Volatile organic compounds in head and neck squamous cell carcinoma—An in vitro pilot study

Owing to the lack of specific symptoms, diagnosis of head and neck squamous cell carcinoma (HNSCC) may be delayed. We evaluated volatile organic compounds in tumor samples from patients suffering from HNSCC and tested the hypothesis that there is a characteristic altered composition in the headspace of HNSCC compared with control samples from the same patient with normal squamous epithelium. These results provide the basis for future noninvasive breath analysis in HNSCC. Headspace air of suspected tumor and contralateral control samples in 20 patients were analyzed using ion-mobility spectrometry. Squamous cell carcinoma was diagnosed in 16 patients. In total, we observed 93 different signals in headspace measurements. Squamous cell carcinomas revealed significantly higher levels of volatile cyclohexanol (0.54 ppb_v, 25th to 75th percentiles 0.35–0.86) compared with healthy squamous epithelium (0.24 ppb_v, 25th to 75th percentiles 0.12–0.3; p < 0.001). In conclusion, head and neck squamous cell carcinoma emitted significantly higher levels of volatile cyclohexanol in headspace compared with normal squamous epithelium. These findings form the basis for future breath analysis for diagnosis, therapy control and the follow-up of HNSSC to improve therapy and aftercare.     

NIR Light-Induced ATRP for Synthesis of Block Copolymers Comprising UV-Absorbing Moieties

NIR exposure at 790 nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [Cu^II/(TPMA)]Br₂ (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol.     

Differential Response of Pentanal and Hexanal Exhalation to Supplemental Oxygen and Mechanical Ventilation in Rats

High inspired oxygen during mechanical ventilation may influence the exhalation of the previously proposed breath biomarkers pentanal and hexanal, and additionally induce systemic inflammation. We therefore investigated the effect of various concentrations of inspired oxygen on pentanal and hexanal exhalation and serum interleukin concentrations in 30 Sprague Dawley rats mechanically ventilated with 30, 60, or 93% inspired oxygen for 12 h. Pentanal exhalation did not differ as a function of inspired oxygen but increased by an average of 0.4 (95%CI: 0.3; 0.5) ppb per hour, with concentrations doubling from 3.8 (IQR: 2.8; 5.1) ppb at baseline to 7.3 (IQR: 5.0; 10.8) ppb after 12 h. Hexanal exhalation was slightly higher at 93% of inspired oxygen with an average difference of 0.09 (95%CI: 0.002; 0.172) ppb compared to 30%. Serum IL-6 did not differ by inspired oxygen, whereas IL-10 at 60% and 93% of inspired oxygen was greater than with 30%. Both interleukins increased over 12 h of mechanical ventilation at all oxygen concentrations. Mechanical ventilation at high inspired oxygen promotes pulmonary lipid peroxidation and systemic inflammation. However, the response of pentanal and hexanal exhalation varies, with pentanal increasing by mechanical ventilation, whereas hexanal increases by high inspired oxygen concentrations.     

Improved upper bounds for partial spreads

A partial \((k-1)\)-spread in \({\text {PG}}(n-1,q)\) is a collection of \((k-1)\)-dimensional subspaces with trivial intersection. So far, the maximum size of a partial \((k-1)\)-spread in \({\text {PG}}(n-1,q)\) was known for the cases \(n\equiv 0\pmod k\), \(n\equiv 1\pmod k\), and \(n\equiv 2\pmod k\) with the additional requirements \(q=2\) and \(k=3\). We completely resolve the case \(n\equiv 2\pmod k\) for the binary case \(q=2\).     

Cover Picture: Supramolecular Self-Assembly as a Tool To Preserve the Electronic Purity of Perylene Diimide Chromophores (Angew. Chem. Int. Ed. 12/2023)

Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited-state quenching due to uncontrolled aggregation limits their use in devices. We report on the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non-aggregated, monomer-like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited-state reservoir in a rare case of benign inter-chromophore interactions in the cage. We show that self-assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach.     

Highly Conjugated Bis(benzo[b]phosphole)-P-oxides: Synthesis and Electrochemical,Optical, and Computational Studies

The first examples of a π-conjugated benzo[b]phosphole P-oxide in which two phosphole P-oxide units are connected by a carbon-carbon double bond are described. The molecules are synthesized as E isomers with respect to the carbon-carbon double bond and exist as stable cis and trans isomers (chiral and meso one respectively) relatively to the two stereogenic P atoms. The optical and electrochemical properties of both isomers have been investigated by experiment and computations.     

The Formation of Methyl Ketones during Lipid Oxidation at Elevated Temperatures

Lipid oxidation and the resulting volatile organic compounds are the main reasons for a loss of food quality. In addition to typical compounds, such as alkanes, aldehydes and alcohols, methyl ketones like heptan-2-one, are repeatedly described as aroma-active substances in various foods. However, it is not yet clear from which precursors methyl ketones are formed and what influence amino compounds have on the formation mechanism. In this study, the formation of methyl ketones in selected food-relevant fats and oils, as well as in model systems with linoleic acid or pure secondary degradation products (alka-2,4-dienals, alken-2-als, hexanal, and 2-butyloct-2-enal), has been investigated. Elevated temperatures were chosen for simulating processing conditions such as baking, frying, or deep-frying. Up to seven methyl ketones in milk fat, vegetable oils, and selected model systems have been determined using static headspace gas chromatography-mass spectrometry (GC-MS). This study showed that methyl ketones are tertiary lipid oxidation products, as they are derived from secondary degradation products such as deca-2,4-dienal and oct-2-enal. The study further showed that the position of the double bond in the precursor compound determines the chain length of the methyl ketone and that amino compounds promote the formation of methyl ketones to a different degree. These compounds influence the profile of the products formed. As food naturally contains lipids as well as amino compounds, the proposed pathways are relevant for the formation of aroma-active methyl ketones in food.     

Cobalt and Iron Stabilized Ketyl,Ketiminyl and Aldiminyl Radical Anions

Carbonyl and iminyl based radical anions are reactive intermediates in a variety of transformations in organic synthesis. Herein, the isolation of ketyl, and more importantly unprecedented ketiminyl and aldiminyl radical anions coordinated to cobalt and iron complexes is presented. Insights into the electronic structure of these unusual metal bound radical anions is provided by X-Ray diffraction analysis, NMR, IR, UV/Vis and Mössbauer spectroscopy, solid and solution state magnetometry, as well as a by a detailed computational analysis. The metal bound radical anions are very reactive and facilitate the activation of intra- and intermolecular C−H bonds.