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

This is the part II 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 II starts with briefly introducing the main quantitation methods and then addresses the performance related to quantification: linearity of signal, sensitivity, precision, trueness, accuracy, stability and measurement uncertainty. The last section is devoted to practical considerations in validation. With every performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to handle it, specifically in the case of LC–MS methods.     

The effect of molecular weight on the separation of semiconducting single‐walled carbon nanotubes using poly(2,7‐carbazole)s

The use of selective interactions between conjugated polymers and single‐walled carbon nanotubes has emerged as a promising method for the separation of nanotubes by electronic type. Although much attention has been devoted to investigating polyfluorenes and their ability to disperse semiconducting carbon nanotubes under specific conditions, other polymer families, such as poly(2,7‐carbazole)s, have been relatively overlooked. Poly(2,7‐carbazole)s have been shown to also preferentially interact with semiconducting carbon nanotubes, however a detailed investigation of polymer parameters, such as molecular weight, has not been performed. We have prepared seven different molecular weights of a poly(2,7‐carbazole), from short chain oligomers to high molecular weight polymers, and have investigated their effectiveness at dispersing semiconducting single‐walled carbon nanotubes. Although all polymer chain lengths were able to efficiently exfoliate carbon nanotube bundles using a mild dispersion protocol, only polymers above a certain threshold molecular weight (M_n ～ 27 kDa) were found to exhibit complete selectivity for semiconducting nanotubes, with no observable signals from metallic species. Additionally, we found the quality of separation to be strongly dependent on the ratio of polymer to carbon nanotube. Contrary to previous reports, we have found that an excess of poly(2,7‐carbazole) leads to incomplete removal of metallic carbon nanotubes. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2510–2516     

A purge and trap technique to capture volatile compounds combined with comprehensive two‐dimensional gas chromatography/time‐of‐flight mass spectrometry to investigate the effect of sulfur‐fumigation on Radix Angelicae Dahuricae

Sulfur‐fumigation is known to reduce volatile compounds that are the main active components in herbs used in herbal medicine. We investigated changes in chemical composition between sun‐dried and sulfur‐fumigated Radix Angelicae Dahuricae using a purge and trap technique to capture volatile compounds, and two‐dimensional gas chromatography/time‐of‐flight mass spectrometry for identification. Using sun‐dried Radix Angelicae Dahuricae samples as a reference, the results showed that 73 volatile compounds, including 12 sulfide compounds, were found to be present only in sulfur‐fumigated samples. Furthermore, 32 volatile compounds that were found in sun‐dried Radix Angelicae Dahuricae samples disappeared after sulfur‐fumigation. The proposed method can be applied to accurately discriminate sulfur‐fumigated Radix Angelicae Dahuricae from different commercial sources. Copyright © 2014 John Wiley & Sons, Ltd.     

Experimental study on the added mass and damping of a disk submerged in a partially fluid-filled tank with small radial confinement

The dynamic response of submerged and confined disk-like structures is of interest in engineering applications, such as in hydraulic turbine runners. This response is difficult to be estimated with accuracy due to the strong influence of the boundary conditions. Small radial gaps as well as short axial distances to rigid surfaces greatly modify the dynamic response because of the added mass and damping effects.In this paper, the influence of the axial nearby rigid distance on the dynamic response of a submerged disk is evaluated when the radial gap is very small. Moreover, the effects of the fluid depth and fluid viscosity on the natural frequencies and damping ratio of the submerged disk are studied. The study has been performed experimentally and numerically using structural–acoustic simulations.For the experimental investigation a test rig has been developed. It consists of a disk attached to a shaft and confined with a small radial gap inside a cylindrical container full of water. The disk can be moved up and down along the shaft to vary the axial distance to the nearby rigid surface. Piezoelectric patches are used to excite the disk and the response is measured with submersible accelerometers. Several excitation patterns can be used due to the disposition of these piezoelectric patches. For each configuration tested, the dynamic response of the structure is studied analyzing the natural frequencies and damping ratio of the disk attached to the shaft. The numerical results have been compared with the experimental results.     

Triostin A Derived Cyclopeptide as Architectural Template for the Alignment of Four Recognition Units

The DNA bisintercalator triostin A is structurally based on a disulfide-bridged depsipeptide scaffold that provides preorganization of two quinoxaline units in 10.5 Å distance. Triostin A analogues are synthesized with nucleobase recognition units replacing the quinoxalines and containing two additional recognition units in between. Thus, four nucleobase recognition units are organized on a rigid template, well suited for DNA double strand interactions. The new tetra-nucleobase binders are synthesized as aza-TANDEM derivatives lacking the N-methylation of triostin A and based on a cyclopeptide backbone. Synthesis of two tetra-nucleobase aza-TANDEM derivatives is established, DNA interaction analyzed by microscale thermophoresis, cytotoxic activity studied and a nucleobase sequence dependent self-aggregation investigated by mass spectrometry.     

质谱检测技术在火星探测中的应用

火星探测对人类寻找地外生命、探索行星产生和演化机制具有重要的科学意义.质谱技术已经在火星探测方面得到了实际应用,获得的数据正在改写着人类对火星的基本认识.本文综述了国内外质谱技术在火星探测任务中的应用现状,特别是我国学者的研究进展、存在问题和应对策略.     

Autonomous conveyer gel driven by frontal polymerization

Autonomous mechanical mass transportation for cargos on the microscale with no need of continuous external powering is of great scientific and technological interest due to their extensive applications. However, it is still challenging to create a self‐driven system applicable to diverse micromaterial transportation demands. In this work, we developed a novel autonomous conveyer gel driven by frontal polymerization (FP). The chemical wave produced in FP was stable, and self‐propagating with a constant velocity, which can be easily monitored by thermal imaging or fluorescence labeling. We investigated the influence of the initiation temperature, swelling ratio of the gel substrate, and the size of the cargos on the motion of driven behavior. Results showed that the driving velocity can be well controlled by altering the initiation temperatures of FP. The swelling ratio and the size of the cargos had a key impact on the feasibility of self‐driven behavior. In addition, powerful driven capability by FP was demonstrated by successfully transporting cargos in series, and further applied for targeted synthesis of CdS nanocrystals. The methodology developed here provides an effective way to convert chemical energy to mechanical work, and may be useful in energy conversion and utilization, mass transportation and other applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1323‐1331     

Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262     

Capturing Transient Endoperoxide in the Singlet Oxygen Oxidation of Guanine

The chemistry of singlet O₂ toward the guanine base of DNA is highly relevant to DNA lesion, mutation, cell death, and pathological conditions. This oxidative damage is initiated by the formation of a transient endoperoxide through the Diels–Alder cycloaddition of singlet O₂ to the guanine imidazole ring. However, no endoperoxide formation was directly detected in native guanine or guanosine, even at ?100 °C. Herein, gas‐phase ion–molecule scattering mass spectrometry was utilized to capture unstable endoperoxides in the collisions of hydrated guanine ions (protonated or deprotonated) with singlet O₂ at ambient temperature. Corroborated by results from potential energy surface exploration, kinetic modeling, and dynamics simulations, various aspects of endoperoxide formation and transformation (including its dependence on guanine ionization and hydration states, as well as on collision energy) were determined. This work has pieced together reaction mechanisms, kinetics, and dynamics data concerning the early stage of singlet O₂ induced guanine oxidation, which is missing from conventional condensed‐phase studies.