Electrospray tandem mass spectrometric analysis of zeaxanthin and its oxidation products

Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample.     

Infrared Observation of the Effects of Aqueous Oxidizing Agents on the Functional Groups on Carbon Surfaces

FTIR photothermal beam deflection spectroscopy (PBDS) was used to record infrared spectra of medium-temperature carbons before and after they had been subjected to treatments with aqueous HNO₃ or H₂O₂ solution. Changes in the functional groups present on the carbon surfaces can be clearly observed.     

Nanoscale imaging of oxidized copper foil covered with chemical vapor deposition-grown graphene layers

Characterization of the geometrical and structural characteristics of oxidized Cu area in high resolution is crucial for tracking the change in morphology, exploring interactions between graphene layers and Cu substrates and revealing the mechanism for the orientation-dependent oxidation of Cu. Here, we reported experimental results on nanoscale imaging of natural oxidation of the polycrystalline Cu substrate coated by partial-coverage chemical vapor deposition (CVD)-grown graphene stored in dryer under ambient conditions for up to 10 months. Scanning electron microscope (SEM), together with atomic force microscope (AFM), Raman, and X-ray photoelectron spectroscopy (XPS), was used for systematically studying the morphological and compositional changes at nanoscale during oxidation. The appearance of oxidized Cu substrates could be unambiguously distinguished from the unoxidized regions based on their distinctly different morphologies in SEM images, and the underlying mechanism was discussed in detail. By analyzing a millimeter-seized polycrystalline Cu substrate, we found that the oxidation of polycrystalline Cu substrate depends sensitively on both orientation of graphene layers and Cu substrates. Furthermore, the time-dependent oxidation evolution of Cu substrate was also established, and the oxidation rate was readily determined. The findings reported here will have important implications for developing protection coatings for Cu.     

Highly oxidized graphene with enhanced fluorescence and its direct fluorescence visualization

We prepared hyper-oxidized graphene (HOG) as a form of graphene derivative by additional oxidation of graphene oxide (GO) sheets. HOG, which formed more functional groups and isolated conjugated clusters on the sheets, accordingly showed high solubility in water and alcohols, high transmittance and film transparence, longer fluorescence decay constant time, and enhanced fluorescence in states of solution and solid. By contrast, GO has much weaker fluorescence in solution and its fluorescence is totally quenched in solid. The influences of concentration, metallic ions, and pH on HOG fluorescence in aqueous solution were also investigated in detail. Due to HOG’s strong fluorescence, direct visualization was realized on substrates and in solution. In addition, direct 3D fluorescence visualizations of HOG phase in polymer composites were achieved. These results show the great potential of HOG in a broad range of applications, from biological labeling, probes, and drug carriers to high-performance composites and nanomanipulation.     

三酰甘油氧化聚合物的制备型快速柱层析-体积排阻色谱测定法

建立了一种简便、灵敏、无需内标的检测油脂中三酰甘油氧化聚合物(TGP)的分析方法。以制备型快速层析柱(PFC)(flash硅胶柱,20 g,40～60μm,6 nm)分离1 g油脂样品中极性组分(PC),经高效体积排阻色谱(HPSEC)(GPC柱,Ф7.8 mm×300 mm,粒径5μm,孔径10 nm)将PC细分为氧化三酰甘油寡聚物(TGO)、氧化三酰甘油二聚物(TGD)、氧化三酰甘油单体(ox-TGM)、二酰甘油(DG)、游离脂肪酸(FFA)。结合重量法测定油脂中PC、面积归一法测定PC中TGP,可准确定量油脂中的TGP含量。结果表明,TGO、TGD分别在28～1 800、11～2 800 mg/L范围内线性关系良好,相关系数(r2)分别为0.998 2、0.998 7,TGO及TGD的检出限(LOD)分别为28、11 mg/L,定量下限(LOQ)分别为113、44 mg/L;相当于油脂中TGP的LOD为0.01%。PFC-HPSEC法检测油脂TGP的相对标准偏差(RSD)均小于10%。PFC对3个PC加标水平(2.27%、8.47%、30.94%)的平均回收率为95%～98%,相对标准偏差(RSD)均低于4%。PFC-HPSEC方法与经典的硅胶柱-HPSEC方法定量油脂TGP的结果吻合度高,相对误差为0～8.9%。该方法能够在2 h内实现各种油脂中TGP含量的定量检测,包括使用过的废弃油脂与未使用的食用油脂,尤其适用于低含量TGP的初榨油和精炼油脂。     

基于微拉曼光谱技术的氧化介孔硅热导率研究

利用基于有效介质理论的介孔硅传热机理,提出一个用于分析氧化介孔硅热导率的理论模型,对影响氧化介孔硅有效热导率的因素进行了理论分析,得出用于计算氧化介孔硅有效热导率的计算公式. 采用双槽电化学腐蚀法制备介孔硅,利用微拉曼光谱技术研究了氧化介孔硅热导率随所制备介孔硅孔隙率的变化规律,比较了经不同温度处理的氧化介孔硅的导热性能差异. 孔隙率为60%,73.4%和78.8%的所制备介孔硅经300℃氧化处理后,其热导率值为8.625W/(m·K),3.846W/(m·K)和1.817W/(m·K);孔隙率为73.4 关键词： 理论模型 氧化介孔硅 微拉曼光谱 有效热导率     

