Highly selective determination of rhodium(III) using silica gel surface-imprinted solid-phase extraction

A novel Rh(III)-imprinted amino-functionalised silica gel sorbent was prepared by a surface imprinting technique for preconcentration and separation of Rh(III) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with the traditional solid sorbents and non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher adsorption capacity and selectivity for Rh(III). The maximum static adsorption capacity of the imprinted and non-imprinted sorbent for Rh(III) was 29.86?mg?g^?1 and 11.23?mg?g^?1, respectively. The imprinted Rh(III) was removed with 2?mL of 3% thiourea?+?2?mol?L^?1 HCl. The obtained imprinted particles exhibited excellent selectivity and rapid kinetics process for Rh(III). The relatively selective factor (α_r) values of Rh(III)/Ru(III), Rh(III)/Au(III), Rh(III)/Pt(IV), Rh(III)/Ir(IV), Rh(III)/Pd(II) were 26.7, 39.0 29.2, 28.1, 43.7, respectively, which were greater than 1. The detection limit (3σ) of the method was 0.26?µg?L^?1. The relative standard deviation of the method was 1.79% for eight replicate determination of 10?µg of Rh³⁺ in 200?mL water sample. The method was validated by analysing standard reference material (GBW 07293), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace rhodium(III) in geological samples with satisfactory results.     

小麦粉中甲醛(吊白块)的测定方法研究

对小麦粉中甲醛提取方法、甲醛与2,4-二硝基苯肼的衍生化反应条件以及甲醛衍生物的提取净化方法进行了研究, 建立了一种小麦粉中甲醛(吊白块)的高压液相色谱测定方法.该方法在甲醛浓度为0.026～0.832 μg/mL范围内与其衍生物的色谱峰面积呈显著线性相关, 相关系数r=0.9986. 小麦粉中甲醛不同添加量的平均回收率＞99%;吊白块不同添加量的平均回收率＞94%(以甲醛量计). 重复测定相对标准偏差平均为4.5%, 甲醛的检出限为9.6 μg/L, 相当于小麦粉中甲醛的最小检出量为0.24 mg/kg.     

Application of silica gel organofunctionalized with 3(1-imidazolyl)propyl in an on-line preconcentration system for the determination of copper by FAAS

This study presents a new procedure for the determination of trace levels of copper(II) in an aqueous matrix, through flow injection (FI) on-line preconcentration with a minicolumn packed with silica gel modified with 3(1-imidazolyl)propyl groups. After the preconcentration stage, the analyte was eluted with a HNO₃ solution and determined by flame atomic absorption spectrometry (FAAS). The measurements of the analytical signals were carried out as peak area and peak height with the objective of evaluating the most appropriate absorption measurement for the proposed method. Four procedures to calculate the experimental enrichment factor (EF) were also studied. For a preconcentration time of 90 s the enrichment factors found in this study varied between 19.5-25.8 and 36.2-42.2 for peak area and peak height, respectively. The precision of the proposed method was calculated for a solution containing 20 μg l⁻¹ of Cu(II), when 11.2 ml of solution was preconcentrated (n=7), and their respective relative standard deviation (R.S.D.) values were 1.2 and 1.4% for peak area and peak height, respectively. The detection limits obtained were 0.4 and 0.2 μg l⁻¹ of Cu(II) for peak area and peak height, respectively, with a preconcentration time of 90 s. The on-line preconcentration system accuracy was evaluated through a recovery test on the aqueous samples and analysis of a certified material.     

A new method for dissolution of silica gel in a pentafluoropropionyl fluoride—tertiary amine system

A new procedure for the preparation of amino complexes of silicon tetrafluoride was proposed. For this purpose, silica gel is dissolved in a fluoroanhydride—methanol system at room temperature followed by the precipitation of SiF₄ solvate that was formed with tertiary amine (pyridine, 1,10-phenanthroline, 2,2′-bipyridyl). The yields of the formed complexes are 69–83%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 421–423, March, 2007.     

