina,silica and ash

The fast neutron activation technique was applied to bulk samples (≈11 kg) of Australian black coal. The determination of alumina is based on the reaction ²⁷Al(n,p)-²⁷Mg by counting the 0.844-MeV peak (t_{$\text{1}\text{2}$} = 9.4 min). Silica is determined by means of the reaction ²⁸Si(n,p)²⁸Al; the 1.78-MeV peak (t_{$\text{1}\text{2}$} = 2.3 min) is counted and a correction for the interference from alumina is applied. The ash content is based on the correlation between ash and the sum of alumina and silica. The accuracies (1 SD) for the determination of alumina, silica and ash were 0.52% Al₂O₃, 0.79% SiO₂ and 1.02% ash, respectively. The ash, alumina and silica contents of the samples were in the ranges 8.8–37.5%, 1.3–10.3% and 6.4–22%, respectively.     

Preparation and evaluation of a vancomycin-immobilized silica monolith as chiral stationary phase for CEC

Enantiomeric separations in CEC with the macrocyclic antibiotic vancomycin immobilized silica monolith as a chiral stationary phase are presented. The monolithic silica capillary columns were prepared by a sol-gel process in fused-silica capillaries with an inner diameter of 50 mum and subsequently in situ immobilization of vancomycin as a chiral selector by reductive amination. Enantioselectivity was obtained for eight pairs of enantiomers in nonaqueous polar organic or aqueous mobile phases and most of them were baseline-separated with high column efficiencies. It was observed that the organic modifier ratio (MeOH/ACN) in the polar organic mobile phase played a significant role in controlling the resolution and efficiency of the enantiomers. In enantiomeric separation of propranolol, repeatability for column efficiency and resolution in the nonaqueous mobile phase was given in terms of RSD values at 1.1 and 2.3% (n = 5) for run-to-run injections and 7.2 and 9.6% (n = 5) for column-to-column testing while repeatability for the separation of thalidomide in the aqueous mobile phase was given in terms of RSD values at 1.5, 2.8% and 6.1, 10.5%, respectively.     

扶正丹中补骨脂素含量的测定方法

采用含０．５％羰甲基纤维素钠硅胶Ｇ薄层色谱分离和ＣＳ－９３０荧光扫描法测定扶正丹中有脂素的含量,不受处方中其他成分的干扰,方法灵敏,特异性强,操作简便,结果可靠,可作为质量控制的定理标准。该法线性回归方程为Ｙ＝４２６１６．８６Ｘ＋１１３０１．９１,ｒ＝０．９９６,加标回收率的１０１．６％,同一样品点样６次测得的ＲＳＤ为２．２５％。     

Oligo-lysine Induced Formation of Silica Particles in Neutral Silicate Solution

Introduction Theformationofsilicastructuresunderthecontrol ofalivingorganism(biosilification)isawidespread phenomenoninnature,whichisfoundinmanylife formssuchasdiatoms,spongesandgrasses,etc.[1,2].Themostattractiveaspectofbiosilificationisthatex quisitestr…     

Transmission electron microscopy study of solvent-induced phase morphologies of environmentally responsive mixed homopolymer brushes on silica particles

We report in this work a transmission electron microscopy study of phase morphologies of environmentally responsive mixed poly( t-butyl acrylate) (P tBA)/polystyrene (PS) brushes and mixed poly(acrylic acid) (PAA)/PS brushes on 180 nm silica particles after treatments with nonselective good solvents and selective solvents, respectively. Mixed P tBA/PS brushes were grown from Y-initiator-functionalized silica particles by sequential atom transfer radical polymerization and nitroxide-mediated radical polymerization. Mixed PAA/PS brushes were prepared from mixed P tBA/PS brushes by removal of the t-butyl groups. For mixed P tBA/PS brushes with P tBA M n of 24.2 kDa and PS M n of 23.0 kDa and the corresponding mixed PAA/PS brushes, random worm-like, nearly bicontinuous nanostructures were formed from lateral microphase separation when the particles were cast from nonselective good solvents (chloroform for mixed P tBA/PS brushes and N, N-dimethylformamide for mixed PAA/PS brushes). The feature sizes were on the order of polymer chain root-mean-square end-to-end distances ( approximately 10 nm). In contrast, mixed P tBA/PS brushes with lower molecular weights (P tBA M n = 10.4 kDa and PS M n = 11.9 kDa) did not strongly phase separate after being cast from chloroform. After the solvents in the particle dispersions were gradually changed to selective solvents ( n-octane for mixed P tBA/PS brushes and H 2O for mixed PAA/PS brushes), isolated microdomains with an average size of 14-19 nm were formed as one grafted polymer collapsed and associated to form isolated microdomains, which were shielded by another grafted polymer yielding surface-tethered micellar structures. These results confirmed the theoretical predictions of the formation of "rippled" nanostructures and surface micellar structures of mixed homopolymer brushes induced by nonselective and selective solvents, respectively.     

