Heat dissipation after nonanatomical lung resection using a laser is mainly due to emission to the environment: an experimental ex vivo study

Laser-directed resection of lung metastases is performed more frequently in recent years. The energy-loaded laser rays heat up the lung tissue, considerably. It is still unclear which mechanism is more important for tissue heat dissipation: the lung perfusion or the tissue emission. Therefore, we created a special experimental model to investigate the spontaneous heat dissipation after nonanatomical lung resection using a diode-pumped laser with a high output power. Experiments were conducted on paracardiac pig lung lobes (n = 12) freshly dissected at the slaughterhouse. Nonanatomical resection of lung parenchyma was performed without lobe perfusion in group 1 (n = 6), while group 2 (n = 6) was perfused at a physiological pressure of 25 cm H(2)O at 37 °C with saline via the pulmonary artery. For this, we used a diode-pumped neodymium-doped yttrium aluminum garnet (Nd:YAG) LIMAX® 120 laser (Gebrüder Martin GmbH & Co. KG, Tuttlingen, Germany) with a wavelength of 1,318 nm and a power output of 100 W. Immediately after completing laser resection, the lungs were monitored with an infrared camera (Type IC 120LV; Trotec, Heinsberg, Germany) while allowed to cool down. The resection surface temperature was taken at 10-s intervals and documented in a freeze-frame until a temperature of 37 °C had been reached. The temperature drop per time unit was analyzed in both groups. Immediately after laser resection, the temperature at the lung surface was 84.33 ± 8.08 °C in group 1 and 76.75 ± 5.33 °C in group 2 (p = 0.29). Group 1 attained the final temperature of 37 °C after 182.95 ± 53.76 s, and group 2 after 121.70 ± 16.02 s (p = 0.01). The temperature drop occurred exponentially in both groups. We calculated both groups’ decays using nonlinear regression, which revealed nearly identical courses. The mean time of tissue temperature of >42 °C, as a surrogate marker for tissue damage, was 97.14 ± 26.90 s in group 1 and 65.00 ± 13.78 s in group 2 (p = 0.02). Heat emission to the environment surpasses heat reduction via perfusion in nonanatomically laser-resected lung lobes. In developing a cooling strategy, a topical cooling method would be promising

Remote participation during glycosylation reactions of galactose building blocks: Direct evidence from cryogenic vibrational spectroscopy

The stereoselective formation of 1,2‐cis‐glycosidic bonds is challenging. However, 1,2‐cis‐selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short‐lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α‐selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium‐type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2‐cis‐glycosidic bonds

Mass Spectrometry-Based Techniques to Elucidate the Sugar Code

Cells encode information in the sequence of biopolymers, such as nucleic acids, proteins, and glycans. Although glycans are essential to all living organisms, surprisingly little is known about the “sugar code” and the biological roles of these molecules. The reason glycobiology lags behind its counterparts dealing with nucleic acids and proteins lies in the complexity of carbohydrate structures, which renders their analysis extremely challenging. Building blocks that may differ only in the configuration of a single stereocenter, combined with the vast possibilities to connect monosaccharide units, lead to an immense variety of isomers, which poses a formidable challenge to conventional mass spectrometry. In recent years, however, a combination of innovative ion activation methods, commercialization of ion mobility–mass spectrometry, progress in gas-phase ion spectroscopy, and advances in computational chemistry have led to a revolution in mass spectrometry-based glycan analysis. The present review focuses on the above techniques that expanded the traditional glycomics toolkit and provided spectacular insight into the structure of these fascinating biomolecules. To emphasize the specific challenges associated with them, major classes of mammalian glycans are discussed in separate sections. By doing so, we aim to put the spotlight on the most important element of glycobiology: the glycans themselves

Controlling the uncontrolled: Are there incidental experimenter effects on physiologic responding?

