Comparison of atmospheric pressure photoionization and atmospheric pressure chemical ionization for normal-phase LC/MS chiral analysis of pharmaceuticals

In this work, we compared APPI and APCI for normal-phase LC/MS chiral analysis of five pharmaceuticals. Performance was compared both by FIA and by on-column analysis using a ChiralPak AD-H column under optimized conditions. By comparison, APPI generated more reproducible signals and was less susceptible to ion suppression than APCI. APPI generated higher peak area and lower baseline noise, and therefore much higher S/N ratios. APPI sensitivity (i.e., S/N ratio) was approximately 2-130 times higher than APCI by FIA and was approximately 2.6-530 times higher than APCI by on-column analysis depending on specific compounds. The better APPI sensitivity as compared to APCI was more dramatic by on-column analysis than by FIA. APCI sensitivity was degraded by ion suppression caused by LC column bleeding components and by elevated APCI baseline noise relative to APPI. On-column APPI LODs (at S/N = 3) were 83, 16, 17, 95, and 7 pg for enantiomer #1, and 104, 23, 19, 122, and 17 pg for enantiomer #2 for benzoin, naringenin, mianserin, mephenesin, and diperodon, respectively, on a Waters ZQ. APPI offers no concern of explosion hazard relative to APCI corona needle discharge or ESI high voltage discharge when flammable solvents (e.g., hexane) are used as mobile phases. Whether APPI dopants are required depends on the IP(s) of mobile-phase solvent(s) and solvent complexes, and photon energies of VUV lamps. Dopant was not necessary for hexane-based mobile phases due to their self-doping effects. Dopants did enhance Kr lamp APPI sensitivity when MeOH was used as the mobile phase. However, dopants became unnecessary for the MeOH mobile phase when the Ar lamp was used.     

Microcavity-integrated graphene photodetector

There is an increasing interest in using graphene (1, 2) for optoelectronic applications. (3-19) However, because graphene is an inherently weak optical absorber (only ≈2.3% absorption), novel concepts need to be developed to increase the absorption and take full advantage of its unique optical properties. We demonstrate that by monolithically integrating graphene with a Fabry-Pérot microcavity, the optical absorption is 26-fold enhanced, reaching values >60%. We present a graphene-based microcavity photodetector with responsivity of 21 mA/W. Our approach can be applied to a variety of other graphene devices, such as electro-absorption modulators, variable optical attenuators, or light emitters, and provides a new route to graphene photonics with the potential for applications in communications, security, sensing and spectroscopy.     

Die mikroskopische Untersuchung von Fleisch- und Wurstwaren

Zusammenfassung Die Ergebnisse der chemischen Untersuchung von Fleisch- und Wurstwaren sind als ausschließliche Grundlage für ihre Beurteilung durchaus ungenügend; denn wir können noch nicht annähernd sämtliche chemischen Einzelbestandteile des Fleisches und der Wurstwaren mittels der im praktischen Laboratorium anwend aren Methoden nachweisen und noch viel weniger diese Einzelbestandteile quantitativ ermitteln. Es läßt sich aber auch im allgemeinen durch die chemische Untersuchung allein nicht feststellen, ob eine unter bestimmten Namen in den Handel gebrachte Ware die in diesem Namen zum Ausdruck gebrachten Fleischbestandteile tatsächlich enthält, wie z. B., ob Leberwurst Leber enthält, ferner ob minderwertige oder verbotene Organund Gewebeteile beigemischt sind oder nicht.Daher ist die mikroskopische Untersuchung, besonders in gerichtlichen Fällen, unerläßlich.Die nur auf mikroskopischem Wege erreichbare Kenntnis der in Fleisch und Wurstwaren enthaltenen Gewebe und Organe erleichtert bezw. ermöglicht die Beurteilung von Fleisch- und Wurstwaren nicht nur in vorgenannter Richtung, sondern sie erleichtert auch sehr wesentlich die Beurteilung ihres Gesamtwertes. Dieser ist verschieden je nach dem Vorhandensein der mikroskopisch nachzuweisenden Gewebe bezw. Organe und nach deren Wassergehalt. Letzterer wiederum ist z. B. bei Muskelfleisch konstanter und liegt in engeren Grenzen als bei den drüsigen Organen; im elastischen Bindegewebe ist er bedeutend niedriger als im kollagenen Bindegewebe oder im Muskelfleisch.In der vorliegenden Arbeit ist der Versuch gemacht, die mikroskopischen Schnitte der wichtigsten in Betracht kommenden Gewebe und Organe in gekochtem Zustande so zu charakterisieren, daß sie in Gemischen einwandfrei identifiziert werden können.Die Technik der mikroskopischen Untersuchung von Fleisch- und Wurstwaren ist unter Angabe bewährter Verfahren eingehend dargestellt.     

Serum Proteomics in Patients with Head and Neck Cancer: Peripheral Blood Immune Response to Treatment

In this real-world study, the aims were to prospectively evaluate the expression of inflammatory proteins in serum collected from head and neck cancer patients before and after treatment, and to assess whether there were differences in expression associated with treatment modalities. The mixed study cohort consisted of 180 patients with head and neck cancer. The most common tumor sites were the oropharynx (n = 81), the oral cavity (n = 53), and the larynx (n = 22). Blood tests for proteomics analysis were carried out before treatment, 7 weeks after the start of treatment, and 3 and 12 months after the termination of treatment. Sera were analyzed for 83 proteins using an immuno-oncology biomarker panel (Olink, Uppsala, Sweden). Patients were divided into four treatment groups: surgery alone (Surg group, n = 24), radiotherapy with or without surgery (RT group, n = 94), radiotherapy with concomitant cisplatin (CRT group, n = 47), and radiotherapy with concomitant targeted therapy (RT Cetux group, n = 15). For the overall cohort, the expression levels of 15 of the 83 proteins changed significantly between the pretreatment sample and the sample taken 7 weeks after the start of treatment. At 7 weeks after the start of treatment, 13 proteins showed lower expression in the CRT group compared to the RT group. The majority of the inflammatory proteins had returned to their pretreatment levels after 12 months. It was clearly demonstrated that cisplatin-based chemoradiation has immunological effects in patients with head and neck cancer. This analysis draws attention to several inflammatory proteins that are of interest for further studies.