静态顶空GC-MS法测定三种不同性状化妆品中的甲醛

建立了三种不同性状化妆品中甲醛的快速、准确的检测方法。采用静态顶空结合GC-MS法,水剂、乳液、膏状物化妆品平衡温度分别为50、60、70℃,平衡时间为15 min。结果表明,甲醛浓度在10~200 mg/kg范围内,线性相关性良好(r=0.9996)。三个浓度系列测定结果的相对标准偏差为1.02%~1.42%,回收率为85.5%~104.2%,方法最低检出浓度为1.25 mg/kg。     

Sampling and determination of formaldehyde using solid-phase microextraction with on-fiber derivatization

Gaseous formaldehyde is sampled by derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) adsorbed onto poly (dimethylsiloxane)/divinylbenzene solid-phase microextraction fibers. The product of the reaction is an oxime which is thermally very stable and insensitive to light. The oxime can be analyzed by gas chromatography with flame ionization detection and other detectors. Loading PFBHA on the fiber is by room-temperature headspace extraction from aqueous solutions of PFBHA. The process of loading and desorption of unreacted PFBHA, and oxime formed, is both highly reproducible and reversible, with more than 200 loading, sampling, and analysis steps possible with one fiber. The standard formaldehyde gas concentrations studied ranged from 15 to 3200 ppbv with sampling times from 10 s to 12 min. Quantification can be achieved via interpolation from calibration curves of area counts as a function of formaldehyde concentration for a fixed sampling time. Sampling for 10 s yields a method detection limit of 40 ppbv and at 300 s the method detection limit is 4.6 ppbv. This is equal to or better than all other conventional grab sampling methods for gaseous formaldehyde employing sampling trains or passive sampling techniques. Alternatively, gaseous formaldehyde can be quantified with an empirically established apparent first-order rate constant (0.0030 ng/(ppbv s) at 25 °C) for the reaction between sorbed PFBHA and gaseous formaldehyde. This first-order rate constant allows for quantitative analyses without a calibration curve, only requiring detector calibration with the oxime. This new method was used for the headspace sampling of air known to contain formaldehyde, as well as other carbonyl compounds, and from various matrixes such as cosmetics and building products.     

Separation and analysis of trace degradants in a pharmaceutical formulation using on-line capillary isotachophoresis-NMR

NMR spectroscopy is widely used in the pharmaceutical industry for the structure elucidation of pharmaceutical impurities, especially when coupled to a separation method, such as HPLC. However, NMR has relatively poor sensitivity compared with other techniques such as mass spectrometry, limiting its applicability in impurity analyses. This limitation is addressed here through the on-line coupling of microcoil NMR with capillary isotachophoresis (cITP), a separation method that can concentrate dilute components by 2-3 orders of magnitude. With this approach, 1H NMR spectra can be acquired for microgram (nanomole) quantities of trace impurities in a complex sample matrix. cITP-NMR was used in this work to isolate and detect 4-aminophenol (PAP) in an acetaminophen sample spiked at the 0.1% level, with no interference from the parent compound. Analysis of an acetaminophen thermal degradation sample revealed resonances of several degradation products in addition to PAP, confirming the effectiveness of on-line cITP-NMR for trace analyses of pharmaceutical formulations. Subsequent LC-MS/MS analysis provided complementary information for the structure elucidation of the unknown degradation products, which were dimers formed during the degradation process.     

Application of solid-phase microextraction in the determination of diazepam binding to human serum albumin

In this paper, protein-drug interactions were studied by solid-phase microextraction (SPME) using diazepam binding to human serum albumin as a model system. Since drug compounds are normally polar and nonvolatile by nature, direct SPME is used in this work. The SPME extraction is an equilibrium process among the concentrations of the analyte partitioned onto the SPME fiber, free and bound drug in the solution. A calibration curve was first constructed by employing the amount of the analytes partitioned on the fiber versus the free analyte concentration in the solution in the absence of protein. In method I, the extraction was performed in the protein solution with known diazepam concentration. In method II, diazepam was first loaded onto the fiber by extracting in solution with known diazepam concentration. This fiber was subsequently transferred into the protein solution for desorption. The amount of the analyte left on the fiber was analyzed after the system reached equilibrium. The free drug concentration was then obtained from the calibration curve for both methods. The Scatchard plot was finally employed to obtain the number of binding sites and the equilibrium binding constants. Since only a very small amount of the protein solution is required (150 microL for each extraction), method II is very useful for circumstances where the protein amount is very limited. The direct measurement method proposed in this paper does not need a GC response factor, which significantly decreases the experimental error. The only measurement needed is the area count change (ratio) of the fiber injections before and after the protein was introduced into the solution. The difference between the direct measurement method for method I and method II is discussed. The result illustrated that the SPME direct measurement method provided both theoretical accuracy and simplicity in such applications.     

