世界上第一个物理技术研究所的建立及其影响

德国夏洛滕堡物理技术研究所（The Physikallisch-Technische Reichanstalt,简称PTR）是世界上第一个国家级的物理技术研究所，它开创了科学研究和技术研究相结合，服务于工业和国家经济之先河。文章从PTR建立的历史背景、早期研究工作和所产生的影响等方面作较为全面的讨论。     

Measurements of the optical absorption coefficient of Ar8+ ion implanted silicon layers using the photothermal radiometry and the modulated free carrier absorption methods

This paper presents a method of the measurement of the optical absorption coefficient of the Ar⁸⁺ ions implanted layers in the p-type silicon substrate. The absorption coefficient is calculated using a value of the attenuation of amplitudes of a photothermal radiometry (PTR) and/or a modulation free carrier absorption (MFCA) signals and the implanted layer thickness calculated by means of the TRIM program. The proposed method can be used to indicate the amorphization of the ions implanted layers.     

Comparison of direct mass spectrometry methods for the on‐line analysis of volatile compounds in foods

For the on‐line monitoring of flavour compound release, atmospheric pressure chemical ionization (APCI) and proton transfer reaction (PTR) combined to mass spectrometry (MS) are the most often used ionization technologies. APCI‐MS was questioned for the quantification of volatiles in complex mixtures, but direct comparisons of APCI and PTR techniques applied on the same samples remain scarce. The aim of this work was to compare the potentialities of both techniques for the study of in vitro and in vivo flavour release. Aroma release from flavoured aqueous solutions (in vitro measurements in Teflon bags and glass vials) or flavoured candies (in vivo measurements on six panellists) was studied using APCI‐ and PTR‐MS. Very similar results were obtained with both techniques. Their sensitivities, expressed as limit of detection of 2,5‐dimethylpyrazine, were found equivalent at 12 ng/l air. Analyses of Teflon bag headspace revealed a poor repeatability and important ionization competitions with both APCI‐ and PTR‐MS, particularly between an ester and a secondary alcohol. These phenomena were attributed to dependency on moisture content, gas/liquid volume ratio, proton affinities and product ion distribution, together with inherent drawbacks of Teflon bags (adsorption, condensation of water and polar molecules). Concerning the analyses of vial headspace and in vivo analyses, similar results were obtained with both techniques, revealing no competition phenomena. This study highlighted the equivalent performances of APCI‐MS and PTR‐MS for in vitro and in vivo flavour release investigations and provided useful data on the problematic use of sample bags for headspace analyses. Copyright © 2013 John Wiley & Sons, Ltd.     

连续调制光热辐射测量技术的三维理论模型

建立了连续调制光热辐射测量(PTR)的三维理论模型.理论值与实验结果符合良好,成功地解释了-维模型不能说明的结果.     

Emission of volatile sesquiterpenes and monoterpenes in grapevine genotypes following Plasmopara viticola inoculation in vitro

The grapevine (Vitis vinifera) is one of the most widely cultivated fruit crops globally, and one of its most important diseases in terms of economic losses is downy mildew, caused by Plasmopara viticola. Several wild Vitis species have been found to be resistant to this pathogen and have been used in breeding programs to introduce resistance traits to susceptible cultivars. Plant defense is based on different mechanisms, and volatile organic compounds (VOCs) play a major role in the response to insects and pathogens. Although grapevine resistance mechanisms and the production of secondary metabolites have been widely characterized in resistant genotypes, the emission of VOCs has not yet been investigated following P. viticola inoculation. A Proton Transfer Reaction‐Time of Flight‐Mass Spectrometer (PTR‐ToF‐MS) was used to analyze the VOCs emitted by in vitro‐grown plants of grapevine genotypes with different levels of resistance. Downy mildew inoculation significantly increased the emission of monoterpenes and sesquiterpenes by the resistant SO4 and Kober 5BB genotypes, but not by the susceptible V. vinifera Pinot noir. Volatile terpenes were implicated in plant defense responses against pathogens, suggesting that they could play a major role in the resistance against downy mildew by direct toxicity or by inducing grapevine resistance. The grapevine genotypes differed in terms of the VOC emission pattern of both inoculated and uninoculated plants, indicating that PTR‐ToF‐MS could be used to screen hybrids with different levels of downy mildew resistance. Copyright © 2015 John Wiley & Sons, Ltd.     

Selective reagent ionisation‐time of flight‐mass spectrometry: a rapid technology for the novel analysis of blends of new psychoactive substances

In this study we demonstrate the potential of selective reagent ionisation‐time of flight‐mass spectrometry for the rapid and selective identification of a popular new psychoactive substance blend called ‘synthacaine’, a mixture that is supposed to imitate the sensory and intoxicating effects of cocaine. Reactions with H₃O⁺ result in protonated parent molecules which can be tentatively assigned to benzocaine and methiopropamine. However, by comparing the product ion branching ratios obtained at two reduced electric field values (90 and 170 Td) for two reagent ions (H₃O⁺ and NO⁺) to those of the pure chemicals, we show that identification is possible with a much higher level of confidence then when relying solely on the m/z of protonated parent molecules. A rapid and highly selective analytical identification of the constituents of a recreational drug is particularly crucial to medical personnel for the prompt medical treatment of overdoses, toxic effects or allergic reactions. Copyright © 2015 John Wiley & Sons, Ltd.     