The degree to which experimenters shape participant behavior has long been of interest in experimental social science research. Here, we extend this question to the domain of peripheral psychophysiology, where experimenters often have direct, physical contact with participants, yet researchers do not consistently test for their influence. We describe analytic tools for examining experimenter effects in peripheral physiology. Using these tools, we investigate nine data sets totaling 1,341 participants and 160 experimenters across different roles (e.g., lead research assistants, evaluators, confederates) to demonstrate how researchers can test for experimenter effects in participant autonomic nervous system activity during baseline recordings and reactivity to study tasks. Our results showed (a) little to no significant variance in participants' physiological reactivity due to their experimenters, and (b) little to no evidence that three characteristics of experimenters that are well known to shape interpersonal interactions-status (using five studies with 682 total participants), gender (using two studies with 359 total participants), and race (in two studies with 554 total participants)-influenced participants' physiology. We highlight several reasons that experimenter effects in physiological data are still cause for concern, including the fact that experimenters in these studies were already restricted on a number of characteristics (e.g., age, education). We present recommendations for examining and reducing experimenter effects in physiological data and discuss implications for replication

Single electron-phonon interaction in a suspended quantum dot phonon cavity

An electron-phonon cavity consisting of a quantum dot embedded in a free-standing GaAs/AlGaAs membrane is characterized in Coulomb blockade measurements at low temperatures. We find a complete suppression of single electron tunneling around zero bias leading to the formation of an energy gap in the transport spectrum. The observed effect is induced by the excitation of a localized phonon mode confined in the cavity. This phonon blockade of transport is lifted at magnetic fields where higher electronic states with nonzero angular momentum are brought into resonance with the phonon energy.Comment: 4 pages, 4 figure

Cryogenic infrared spectroscopy provides mechanistic insight into the fragmentation of phospholipid silver adducts

Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a fragment spectrum can often be increased by the addition of metal cations. In particular, the use of silver ions is deeply rooted in the history of lipidomics due to their propensity to coordinate both electron-rich heteroatoms and C = C bonds in aliphatic chains. Not surprisingly, coordination of silver ions was found to enable the distinction of sn-isomers in glycerolipids by inducing reproducible intensity differences in the fragment spectra, which could, however, not be rationalized. Here, we investigate the fragmentation behaviors of silver-adducted sn- and double bond glycerophospholipid isomers by probing fragment structures using cryogenic gas-phase infrared (IR) spectroscopy. Our results confirm that neutral headgroup loss from silver-adducted glycerophospholipids leads to dioxolane-type fragments generated by intramolecular cyclization. By combining high-resolution IR spectroscopy and computational modelling of silver-adducted fragments, we offer qualitative explanations for different fragmentation behaviors of glycerophospholipid isomers. Overall, the results demonstrate that gas-phase IR spectroscopy of fragment ions can significantly contribute to our understanding of lipid dissociation mechanisms and the influence of coordinating cations

Unveiling Glycerolipid Fragmentation by Cryogenic Infrared Spectroscopy

Mass spectrometry is routinely employed for structure elucidation of molecules. Structural information can be retrieved from intact molecular ions by fragmentation; however, the interpretation of fragment spectra is often hampered by poor understanding of the underlying dissociation mechanisms. For example, neutral headgroup loss from protonated glycerolipids has been postulated to proceed via an intramolecular ring closure but the mechanism and resulting ring size have never been experimentally confirmed. Here we use cryogenic gas-phase infrared (IR) spectroscopy in combination with computational chemistry to unravel the structures of fragment ions and thereby shed light on elusive dissociation mechanisms. Using the example of glycerolipid fragmentation, we study the formation of protonated five-membered dioxolane and six-membered dioxane rings and show that dioxolane rings are predominant throughout different glycerolipid classes and fragmentation channels. For comparison, pure dioxolane and dioxane ions were generated from tailor-made dehydroxyl derivatives inspired by natural 1,2- and 1,3-diacylglycerols and subsequently interrogated using IR spectroscopy. Furthermore, the cyclic structure of an intermediate fragment occurring in the phosphatidylcholine fragmentation pathway was spectroscopically confirmed. Overall, the results contribute substantially to the understanding of glycerolipid fragmentation and showcase the value of vibrational ion spectroscopy to mechanistically elucidate crucial fragmentation pathways in lipidomics