Potentiometric study using chemically modified silica gel with pyridinium as membrane for ClO 4 − ions

A potentiometric sensor for the perchlorate anion was developed by mixing chemically modified silicagel with pyridinium perchlorate, with an epoxy polymer and graphite. The electrode showed Nernstian response between 1.0 × 10^–2 and 1.0 × 10^–3 M perchlorate concentrations. The electrode showed high selectivity to this ion at solutions pH between 5.5 and 8.0. The presence of IO ₄ ^– , NO ₃ ^– ,Br^–, IO ₃ ^– , Cl^– and SO ₄ ^2– ions in the solutions, had only small interference in the electrode response in the range mentioned.     

A deprotection procedure using SO3H silica gel to remove non-silyl protecting groups

Protecting groups are indispensable in organic synthesis and there is a great need for a variety of deprotection methods. Here, we investigated the scope of the application of a deprotection procedure using SO₃H silica gel, which we have previously reported as a desilylation procedure. Under these conditions, -OMOM, -OSEM, -OTHP, and -OAc groups and dimethyl acetal were cleaved. Pivaloyloxy, benzyloxy and methoxy carbonyl groups remained intact and selective deprotection of TBS groups in the presence of other protecting groups was accomplished. We succeeded in cleaving an acetyl group on a secondary alcohol in a highly polar nortropine derivative. Our findings here provide another deprotection option and would be helpful in the synthesis of multifunctional compounds.     

On-line solid-phase extraction using alizarin violet functionalized silica gel for determination of trace lead in environmental samples and wastewater by sequential injection spectrophotometry

Trace of Pb(Ⅱ) has been on-line separated and enriched from environmental samples and wastewater by using the self-made alizarin violet functionalized silica gel micro-column coupling with a sequential injection sampling technology. The determination is based on the color reaction of Pb(Ⅱ) with iodide and crystal violet to form an ionic association complex in the presence of polyvinyl alcohol and hydrochloric acid. The use of the microcolumn can prevent the interference of most familiar metal ions, and ther...     

Development and comparison of different fluorimetric HPLC-methods with standard methods for the determination of formaldehyde in the atmosphere

Summary Three different fluorimetric methods for the measurement of atmospheric formaldehyde are described. The relatively unknown 2-diphenylacetylindan-1,3-dionhydrazine (DAIH) method was developed and optimized with an improved limit of detection of 2 ppbv corresponding to a sample volume of 7.5 L. Separation of lutidines necessary for the Nash method was successfully carried out and the separation time was reduced by a factor of 5. The detection limit of the Nash method was improved to 1 ppbv. In comparison, the N,N-diphenyl-1-naphthylamine-5-sulfonhydrazine (DNSH) method performed in a similar manner, reached an LOD of 0.5 ppbv. Finally, measurements made in candle smoke using the three different fluorimetric methods and three standard methods yielded very similar results.     

Probing the dynamics of domain III of human serum albumin entrapped in sol–gel derived silica using a Sudlow’s site II specific fluorescent ligand

Previous studies from our lab reported on the use of time-resolved fluorescence anisotropy (TRFA) to probe the dynamics of domains I and II within the model protein, human serum albumin (HSA), in solution and when entrapped into sol–gel derived silica. In order to further our understanding of the dynamics within this multi-domain protein, TRFA was used to measure the dynamics of domain III of the protein. For this purpose, the fluorescence ligand dansylsarcosine (DS), which has a 400-fold higher emission intensity in the bound state relative to the free state and an emission lifetime of >22 ns when bound to Sudlow’s site II (domain III) in HSA, was selected. This probe is able to accurately report on slow rotational motions (up to 300 ns correlation time) and the bound form of the probe can be selectively measured at 475 nm, ensuring that the dynamics reflect only the properly folded form of the protein. The mobility of HSA with bound dansylsarcosine (HSA–DS) was evaluated in solution and after entrapment in sol–gel derived silica prepared from sodium silicate under varying ionic strength and pH conditions. The results here show that (1) the 43 ns global rotational correlation time of HSA in buffered solution can be accurately measured via labeling with DS with no interference from faster local or segmental motions; (2) the global motion of HSA in silica is greatly hindered immediately after encapsulation, with no correlation time faster than 300 ns discernable, indicative of strong templating of the silica around domain III of the native protein; and (3) the addition of salt and variation of pH have essentially no effect on HSA mobility, ruling out electrostatics as the primary interaction restricting HSA motion. The results from this study are compared to past studies using intrinsic tryptophan fluorescence (domain II) or fluorescein-labeled HSA (domain I), and demonstrate that motion observed using such probes likely reflects differential mobility of the three domains, consistent with domain III of HSA adsorbing to or templating with silica upon entrapment while the other domains protrude into the pore. Restricted motion of domain III of HSA was also observed in silica materials derived from diglycerylsilane or tetraethylorthosilicate, showing that templating is not dependent on the silica precursor or processing conditions.     