New way to crosslink chitosan in aqueous solution

In this paper, the reaction between o-phthaldialdehyde and free NH₂ of chitosan is investigated; at a very low molar ratio between the two reactants ([dialdehyde]/[NH₂] ∼ 2.5 × 10⁻⁴), an increase of the apparent molecular weight is obtained as evidenced from the rheological behaviour. Then, three non-ionic polysaccharides (galactomannan, maltodextrins, methylcellulose) are oxidised to 10% with sodium metaperiodate to obtain polyaldehydic derivatives able to react with free NH₂ of chitosan after their direct dissolution into chitosan solution at a molar ratio [monosaccharide units]/[NH₂ ] ∼ 0.6. Stable swollen porous gels are obtained with an excellent yield in the presence of a reducing agent (NaBH₃CN) chosen to reduce the Schiff base; nearly no influence of the structure of the initial non-ionic polysaccharides is observed when the polysaccharides are oxidized in the same conditions. Different parameters for the reaction of oxidized methylcellulose (Me-ox) with chitosan are tested: influence of the degree of oxidation (up to 50%), and of the oxidised methylcellulose concentration. The larger is the degree of oxidation or the Me-ox concentration, the lower is the degree of swelling (i.e., the larger is the degree of chitosan cross-linkage). The swollen gels formed immediately after reaction are isolated and re-swell in aqueous acidic conditions, a good solvent of initial chitosan, to purify the gel and determine the yield of the reaction and the swelling degree. At the end, preliminary tests of biodegradability of these new gels are performed using specific enzymatic degradation with lysozyme and cellulase in the case of chitosan/Me-ox cogels chosen as example.     

Open tubular capillary electrochromatography: A useful microreactor for collagen I glycation and interaction studies with low-density lipoprotein particles

Diabetes, a multifunctional disease and a major cause of morbidity and mortality in the industrialized countries, strongly associates with the development and progression of atherosclerosis. One of the consequences of high level of glucose in the blood circulation is glycation of long-lived proteins, such as collagen I, the most abundant component of the extracellular matrix (ECM) in the arterial wall. Glycation is a long-lasting process that involves the reaction between a carbonyl group of the sugar and an amino group of the protein, usually a lysine residue. This reaction generates an Amadori product that may evolve in advanced glycation end products (AGEs). AGEs, as reactive molecules, can provoke cross-linking of collagen I fibrils. Since binding of low-density lipoproteins (LDLs) to the ECM of the inner layer of the arterial wall, the intima, has been implicated to be involved in the onset of the development of an atherosclerotic plaque, collagen modifications, which can affect the affinity of native and oxidized LDL for collagen I, can promote the entrapment of LDLs in the intima and accelerate the progression of atherosclerosis.In this study, open tubular capillary electrochromatography is proposed as a new microreactor to study in situ glycation of collagen I. The kinetics of glycation was first investigated in a fused silica collagen I-coated capillary. Dimethyl sulphoxide, injected as an electroosmotic flow marker, gave information about the charge of coating. Native and oxidized LDL, and selected peptide fragments from apolipoprotein B-100, the protein covering LDL particles, were injected as marker compounds to clarify the interactions between LDLs and the glycated collagen I coating. The method proposed is simple and inexpensive, since only small amounts of collagen and LDL are required. Atomic force microscopy images complemented our studies, highlighting the difference between unmodified and glycated collagen I surfaces.     

过渡金属卤化物改性非碳基吸附剂脱汞研究

以6种大比表面积非碳基成分为载体,经过渡金属卤化物改性处理后制成汞吸附剂,并对其不同烟气气氛和温度下的汞吸附性能及汞氧化率进行了研究。CuCl_2改性氧化铝在各种烟气条件下均表现出较好的汞吸附性能。FeCl_3改性沸石的汞脱除率相对略低,但它制作成本较低。这两种非碳基吸附剂在未来有较好的应用前景。改性吸附剂的最适宜反应温度100～200℃。     

Threshold Al KLL Auger spectra of oxidized aluminium foils

Threshold Al KLL Auger electron spectroscopy and K‐edge x‐ray absorption fine structure spectroscopy have been used to examine technical purity (99.5%) aluminium foil before and after chemical treatment that altered the thickness and degree of hydroxylation of the oxidized layer. Comprehensive surface chemical characterization was effected by means of monochromatized Al Kα‐excited photoelectron spectroscopy. Threshold Al KL_{2, 3}L_{2, 3} spectra were obtained for three of the foils investigated and these spectra were in broad agreement with those observed previously for pure Al foil. The relative intensities of the spectral components for two of the foils were clearly consistent with the previously proposed assignment of the resonantly enhanced Auger component, situated between those arising from the metal and Al(III) oxide, to a thin interfacial layer. The threshold Auger spectra from the aluminium foil bearing the thickest and most hydroxylated oxidized layer were not obviously consistent with the interfacial layer model but O K‐edge spectra revealed that this surface layer was fundamentally different from the others and could have had a greater interfacial surface area. Copyright © 2003 John Wiley & Sons, Ltd.