The Effect of Pristine and Hydroxylated Oxide Surfaces on the Guaiacol HDO Process: A DFT Study

The acid-base character of oxide supports is crucial for catalytic reactions. In this work, the acid-base properties of five oxide surfaces common in heterogeneous catalysis were investigated and related to their interaction with monolignol compounds derived from lignin. We have used density functional theory simulations also to understand the role of the surfaces’ hydroxylation state. The results show that moderate hydroxyl coverage on the amphoteric γ-Al₂O₃ (110) slightly strengthens the oxy-compounds’ adsorption due to an increase in Lewis acidity. Similarly, low hydroxyl coverage on the reducible TiO₂ (101) enlarges its adsorption capacity by up to 42 % compared with its clean surface. The higher affinity is attributed to the more favourable interaction between the surface-OH groups and the aromatic rings. Overall, the results indicate that hydroxyl coverage enhances the amphoteric and reducible adsorption capacity towards aromatic species.     

Determination of hydroxylated polychlorinated biphenyls by ion trap gas chromatography–tandem mass spectrometry

Hydroxylated polychlorinated biphenyls also known as biphenylols, are suspected estrogen mimics found in the environment. Various derivatization schemes were evaluated and a gas chromatography–ion trap mass spectrometry method was developed for the trifluoroacetyl derivative using MS–MS techniques for the analysis of eleven biphenylols. A time-segmented chromatographic method was developed using the respective MS–MS parameters to analyze all the eleven biphenylols in a single chromatographic run. Isomers were differentiated based on the MS–MS data of the trofluoroacetyl-biphenylol derivatives. The method was applied to detect 40 pg on-column of these compounds in a spiked egg sample which simulates a real world sample.     

Linear polyurethanes made from naturally occurring tartaric acid

Naturally occurring tartaric acid was used as raw material for the synthesis of novel linear polyurethanes (PURs) bearing two carboxylate side‐groups in the repeating unit. Aliphatic and aromatic PURs were obtained by reaction in solution of alkyl and benzyl tartrates with hexamethylene diisocyanate and 4,4′‐methylene‐bis(phenyl isocyanate), respectively. All the novel PURs were thermally stable and optically active. The aliphatic carboxylate‐containing PURs had M_w in the 40–70 kDa range, with PD between 2.1 and 2.5; all were semicrystalline polymers with melting temperatures between 100 and 150 °C and T_g in the 50–80 °C range. The aromatic PURs were amorphous materials with molecular weights between 18 kDa and 25 kDa and T_g above 130 °C. Hydrogenolysis of the PUR made from hexamethylene diisocyanate and benzyl tartrate yielded PURs containing up to 40% of free carboxylic side‐groups. The tartrate‐derived PURs displayed enhanced sensitivity to hydrolysis compared with their unsubstituted 2,6‐PUR homologs. The PURs bearing free carboxylic groups were unique in being degraded by water upon incubation under physiological conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2391–2407, 2009     

Photochemical behaviour of propranolol in environmental waters: the hydroxylated photoproducts

The UV irradiation of propranolol, one of the beta-blockers currently used in cardiac medicine, was studied. During irradiation, the samples were analysed by LC/MS/MS, using a Waters Symmetry C₁₈ (3.5?µm 150?×?2.1?mm) column. The main photoproducts were identified from mono-, di- and tri-hydroxylation of the propranolol naphthalenic skeleton. Hydroxyl group positions were predicted by means of theoretical calculations. Partial charge calculations of the propranolol atoms predicted the formation of four mono-hydroxylated compounds, two of them being the most probable. From these two compounds, three di-hydroxylated compounds were predicted. Then the calculations from the two most probable di-hydroxylated compounds were used to propose three tri-hydroxylated propranolol compounds. It was found that the same hydroxylated photoproducts are formed in pure water and in treatment plant waste water.     

Identification of metabolites of gardenin A in rats by combination of high‐performance liquid chromatography with linear ion trap–Orbitrap mass spectrometer based on multiple data processing techniques