A novel fluorescent sensor for hydrophobic amines in aqueous solution

A novel fluorescent tweezer was designed and synthesised to sense hydrophobic amines in aqueous solution. Association of the guest was driven by both hydrophobic effect and electrostatic interactions, with the hydrophobic interactions being dominant. The affinity and selectivity of the sensor for amine-based stimulants are reported.     

A novel fluorescent probe for formaldehyde based-on monomer-excimer conversion and its imaging in live cells

A novel fluorescent probe was developed for formaldehyde, which can be synthesized by one-step Buchwald–Hartwig reaction. When hydrazino-group of probe reacted with formaldehyde, hydrophobic reaction product aggregates into nanoparticles and results in the blue fluorescence due to the monomer-excimer effect. With enough sensitivity, high selectivity, good stability in physiological pH range and excellent biocompatibility, this probe can image formaldehyde in living cells.     

A novel nonenzymatic fluorescent sensor for glucose based on silica nanoparticles doped with europium coordination compound

Amino-functionalized luminescent silica nanoparticles (LSNPs) doped with the europium(III) mixed complex, Eu(TTA)₃phen with 2-thenoyltrifluoroacetone (TTA) and 1,10-phenanthroline(phen) were synthesized successfully using an revised Stöber method. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR), and fluorescence spectroscopy were performed for characterizing the synthesized nanoparticles. In the presence of glucose, the fluorescence intensity of the amino-functionalized LSNPs was enhanced due to the enhanced fluorescence resonance energy transfer. Based on fluorescence-enhancing effect, a simple and sensitive method for the determination of glucose was proposed. Under the optimized experimental conditions, the enhanced fluorescence intensity ratio (ΔF/F₀) was linear with the concentration of glucose (c) in the range of 0.0-180 μg ml⁻¹ with a detection limit of 0.8 μg ml⁻¹ (S/N = 3). The R.S.D. values were 0.33% and 0.37% at the levels of 22.5 and 100 μg ml⁻¹, respectively. The proposed method was applied to the determination of glucose in synthetic samples with satisfactory results. The proposed method was also performed to the analysis of blood glucose in human serum samples and the results were in good agreement with clinical data provided by the hospital, which indicates that the method presented here is not only simple, sensitive, but also reliable and suitable for practical applications.     

Selective water sorbents for multiple applications, 5. LiBr confined in mesopores of silica gel: Sorption properties

This paper presents sorption properties of a selective water sorbent based on mesoporous KSKG silica gel as a host matrix and lithium bromide as a hygroscopic salt. Sorption isobars, isochores and isotherms measured at T=40–120°C and partial vapor pressures of 7.5–81.0 mbar indicated two types of water sorption: 1) formation of a solid crystalline LiBr monohydrate at low amounts of sorbed water, and 2) vapor absorption by the salt solution at higher sorptions. Sorption properties of the LiBr monohydrate are found to change significantly due to salt impregnation into the mesoporous silica gel, whereas the solution confinement to the mesopores did not change its water sorption properties as compared to the bulk solution. Desorption curves follow a first order kinetics in the temperature range of 60–130°C at different vapor pressures.     

