Locating Gases in Porous Materials: Cryogenic Loading of Fuel‐Related Gases Into a Sc‐based Metal–Organic Framework under Extreme Pressures

An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single‐crystal of a porous metal–organic framework, is demonstrated to have considerable advantages over other gas‐loading methods when investigating host–guest interactions. Specifically, loading the metal–organic framework Sc₂BDC₃ with liquefied CO₂ at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH₄ at 3–25 kbar demonstrates hyperfilling of the Sc₂BDC₃ and two high‐pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.     

Understanding guest and pressure‐induced porosity through structural transition in flexible interpenetrated MOF by Raman spectroscopy

Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)_0.5 · DMF(H₂O)_0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO₂ and its librational mode at 149 cm⁻¹ suggests cooperative adsorption of CO₂ in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd.     

High P–T Raman study of transitions in relaxor multiferroic Pb(Fe0.5Nb0.5)O3

The vibrational and structural properties of Pb(Fe_0.5Nb_0.5)O₃ have been investigated using Raman spectroscopy up to 40 GPa at 300 K and from 300 to 415 K at selected pressures. The measurements reveal three phase transitions, at 5.5, 8.7, and 24 GPa at room temperature. The temperature dependences of the spectra indicate transitions at 1.5 GPa, at 335 and 365 K. The results are consistent with the appearance of an intermediate tetragonal P4mm phase between the ferroelectric R3m and paraelectric Pm‐3m phases. A P–T phase diagram is proposed that allows further insight into the magnetoelectric coupling present in this material. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopic detection for liquid and solid targets using a spatial heterodyne spectrometer

Spatial heterodyne Raman spectroscopy (SHRS) is a new type of effective method for the analysis of structure and composition of liquid and solid targets with the characteristics of no moving parts, high spectral resolution, high optical throughput and large field of view. The technique is very suitable for detecting the targets from long distances or under the conditions with ambient light, which is essential for the exploration of planetary surface. In order to have a better understanding of the ability of SHRS for the detection of liquid and solid targets, a breadboard was designed, built and calibrated. Signal to noise was estimated at different integration time or laser power for carbon tetrachloride. Pure materials or materials contained in bottles were both tested. The mixture of organic liquids or inorganic solids were tested. In order to test the detection ability for natural targets, some composition‐unknown rocks and pebbles were tested. The results have shown that SHRS can meet the requirements for the detection of weak Raman signal scattered from artificial or natural targets. Standoff detection of sulfur from 5‐m or 10‐m distance without using any telescope or collimation optics was also tried to test the high optical throughput of SHRS. The potential feasibility of standoff detection has been proved. Copyright © 2015 John Wiley & Sons, Ltd.     

Diversity‐Oriented Approach for Chemical Biology

Synthetic molecules that modulate and probe biological events are critical tools in chemical biology. Utilizing combinatorial and diversity‐oriented synthetic strategies, access to large numbers of small molecules is becoming more and more feasible, and research groups in this field can take advantage of the power of chemical diversity. Since the majority of early studies were focused on the discovery of compounds that perturb protein functions, diversity‐based approaches are often considered as therapeutic lead discovery tactics. However, the diversity‐oriented approach can also be applied to advance distinct aims, such as target protein identification, or the development of imaging probes and sensors. This review provides a personal perspective of the chemical‐diversity‐based approach and how this principle can be adapted to various chemical biology studies.     