Gardenin A is one of the less abundant hydroxylated polymethoxyflavonoids (OH‐PMFs) in nature, and has many potential significant health benefits. In the present study, an efficient strategy was established using high‐performance liquid chromatography coupled with linear ion trap–Orbitrap mass spectrometer to profile the in vivo metabolic fate of gardenin A in rat plasma and various tissues. First, an online LC‐MSⁿ data acquisition method was developed to trace all the probable metabolites. Second, a combination of offline data processing methods including extracted ion chromatography and multiple mass defect filters was employed to screen the common and uncommon metabolites from the background noise and endogenous components. Finally, structures of the metabolites were elucidated based on an accurate mass measurement, the diagnostic product ions of PMFs, and relevant drug biotransformation knowledge. Based on the proposed strategy, a total of 26 metabolites were observed and characterized. The results indicate that some biotransformations, such as methylation, demethoxylation, demethylation, glucuronide conjugation, sulfate conjugation and their composite reactions, have been discovered for OH‐PMFs. Moreover, some diagnostic biotransformation pathways are summarized. Overall, this study gives us a first insight into the in vivo metabolism of gardenin A. The study also provides a practical strategy for rapidly screening and identifying metabolites, which can be widely applied for the other biotransformations. Copyright © 2014 John Wiley & Sons, Ltd.     

A QSRR Study on the Chromatographic Retention Indices of Hydroxylated Polychlorinated Biphenyls

Hydroxylated Polychlorinated Biphenyls (HO-PCBs) are the metabolite of polychlorinated biphenyls and have drawn much attention because they have hazard on human health and ecosystems. Molecular connectivity index calculation has been performed for 19 HO-PCB compounds. A number of statistically based parameters have been extracted. Linear relationship between chromatographic retention index (RI) and the molecular connectivity index of 15 compounds in the training set has been established by multiple linear regression method. The other 4 HO-PCBs are used as the external test set. The result shows that the parameters can be well used to express the quantitative structure-retention relationship (QSRR) of HO-PCBs. Good stability and predictive ability have been demonstrated by leave-one-out cross-validation and the external test set.     

Density function studies on the PtCl2‐catalyzed asymmetric cycloisomerization reaction of hydroxylated enynes

The PtCl₂‐catalyzed asymmetric cycloisomerization reaction of hydroxylated enynes was studied using density functional theory (DFT). All structures have been optimized completely at the B3LYP/6‐311G(d,p) level. As shown, the cycloisomerization reaction is exothermic. The cycloisomerization reaction mainly undergoes the formation of catalyst‐hydroxylated enzyme coordination, the asymmetric cyclopropyl platinum carbene, catalyst–cyclopropyl enol coordination, and catalyst–cyclopropyl ketone coordination. The chirality‐limiting step for the asymmetric cycloisomerization reaction is the formation of the asymmetric cyclopropyl platinum carbene, and the rate‐determining step for this reaction is the formation of the catalyst–cyclopropyl ketone coordination. The dominant products predicted theoretically are (R,S) ‐syn_5a, in agreement with the experiment. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Solid-phase Synthesis of a Novel Kind of Hydroxylated Heterocyclic Ketene Aminals

An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.     

三维多孔碳纳米管-还原氧化石墨烯复合气凝胶应用于高性能对称超级电容器

以羟基化的碳纳米管(CNT-OH)和自制的氧化石墨烯(GO)为原料,通过氧化还原自组装的水热合成策略制备了碳纳米管-还原氧化石墨烯(CNTs-rGO)三维气凝胶,并探究了水热温度对三维气凝胶的影响,利用扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱(Raman)和X射线光电子能谱(XPS)对材料的结构、形貌进行了表征,并对其进行电化学性能测试。其中,在140℃下合成的气凝胶CNTs-rGO展示了最佳的电化学性能,在1 A·g^-1电流密度下的比电容高达294.65 F·g^-1,循环伏安曲线在50 mV·s^-1扫速下的形状仍然近似于矩形,展示了良好的可逆性。将其作为正极和负极材料组装的对称超级电容器在功率密度为249.8 W·kg^-1时的最大能量密度为3.744 Wh·kg^-1,在1 A·g^-1下循环10 000次后,其电容保持率和库仑效率均约为100%。优异的电化学性能主要归因于CNTs-rGO复合材料疏松多孔的三维立体结构,这保证了离子的快速运输,同时CNTs和rGO的交联结构提高了电导率,充分发挥了CNTs和rGO的化学和电学性能。     

One-Step Synthesis of Janus Fluorographene Derivatives

Fluorographene, a two-dimensional derivative of graphene, is an excellent starting material for the synthesis of graphene derivatives. In this work, a one-step, substrate-free method for the asymmetric functionalization of fluorographene layers with hydroxyl groups by a facile nucleophilic substitution reaction is reported. Such a chemical modification occurs in a biphasic aqueous–organic system under mild conditions, leading to Janus graphene nanosheets functionalized by hydroxyl groups on one side and retaining fluorine atoms on the other. The reported experimental route paves the way for two-dimensional bifacial graphene templates, thus broadening the application potential of graphene materials.