An efficient synthesis of propargylamines using a silica gel anchored copper chloride catalyst in an aqueous medium

The design and development of a silica gel anchored copper chloride heterogeneous catalyst for the synthesis of propargylamines using an amine, an aldehyde, and an alkyne through C-H activation in water is described. Both aliphatic and aromatic aldehydes and amines are used for the reaction. The catalyst was recovered quantitatively by simple filtration and reused several times.     

A study of using luminophore-doped silica nanoparticles as fluorescent probe in protein microarray assay

A convenient method for the synthesis of tris(2,2′-bipyridyl) dichlororuthenium(II) hexahydrate-doped amino-modified double-layer silica nanoparticles is presented in this paper. The synthesized nanoparticles are uniform and photostable, and can be well dispersed in a water solution. Proteins could be directly immobilized onto these nanoparticles by a simple coupling process without losing their biological activities. These nanoparticles were further used as fluorescent probes in protein microarray assay for the quantitative detection of protein. The results obtained by these nanoparticles, with the detection limit of as low as 3.5 μg/mL, were much better than those involving the use of conventional FITC probe. Translated from Chinese Journal of Analytical Chemistry, 2006, 34(9): 1227–1230 (in Chinese)     

Determination of chromium(III) and total chromium in natural waters using a surface ion-imprinted silica gel as selective adsorbent

A sensitive and selective method has been developed to determine Cr(III) and total Cr in natural water samples by ICP-AES with a Cr(III)-imprinted aminopropyl-functionalised silica gel adsorbent. The Cr(III)-imprinted and non-imprinted adsorbent were prepared by an easy one-step reaction with a surface imprinting technique. Their maximum static adsorption capacities for Cr(III) were 11.12 mg g^?1 and 3.81 mg g^?1, respectively. The relative selectivity factors (α _r) for Cr(III)/Co(II), Cr(III)/Au(III), Cr(III)/Ni(II), Cr(III)/Cu(II), Cr(III)/Zn(II), and Cr(III)/Cr(VI), were 377, 21.4, 15.4, 27.7, 26.4, and 31.9, respectively. Under the optimal conditions, Cr(III) can be absorbed quantitatively, but Cr(VI) was not retained. Total chromium was obtained after reducing Cr(VI) to Cr(III) with hydroxyammonium chloride. The detection limit (3σ) for Cr(III) was 0.11 ng mL^?1. The relative standard deviation was 1.2%. The proposed method has been validated by analysing two certified reference materials and successfully applied to the determination and speciation of chromium in natural water samples with satisfactory results.     

Adsorption of three selected flavonoids with humic fraction-modified silica gel in hexane: A mechanism study

Three selected flavonoids, commonly found in spices, red-purple fruits, and vegetables, were adsorbed on humic fraction-modified silica gel in hexane. The percentage of adsorption in hexane for all examined analytes was nearly 100% after 1 hr, as a result of the strong dipole–dipole interaction. The increasing amount of adsorbent involved in the process improved the percentage of adsorption, which in turn shortened the time needed to reach the maximum by providing more binding sites. However, adsorption was not observed in other liquid phases under the same conditions, such as acetonitrile and ethyl ether. The mechanism leading to the adsorption was explored chromatographically, as well as by fourier transform infrared spectroscopy (FTIR) and theoretical simulations.     

A silica gel orthogonal high-performance liquid chromatography method for the analyses of steviol glycosides: novel tetra-glucopyranosyl steviol

A silica gel orthogonal method using acetonitrile: water was developed for the analyses of fractions rich in very polar steviol glycosides and resolve regions of co-elution of these compounds in reversed-phase. Additionally, we also used this normal phase analytical method to scale up the purification process of steviol glycosides. Using these approaches, one novel minor tetra-glucopyranosyl diterpene glycosides together with three known compounds were purified from a commercial Stevia rebaudiana leaf extract. Compound 1 was unambiguously elucidated as 13-[(2-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]ent-kaur-16-en-19-oic acid-(6-O-β-D-glucopyranosyl-β-D-glucopyranosyl) ester (rebaudioside Y) based on high-performance liquid chromatography retention times, tandem mass spectrometry dissociation pattern and 1D and 2D NMR experiments. Known compounds were isolated in gram quantities and identified as rebaudioside D, E and M.