Persistent LHPA Activation in German Individuals Raised in an Overprotective Parental Behavior

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.Parental upbringing may affect their offspring’s mental state across the entire lifespan. Overprotective parental child-rearing style may increase the disease burden in the offspring. Furthermore, this child-rearing style may also play a pathogenetic role by transmitting trauma- and stressor-related disorders (TSRD) across generations. Studies with animals have demonstrated that the mother’s immediate and expansive protection of the newborn decreases the limbic-hypothalamic-pituitary-adrenal (LHPA) axis activity in the offspring. However, few studies have investigated how stress impact humans raised in an overprotective manner. In a cross-sectional study with 40 healthy students recalling their overprotective upbringing, we show an increase in the dehydroepiandrostendione (DHEA) concentration and a reduction in the cortisol/DHEA-ratio in hair. Additionally, this child rearing style was associated with heightened indications of mental burden, depressiveness, and sense of coherence. Our results provide insight into the roots and consequences of psychological trauma across several generations. Further investigations focusing particularly on multigenerational transmission in extremely burdened families will augment our results

Studying the Key Intermediate of RNA Autohydrolysis by Cryogenic Gas-Phase Infrared Spectroscopy

Over the course of the COVID-19 pandemic, mRNA-basedvaccineshave gained tremendous importance. The development and analysis of modified RNA moleculesbenefit from advanced mass spectrometry and require sufficient understanding of fragmentation processes.Analogous tothe degradation of RNA in solution by autohydrolysis,backbone cleavage of RNA strands wasequally observedin the gas phase; however, the fragmentation mechanism remained elusive.In this work,autohydrolysis-like intermediates weregenerated from isolated RNA dinucleotidesin the gas phaseand investigatedusing cryogenic infrared spectroscopy in helium nanodroplets.Data from both experiment and density functional theory provide evidence forthe formation of a five-membered cyclic phosphateintermediateand rule outlinear orsix-membered structures. Furthermore, the experiments show that another prominent condensed-phase reactionof RNA nucleotides can be induced in the gas phase: the tautomerization of cytosine.Both observed reactions aretherefore highlyuniversal and intrinsic properties of the investigated molecules

Untersuchung des reaktiven Intermediats der RNA Autohydrolyse mittels kryogener Infrarotspektroskopie in der Gasphase

Im Laufe der COVID-19 Pandemie haben mRNA-basierte Impfstoffe an immenser Bedeutung gewonnen. Massenspektrometrie ist für die Entwicklung und Analyse von modifizierten RNA Molekülen unerlässlich, setzt jedoch ein grundlegendes Verständnis über Fragmentierungsprozesse voraus. Analog zu der Zersetzung von RNA in Lösung durch Autohydrolyse, kann die Spaltung des RNA Rückgrats ebenso in der Gasphase stattfinden. Bislang sind die Fragmentierungsmechanismen jedoch unzureichend untersucht. In dieser Arbeit wurden Intermediate aus isolierten RNA Dinukleotiden in der Gasphase generiert und mittels kryogener Infrarotspektroskopie in Helium-Nanotröpfchen untersucht. Die experimentellen Daten, unterstützt durch Dichtefunktionaltheorie, liefern Hinweise dafür, dass die Bildung eines fünfgliedrigen zyklischen Phosphat-Intermediats begünstigt ist, während lineare oder sechsgliedrige Strukturen ausgeschlossen werden können. Weiterhin zeigen die Experimente, dass eine zusätzliche, bekannte Reaktion von RNA Nukleotiden in Lösung auch in der Gasphase induziert werden kann: die Tautomerisierung von Cytosin. Die beiden beobachteten Reaktionen spiegeln daher universelle und intrinsische Eigenschaften der untersuchten Moleküle wider