Analysis of the (Trimethylsilyl)propionic Acid-β(12-28) Peptide Binding Equilibrium with NMR Spectroscopy

The binding of a small molecule, (trimethylsilyl)propionic acid (TSP), to a 17-residue peptide, β(12-28), is examined using (1)H NMR spectroscopy. β(12-28) (VHHQKLVFFAEDVGSNK) is a central fragment of the 40-42-residue Alzheimer's-associated Aβ peptide. This peptide has been previously shown to form soluble aggregates in low-pH aqueous solution. The TSP resonance is broadened appreciably in solutions containing relatively high concentrations (～2 mM) of the peptide. The changes in TSP line width measured by titration of a peptide solution with TSP indicate a 1:1 binding stoichiometry. If the concentrations of both the peptide and TSP are reduced by 1 order of magnitude, the resonances of both species are sharp, suggesting that TSP binds predominately to the aggregated peptide. Nuclear Overhauser effect experiments indicate that the TSP interacts predominately with the side chains of the aliphatic peptide residues Leu(17) and Val(18). Pulsed-field gradient NMR measurements of TSP and peptide diffusion coefficients provide a more quantitative picture of the TSP-peptide binding equilibrium. The measured diffusion coefficients were used to calculate the fractions of the free and bound TSP. These results substantiate the conclusion that the stoichiometry of the TSP-peptide binding equilibrium is essentially 1:1 and further indicate anticooperative behavior in solutions containing an excess of TSP resulting in a dissociation of the peptide aggregates.     

包装印刷材料中甲醛快速检测方法的探索研究

本文开展了包装印刷材料中甲醛快速检测方法的探索研究,基于比色法,系统研究了关键因素显色剂和比色方式对显色产物的稳定性和灵敏度的影响,研究开发了甲醛检测的膜富集-紫外可见光谱法。结果表明：1)乙酰丙酮显色法具有良好的抗干扰能力和稳定性。2)直接比色法适用于包装印刷材料中甲醛定性快速筛查;紫外可见光谱法适用于包装印刷材料中甲醛的定量检测。3)膜富集-紫外可见光谱法相比较传统紫外可见光谱法灵敏度更高,适合于低含量甲醛检测。该研究有望为印刷材料中甲醛的快速检测提供参考,为产品包装的绿色、安全印刷提供技术支撑。     

The role of surfactant adsorption during ultrasonication in the dispersion of single-walled carbon nanotubes

The ionic surfactant-assisted dispersion of single-walled carbon nanotubes in aqueous solution has been studied by Raman and fluorescent spectroscopy during ultrasonic processing. During the process, an equilibrium is established between free individuals and aggregates or bundles that limits the concentration of the former that is possible. This equilibrium is a function of free sodium dodecyl sulfate concentration. At surfactant concentrations below this value, fluorescence is shifted to a lower energy due to an increase in micropolarity from water association at the nanotube surface. The mechanism of dispersion is postulated as the formation of gaps or spaces at the bundle ends in the high shear environment of the ultrasonicated solution. Surfactant adsorption and diffusion then propagate this space along the bundle length, thereby separating the individual nanotube. The former is found to be controlling, with the use of a derived kinetic model for the dispersion process and extraction of the characteristic rate of nanotube isolation.     

室温下MnOx/HZSM-5催化氧化甲醛的性能和机理分析

以HZSM-5分子筛、高锰酸钾和甲醇为原料制备MnOx/HZSM-5催化剂,室温催化氧化甲醛。采用X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)、透射电镜(TEM)、光电子能谱(XPS)等表征方法分析催化剂的形貌结构、化学成分,研究MnOx/HZSM-5的催化性能和再生性能,探讨其对甲醛的催化氧化机理。结果表明,MnOx/HZSM-5具有良好的催化活性和再生能力,动态测试1020min后MnOx/HZSM-5对甲醛的清除率仍然保持在90%,再生5次后,MnOx/HZSM-5对甲醛清除率仍然保持在91%,静态测试中甲醛清除率达到97%,甲醛转化率达到92%。对MnOx/HZSM-5氧化甲醛的机理分析后发现,甲醛首先被催化剂吸附至MnOx活性位点,之后被初步氧化为甲酸盐或碳酸盐等中间产物,最后被深度氧化为二氧化碳和水。     

Synthesis of silicon oxynitride from a polymeric precursor

Proton nuclear magnetic resonance (¹H NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy and gas chromatography (GC) have been used to study the products of ammonolysis of dichloromethylsilane in diethyl ether at 0 °C. Results indicate that the major products are trimethylcyclotrisilazane and tetramethylcyclotetrasilazane. Hydrolysis of the cyclosilazanes has also been qualitatively investigated. A simple and useful method for the identification of cyclosilazanes has been developed using the ¹H NMR technique.     