Theoretical chemical ionization rate constants of the concurrent reactions of hydronium ions (H3O+) and oxygen ions (O ) with selected organic iodides

Short chain volatile iodinated organic compounds (VIOCs) are of great importance in many fields that include atmospheric chemistry, agriculture, and environmental chemistry related to nuclear power plant safety. Proton‐transfer‐reaction mass spectrometry (PTR‐MS) allows for fast, sensitive, and online quantification of VIOCs if the chemical ionization (CI) reaction rate coefficients are known. In this work, the theoretical CI rate coefficients for the reactions of hydronium ions (H₃O⁺) and oxygen ions (O ) with selected atmospherically important short chain VIOCs are determined. The neutral CH₃I, CH₂I₂, C₂H₅I, iso‐C₃H₇I, n‐C₃H₇I, n‐C₄H₉I, 2‐C₄H₉I, n‐C₅H₁₁I, 2‐C₅H₁₁I, and 3‐C₅H₁₁I have been chosen because these compounds are of atmospheric and environmental importance in the field of safety of nuclear plant reactors. Theoretical ion‐molecule collision rate coefficients were determined using the Su and Chesnavich theory based on parametrized trajectory calculations. The proton affinity, ionization energy, dipole moment, and polarizability values of the neutral molecules were determined from density functional theory and coupled‐cluster calculations. The newly calculated rate constants facilitate the use of the CI mass spectrometry in the atmospheric quantification of selected VIOCs.     

Glyoxal measurement with a proton transfer reaction time of flight mass spectrometer (PTR‐TOF‐MS): characterization and calibration

We examine the potential for PTR‐TOF‐MS systems to quantitatively measure glyoxal in ambient air by characterizing the response of the instrument to a dilute glyoxal sample, calibrating the system as a function of humidity. The concentration of glyoxal in a sample air‐stream was measured with an UV absorption spectrometer in parallel to a PTR‐TOF‐MS. This calibration demonstrated that the PTR‐TOF‐MS has a relatively low sensitivity to glyoxal particularly at high humidity. Extensive fragmentation of glyoxal to formaldehyde was observed. This behaviour not only desensitizes PTR‐MS system to glyoxal; it may also pose a problem to the quantification of formaldehyde. © 2016 The Authors. Journal of Mass Spectrometry Published by John Wiley & Sons Ltd.     

Static and dynamic headspace analysis of instant coffee blends by proton‐transfer‐reaction mass spectrometry

Instant coffee is a widespread product, generally related to a high consumer acceptability, also because of its ease of preparation. The present work addresses the characterization of the headspace of freshly brewed instant coffees resulting from different blends, during and immediately after preparation. The sample set consisted of 10 coffees, obtained by mixing three different blends in different proportions. The employment of Proton Transfer Reaction‐Mass Spectrometry (PTR‐MS) allowed for direct and real‐time sampling from the headspace, under conditions that mimic those that are encountered above the cup during and right after brewing. Different coffee brews were separated on the basis of the respective volatile profiles, and data showed good consistency with the respective blend compositions. When the headspace evolution was monitored during preparation, similar results were obtained in terms of blend separation; moreover, different blends displayed different and reproducible ‘signatures’ in terms of time evolution. A straightforward method for the prediction of headspace composition is proposed, allowing to predict the volatile profiles of two‐component and three‐component blends on the basis of the respective parent components. Overall, the results constitute a successful example of the applicability of PTR‐MS as a tool for product development in food science. Copyright © 2015 John Wiley & Sons, Ltd.     

Distinguishing two isomeric mephedrone substitutes with selective reagent ionisation mass spectrometry (SRI‐MS)

The isomers 4‐methylethcathinone and N‐ethylbuphedrone are substitutes for the recently banned drug mephedrone. We find that with conventional proton transfer reaction mass spectrometry (PTR‐MS), it is not possible to distinguish between these two isomers, because essentially for both substances, only the protonated molecules are observed at a mass‐to‐charge ratio of 192 (C₁₂H₁₈NO⁺). However, when utilising an advanced PTR‐MS instrument that allows us to switch the reagent ions (selective reagent ionisation) from H₃O⁺ (which is commonly used in PTR‐MS) to NO⁺, O₂⁺ and Kr⁺, characteristic product (fragment) ions are detected: C₄H₁₀N⁺ (72 Da) for 4‐methylethcathinone and C₅H₁₂N⁺ (86 Da) for N‐ethylbuphedrone; thus, selective reagent ionisation MS proves to be a powerful tool for fast detection and identification of these compounds. Copyright © 2013 John Wiley & Sons, Ltd.