气相色谱/高分辨质谱联用测定环境样品中的二噁英和类二噁英多氯联苯

样品采用索氏抽提,抽提液依次经酸性硅胶床、多段混合硅胶柱和凝胶渗透色谱柱(GPC)净化后,用Florisil硅藻土柱分离出样品中的二噁英(PCDD/Fs)和类二噁英多氯联苯(dioxin-like PCBs),采用同位素稀释法和气相色谱/高分辨质谱联用仪(GC/HRMS)测定了其中的17个2,3,7,8-氯取代二噁英类化合物和12个类二噁英多氯联苯。结果表明,用该法分析二噁英和多氯联苯标准溶液,平行4次的分析结果为:RSD(PCDD/Fs)<8.9%,RSD(PCBs)<11.4%;回收率可达60%-105%。PCDD/Fs和PCBs的检出限分别为0.1-0.8 pg/g和0.05-0.6 pg/g。应用本方法成功测定了沉积物、淤泥、土壤和飞灰中的二噁英和类二噁英多氯联苯,并计算出它们的毒性当量。     

Sol-gel synthesis of low-dimensional silica within coordination nanochannels

Sol-gel condensation of tetramethoxysilane (TMOS) inside the channels of a coordination pillared layer structure [Cu2(pzdc)2(dpe)]n (1a; pzdc = pyrazine-2,3-dicarboxylate, dpe = 1,2-di(4-pyridyl)ethylene) produced subnanosized silica dispersed within the host framework. In this system, the growth of silica is effectively constrained, and the resultant silica shows a drastic decrease of its crystallization temperature because of its minute size.     

The structural and electronic properties of Ag-adsorbed (SiO2)n (n=1-7) clusters

Equilibrium geometries, charge distributions, stabilities, and electronic properties of the Ag-adsorbed (SiO(2))(n) (n=1-7) clusters have been investigated using density functional theory with generalized gradient approximation for exchange-correlation functional. The results show that the Ag atom preferably binds to silicon atom with dangling bond in nearly a fixed direction, and the incoming Ag atoms tend to cluster on the existing Ag cluster leading to the formation of Ag islands. The adsorbed Ag atom only causes charge redistributions of the atoms near itself. The effect of the adsorbed Ag atom on the bonding natures and structural features of the silica clusters is minor, attributing to the tendency of stability order of Ag(SiO(2))(n) (n=1-7) clusters in consistent with silica clusters. In addition, the energy gaps between the highest occupied and lowest unoccupied molecular orbitals remarkably decrease compared with the pure (SiO(2))(n) (n=1-7) clusters, eventually approaching the near infrared radiation region. This suggests that these small clusters may be an alternative material which has a similar functionality in treating cancer to the large gold-coated silica nanoshells and the small Au(3)(SiO(2))(3) cluster.     

硅氧团簇(SiO2)nO2H4的密度泛函理论研究

提出硅氧团簇(SiO2)nO2H4的两种新构型: 基于笼状结构和环状结构的构型, 并与链状构型相比较, 用密度泛函理论的B3LYP方法在6-31G(d)基组水平上计算了三种构型n=2～22(n取偶数)的几何结构、平均结合能、能隙以及能量的二次差分. 分析计算结果发现, 笼状构型不但在n=4和8处存在幻数团簇(实验上已经观察到), 而且预测在n=14处也存在类似的幻数团簇; 此外, 与(SiO2)n团簇不同的是, (SiO2)nO2H4团簇的环状构型的稳定性从n=4开始大于链状构型, 意味着水的加成对硅氧团簇的稳定性有着重要的影响.     

Development and validation of a method for determination of caffeine in diuretic tablets and capsules by high-performance thin-layer chromatography on silica gel plates with a concentration zone using manual spotting and ultraviolet absorption densitometry

A new quantitative method using silica gel high-performance thin-layer chromatography plates with channels and a concentration zone, manual application of standards and samples, development with methanol-ethyl acetate (15 + 85) mobile phase, and ultraviolet absorption densitometry is reported for the determination of caffeine in diuretic pharmaceutical preparations. Tablet and capsule products containing potassium salicylate, acetaminophen, and salicylamide as active ingredients were analyzed to test the applicability of the new method, and precision, accuracy, linearity, limits of detection and quantitation, and selectivity were validated. The milligrams of caffeine in each tablet ranged from 48.0 to 51.0, and the milligrams in each capsule from 37.9 to 40.3. Within-day precision was 1.48 and 1.78% (n=6), and interday precision 0.723 and 1.26% (n=5) for analysis of 2 tablets and 2 capsules, respectively. Accuracy validation of the tablet and capsule results produced errors of 1.0 and 1.9% for spiked blank analyses and 2.6 and 3.5% for standard addition analyses, respectively. A comparative study using a caffeine standard solution and a multicomponent analgesic tablet solution containing caffeine, acetaminophen, and acetylsalicylic acid showed that manual application on the concentration zone, instrumental application on the concentration zone, and instrumental application on the silica gel gave quite similar results in terms of number of theoretical plates, resolution, limit of detection, and linearity.