Facile syntheses and enhanced electrocatalytic activities of Pt nanocrystals with {<Emphasis Type="Italic">hkk</Emphasis>} high-index surfaces

Platinum (Pt) is an outstanding catalyst for many important industrial products. Because of its high cost and scarce reserves, it is very important to improve the performance of Pt catalysts. As the metal nanocrystals (NCs) with high-index surfaces usually show very good catalytic activity because of their high density of atomic steps and kinks, the preparation of Pt NCs with high-index facets has become a very important and hot research topic recently. In this article, we report a facile synthesis of high-yield Pt NCs with a series of {hkk} high-index facets including {211} and {411} via a solvothermal method using Pt(II) acetylacetonate as the Pt source, 1-octylamine as the solvent and capping agent, and formaldehyde as an additional surface structure regulator. Multipod Pt NCs with dominant {211} side surfaces were produced without formaldehyde, while concave Pt NCs with dominant {411} surfaces formed under the influence of formaldehyde. By analyzing the products by IR spectroscopy, we found the presence of CO on the surface of concave Pt NCs with {411} surfaces prepared from the solution containing formaldehyde. It was concluded that amine mainly stabilized the monoatomic step edges, resulting in the {211} exposed surface; with addition of formaldehyde, it decomposed into CO, leading to the formation of {411} surfaces by the additional adsorption of the CO on the {100} terraces. In addition, it was found that the as-prepared Pt NCs with high-index {211} and {411} surfaces exhibited much better catalytic activity in the electro-oxidation of ethanol than a commercial Pt/C catalyst or Pt nanocubes with low-index {100} surfaces, and the catalytic activities of Pt crystal facets decreased in the sequence {411}>{211}>{100}.      

1-Alkylcarbonyl-5-fluorouracil Prodrugs: Synthesis,Thermal and Hydrolytic Stability

Abstract

Six homologous 1 -alkylcarbonyl derivatives of 5-fluorouracil (5-FU) have been synthesized and characterized by ¹H NMR, infrared and UV spectroscopy. The derivatives were found to hydrolyze rapidly in pH 7.1 buffer at 32°C (t_1/2 = 3-5 min). Although the hydrolysis was found to be catalyzed by hydrated formaldehyde, only 5-FU was observed as a product of the hydrolysis: no 1- or 3-alkylcarbonyloxymethyl products were observed. The 1 -alkylcarbonyl derivatives were recovered intact upon heating at 145°C for 1 h, but, upon heating at 205°C for 1 h, 25% of the sample decomposed to 5-FU with the assumed loss of ketene. The 1-alkylcarbonyl derivatives were stable when stored in a desiccator but decomposed to carboxylic acid and 5-FU upon exposure to atmospheric moisture.     

Estimation of atmospheric lifetimes of hydrofluorocarbons, hydrofluoroethers, and olefins by chlorine photolysis using gas-phase NMR spectroscopy

An empirical correlation has been derived between accepted atmospheric lifetimes of a set of hydrofluorocarbons and hydrofluoroethers and relative rates of reaction with photolyzed chlorine in excess at ambient temperature. These kinetic systems were studied by nuclear magnetic resonance (NMR) spectroscopy in the gas phase, marking the first application of NMR spectroscopy to this field. The square of the Pearson coefficient R for the linear correlation between observed reaction rates and accepted atmospheric lifetimes was 0.87 for compounds of lifetime less than 20 years. The method was extended to the study of ethene and propene; the rate of reaction of propene was found to be 1.25 times that of ethene at 23 degrees C. The chief advantage of this method is its simplicity and reliance only on common tools and techniques of an industrial chemical laboratory.     