Systematic chemical profiling of a multicomponent Chinese herbal formula Huo Luo Xiao Ling Dan by ultra high performance liquid chromatography coupled with electrospray ionization quadrupoletime‐of‐flight mass spectrometry

Huo Luo Xiao Ling Dan, a Chinese herbal formula consisting of 11 different herbs, has been used in folk medicine for the treatment of arthritis and other chronic inflammatory diseases. However, the chemical compositions of Huo Luo Xiao Ling Dan are not completely characterized. In the present study, an ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time‐of‐flight mass spectrometry method in positive and negative ion modes was employed to identify biochemical constitutes in Huo Luo Xiao Ling Dan. As a result, a total of 76 compounds including alkaloids, monoterpene glycosides, iridoids, phenolic acids, and tanshinones, coumarins, lactones, flavones, and their glycosides, triterpenes, and triterpene saponins were characterized by comparing the retention time and mass spectrometry data with reference standards within 5 ppm error or by reference to the reference literature. These results would provide the basis for a further in vivo study of Huo Luo Xiao Ling Dan and information for potential new drug candidates for treating arthritis and other chronic inflammatory diseases.     

Analysis of corrosion scales formed on steel at high temperatures in hydrocarbons containing model naphthenic acids and sulfur compounds

Corrosive naphthenic acids and sulfur compounds in crude oils present a major challenge for refineries from a corrosion perspective. Although it is accepted that some sulfur compounds may form protective FeS scales on the metal surface and deter corrosion, attempting to correlate the characteristics of FeS scale with its protective properties has not been successful. Given the complex chemical compositions of real crudes, model sulfur compound and model naphthenic acids were used to mimic the corrosion by crude fractions in the present study. The iron sulfide scale formed by the model sulfur/acid compounds was challenged by naphthenic acids under high‐velocity conditions to examine its protectiveness against corrosion. Moreover, the scale was analyzed with transmission electron microscope/energy dispersive X‐ray spectroscopy technique, and a layer of iron oxide formed on the 5Cr steel was found when naphthenic acids were present in the solution. The iron oxide layer appeared to be important for maintaining protection against naphthenic acid corrosion, and further analysis revealed that it was composed of magnetite. Copyright © 2015 John Wiley & Sons, Ltd.     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

Profiling monoterpenol glycoconjugation in Vitis vinifera L. cv. Muscat of Alexandria using a novel putative compound database approach,high resolution mass spectrometry and collision induced dissociation fragmentation analysis

In this work we present a novel approach for the identification of plant metabolites using ultrahigh performance liquid chromatography coupled to accurate mass time-of-flight mass spectrometry. The workflow involves developing an in-house compound database consisting of exact masses of previously identified as well as putative compounds. The database is used to screen accurate mass spectrometry (MS) data to identify possible compound matches. Subsequent tandem MS data is acquired for possible matches and used for structural elucidation. The methodology is applied to profile monoterpene glycosides in Vitis vinifera cv. Muscat of Alexandria grape berries over three developmental stages. Monoterpenes are a subclass of terpenes, the largest class of plant secondary metabolites, and are found in two major forms in the plant, “bound” to one or more sugar moieties or “free” of said sugar moieties. In the free form, monoterpenes are noted for their fragrance and play important roles in plant defense and as attractants for pollinators. However, glycoconjugation renders these compounds odorless, and it is this form that the plant uses for monoterpene storage. In order to gain insight into monoterpene biochemistry and their fate in the plant an analysis of intact glycosides is essential. Eighteen monoterpene glycosides were identified including a monoterpene trisaccharide glycoside, which is tentatively identified here for this first time in any plant. Additionally, while previous studies have identified monoterpene malonylated glucosides in other grapevine tissue, we tentatively identify them for the first time in grape berries. This analytical approach can be readily applied to other plants and the workflow approach can also be used for other classes of compounds. This approach, in general, provides researchers with data to support the identification of putative compounds, which is especially useful when no standard is available.     

加速溶剂萃取-凝胶色谱净化高效液相色谱法测定动物源性食品中的胆固醇

采用加速溶剂萃取-凝胶色谱净化建立了动物源性食品中胆固醇检测的高效液相色谱方法。结果表明,胆固醇浓度在1.0~40.0mg/L范围内线性关系良好,加标回收率为89.1%~99.8%,相对标准偏差为3.1%~7.8%。该方法准确、灵敏度高,适用于富含脂类的动物源性食品中胆固醇的检测。