Between-person comparison of metabolite fitting for NMR-based quantitative metabolomics

Nuclear magnetic resonance (NMR) spectroscopy is widely used as an analytical platform for metabolomics. Many studies make use of 1D spectra, which have the advantages of relative simplicity and rapid acquisition times. The spectral data can then be analyzed either with a chemometric workflow or by an initial deconvolution or fitting step to generate a list of identified metabolites and associated sample concentrations. Various software tools exist to simplify the fitting process, but at least for 1D spectra, this still requires a degree of skilled operator input. It is of critical importance that we know how much person-to-person variability affects the results, in order to be able to judge between different studies. Here we tested a commercially available software package (Chenomx' NMR Suite) for fitting metabolites to a set of NMR spectra of yeast extracts and compared the output of five different people for both metabolite identification and quantitation. An initial comparison showed good agreement for a restricted set of common metabolites with characteristic well-resolved resonances but wide divergence in the overall identities and number of compounds fitted; refitting according to an agreed set of metabolites and spectral processing approach increased the total number of metabolites fitted but did not dramatically increase the quality of the metabolites that could be fitted without prior knowledge about peak identity. Hence, robust peak assignments are required in advance of manual deconvolution, when the widest range of metabolites is desired. However, very low concentration metabolites still had high coefficients of variation even with shared information on peak assignment. Overall, the effect of the person was less than the experimental group (in this case, sampling method) for almost all of the metabolites.     

Concentration Measurement by Proton NMR Using the ERETIC Method

The ERETIC method (Electronic REference To access In vivo Concentrations) provides a reference signal, synthesized by an electronic device, which can be used for the determination of absolute concentrations. The results presented here demonstrate the accuracy and precision of the method in the case of (1)H high resolution NMR. Five tubes were filled with D(2)O solutions of trimethylamine hydrochloride (TMA) 3.84 mM and sodium lactate at concentrations ranging from 5.25 to 54.11 mM. Results obtained with the ERETIC method were compared to those obtained by using TMA as an internal reference. The standard deviations were the same for the two methods and always lower than 1% of the mean. The accuracy (difference between true value and measured value) was slightly better for the ERETIC method than for the internal reference. No significant variation was observed when the experiments were performed over 56 h. Measurements were repeated once a month during three months. As the values obtained showed a standard deviation of only 3%, we can conclude that the ERETIC method has a good stability and only requires monthly calibration. Furthermore, it must be noted that nothing is added to the sample and that the reference signal frequency can be freely chosen to fall within a transparent region of the spectrum.     

Analysis of nitro musk compounds and their amino metabolites in liquid sewage sludges using NMR and mass spectrometry

A method using HRGC ion trap MS/MS for measuring simultaneously amino metabolites and the parent compounds, the nitro musks, an important group of organic fragrance components found in sewage sludges, was developed. The monoamino metabolites were synthesized and characterized by 1H/13C NMR and mass spectroscopy. Among the nitro musks, musk ketone was the major compound, found at an average concentration of 5 microg/kg of dry mass (dm) whereas musk xylene was detected in only one sample (30 microg/kg dm). Three amino metabolites were identified, namely, 1-tert-butyl-3,5-dimethyl-4-amino-2,6-dinitrobenzene, 1,1,3,3,5-pentamethyl-4-nitro-6-aminoindane, and 4-acetyl-1-tert-butyl-3,5-dimethyl-2-nitro-6-aminobenzene, the corresponding reduction products of the nitro musks xylene, moskene, and ketone. These metabolites were present in partly higher concentrations in the sludges than the corresponding nitro musk compounds. Musk xylene and musk moskene were mainly found as their monoamino metabolites, underlining the importance of anaerobic reduction processes in the sewage treatment plant.     

Interactions of bupivacaine with a molecularly imprinted polymer in a monolithic format studied by NMR

A trimethylolpropane trimethacrylate-based monolith of dimensions carefully chosen to fit exactly in a standard 4-mm solid-state CP/MAS NMR rotor was photopolymerized and subsequently molecularly imprinted with bupivacaine using a grafting protocol with methacrylic acid and ethylene dimethacrylate as monomers. As no crushing or grinding of the monolith was necessary, additional unspecific surface area was not created. This procedure ascertains that differences observed between imprinted and nonimprinted polymers are due only to graft imprinted surfaces and give therefore better results in NMR spectroscopy due to less unspecific interactions between analyte and monolith. This improves the comparability to chromatographic evaluations where uncrushed monolithic columns are also used. To track interactions between analyte and stationary phase, the saturation transfer difference (STD) technique was applied on the polymer in the suspended state using the same solvent as in the chromatographic evaluation. This relatively new NMR method has to our knowledge not been used on chromatographic materials before. By using STD NMR on pristine monoliths, it was possible to measure large differences between the imprinted or nonimprinted polymers and the analyte indicating significant differences in the interaction mechanisms. These could be directly correlated with retention differences observed in chromatographic evaluations.     

A simple and efficient method to prepare graphene by reduction of graphite oxide with sodium hydrosulfite

Inspired by an ancient reducing method used in textile production, sodium hydrosulfite was used to reduce graphite oxide as an efficient reducing agent in our work. The reduced materials were characterized by x-ray photoelectron spectroscopy, thermogravimetric analysis, wide-angle x-ray scattering, Raman spectroscopy, solid state (13)C NMR spectroscopy and electrical conductivity measurements, respectively. The results showed that graphite oxide can be reduced with sodium hydrosulfite in a few minutes, with a degree of reduction comparable to those achieved with hydrazine. It provides an efficient method to reduce graphite oxide and could be used as a method to prepare novel composites.     

Preparation of covalently functionalized graphene using residual oxygen-containing functional groups

When fabricated by thermal exfoliation, graphene can be covalently functionalized more easily by applying a direct ring-opening reaction between the residual epoxide functional groups on the graphene and the amine-bearing molecules. Investigation by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) all confirm that these molecules were covalently grafted to the surface of graphene. The resulting dispersion in an organic solvent demonstrated a long-term homogeneous stability of the products. Furthermore, comparison with traditional free radical functionalization shows the extent of the defects characterized by TEM and Raman spectroscopy and reveals that direct functionalization enables graphene to be covalently functionalized on the surface without causing any further damage to the surface structure. Thermogravmetric analysis (TGA) shows that the nondestroyed graphene structure provides greater thermal stability not only for the grafted molecules but also, more importantly, for the graphene itself, compared to the free-radical grafting method.     

Analysis of extracellular matrix production in artificial cartilage constructs by histology, immunocytochemistry, mass spectrometry, and NMR spectroscopy

Artificial cartilage constructs based on primary porcine chondrocytes embedded in agarose gel were cultivated for six weeks under static, free swelling conditions. Standard biochemical assays, immunocytochemical staining methods, MALDI-TOF mass spectrometry, and non-invasive 13C solid-state NMR spectroscopy were used to assess cell proliferation, chondrocyte metabolism, extracellular matrix composition, matrix production, and the nanoarchitecture of the macromolecules in the constructs. In particular the production of sulphated glycosaminoglycans such as chondroitin sulphate was investigated quantitatively. Standard methods such as histological and immunocytochemical tools as well as spectrophotometric assays indicated the production of extracellular matrix in the artificial cartilage constructs. In addition, MALDI-TOF mass spectrometric data allowed to clearly identify the production of chondroitin sulphate in the tissue engineered cartilage. While all these methods require invasive sample treatment, 13C NMR spectroscopy allows to study the composition of the artificial cartilage constructs without previous manipulations. Though lower in sensitivity, 13C NMR spectra clearly showed the presence of chondroitin sulphate in the constructs. To increase the sensitivity of the NMR method, a culture medium that contained uniformly 13C labelled glucose but no sodium pyruvate or L-glutamine was used. Thus, further insights into the chondrocyte metabolism ex vivo are possible. Therefore, MALDI-TOF mass spectrometry and 13C solid-state NMR are useful experimental techniques that can assist the quantitative evaluation and quality control of artificially engineered tissues.     

Chemical shift correlations from hyperpolarized NMR by off-resonance decoupling

Nuclear magnetic resonance, through observation of chemical shift, allows the separate identification of each atom in a molecule. Thus, NMR spectra impart an often unrivaled wealth of information on molecular structure. A particular advantage of NMR spectroscopy is the ability to record multidimensional spectra, which provide correlations between atoms. When compared to other techniques, such as optical spectroscopy, the acquisition of NMR spectra is however an insensitive process, requiring samples of high concentration and long acquisition times. Recently, it has been demonstrated that dynamic nuclear polarization, a hyperpolarization technique, can increase the NMR signal by several orders of magnitude. Here, we present a robust method that allows recording two-dimensional chemical shift correlations from such hyperpolarized molecules. The method makes use of an apparent scaling of the scalar coupling observed on one type of atom, when an off-resonance decoupling field is applied to another type of atom. Thus, two-dimensional chemical shift correlations can be read directly from a small number of scans acquired using a hyperpolarized sample. Due to the ease of implementing this technique on commercial hyperpolarization and NMR equipment, it appears ideally suited for routine application, for example, to obtain carbon-proton chemical shift correlations in organic molecules.