Infrared Photodissociation Spectroscopy of Water-Tagged Ions with a Widely Tunable Quantum Cascade Laser for Planetary Science Applications.

This work presents a benchtop method for collecting the room temperature gas phase infrared (IR) action spectra of protonated amino acids and their isomers. The adopted setup uses a minimally modified commercial electrospray ionization linear ion trap mass spectrometer (ESI-LIT-MS) coupled to a broadband continuous wave (cw) quantum cascade laser (QCL) source. This approach leverages messenger assisted action spectroscopic techniques using water-tagged molecular ions with complex formation, irradiation, and subsequent analysis, all taking place within a single linear ion trap stage. This configuration thus circumvents the use of multiple mass selection and analysis stages, cryogenic buffer cells, and complex high-power laser systems typically called upon to execute these techniques. The benchtop action spectrometer is used to collect the 935-1600 cm-1 (6.2-10.7 µm) IR action spectrum of a collection of amino acids and a dipeptide with results cross referenced against literature examples obtained with a free electron laser source. Recorded IR spectra are used for the analysis of binary mixture samples composed of constitutional isomers α-alanine and ß-alanine with ratios determined to ∼4% measurement uncertainty without the aid of a front-end separation stage. This turn-key QCL-based approach is a major step in showing the viability of tag-based action spectroscopic techniques for use in future in situ planetary science sensors and general analytical applications.

Investigation of Venus Cloud Aerosol and Gas Composition Including Potential Biogenic Materials via an Aerosol-Sampling Instrument Package.

A lightweight, low-power instrument package to measure, in situ, both (1) the local gaseous environment and (2) the composition and microphysical properties of attendant venusian aerosols is presented. This Aerosol-Sampling Instrument Package (ASIP) would be used to explore cloud chemical and possibly biotic processes on future aerial missions such as multiweek balloon missions and on short-duration (<1 h) probes on Venus and potentially on other cloudy worlds such as Titan, the Ice Giants, and Saturn. A quadrupole ion-trap mass spectrometer (QITMS; Madzunkov and Nikolic, J Am Soc Mass Spectrom 25:1841-1852, 2014) fed alternately by (1) an aerosol separator that injects only aerosols into a vaporizer and mass spectrometer and (2) the pure aerosol-filtered atmosphere, achieves the compositional measurements. Aerosols vaporized <600°C are measured over atomic mass ranges from 2 to 300 AMU at <0.02 AMU resolution, sufficient to measure trace materials, their isotopic ratios, and potential biogenic materials embedded within H2SO4 aerosols, to better than 20% in <300 s for H2SO4 -relative abundances of 2 × 10-9. An integrated lightweight, compact nephelometer/particle-counter determines the number density and particle sizes of the sampled aerosols.

Chemical Ionization Mass Spectrometry: Applications for the In Situ Measurement of Nonvolatile Organics at Ocean Worlds.

A new technique that has applications for the detection of nonvolatile organics on Ocean Worlds has been developed. Here, liquid mixtures of fatty acids (FAs) and/or amino acids (AAs) are introduced directly into a miniature quadrupole ion trap mass spectrometer (QITMS) developed at Jet Propulsion Laboratory and analyzed. Two ionization methods, electron impact and chemical ionization (EI and CI, respectively), are compared and contrasted. Further, multiple CI reagents are tested to explore their potential to "soften" ionization of FAs and AAs. Both EI and CI yield mass spectra that bear signatures of FAs or AAs; however, soft CI yields significantly cleaner mass spectra that are easier to interpret. The combination of soft CI with tandem mass spectrometry (MS/MS) has also been demonstrated for AAs, generating "fingerprint" mass spectra of fragments from protonated parent ions. To mimic potential Ocean World conditions, water is used as the primary collision gas in MS/MS experiments. This technique has the potential for the in situ analysis of molecules in the cryogenic plumes of Ocean Worlds (e.g., Enceladus) and comets with the ultimate goal of detecting potential biosignatures.

Cytoreductive surgery and hyperthermic intraperitoneal chemotherapy for the treatment of advanced epithelial and recurrent ovarian carcinoma: a single center experience.

BACKGROUND: With standard treatment of epithelial ovarian cancer (EOC), prognosis is very poor. The aim of this study is to show early and late results in patients who underwent cytoreductive surgery and intraperitoneal chemotherapy. PATIENTS AND METHODS: This was a retrospective single centre study. All patients with advanced and recurrent ovarian cancer treated with cytoreductive surgery and hyperthermic intraperitoneal chemotherapy (HIPEC) or modified early postoperative intraperitoneal chemotherapy (EPIC) were included in the study. RESULTS: In the period 1995-2014, 116 patients were treated, 55 with primary EOC and 61 with recurrent EOC. The mean age was 59 years (26-74). Statistically, median survival time was significantly longer in the group with primary advanced cancer of the ovary (41.3 months) compared to relapsed ovarian cancer (27.3 months). Survival for the primary EOC was 65 and 24% at 3 and 5 years, respectively. Survival for recurrent EOC was 33 and 16% at 3 and 5 years, respectively. Mortality was 1/116 (0.8%). Morbidity was 11/116 (9.5%). Peritoneal cancer index (PCI) was ≤20 in 59 (51%) patients and statistically, their average survival was significantly longer than in the group of 57 (49%) patients with PCI >20 (p = 0.014). CONCLUSIONS: In advanced or recurrent EOC, a curative therapeutic approach was pursued that combined optimal cytoreductive surgery and intraperitoneal chemotherapy. PCI and timing of the intervention (primary or recurrent) were the strongest independent prognostic factors.

Computer Modeling of an Ion Trap Mass Analyzer, Part I: Low Pressure Regime.

We present the multi-particle simulation program suite Computational Ion Trap Analyzer (CITA) designed to calculate the ion trajectories within a Paul quadrupole ion trap developed by the Jet Propulsion Laboratory (JPL). CITA uses an analytical expression of the electrodynamic field, employing up to six terms in multipole expansion and a modified velocity-Verlet method to numerically calculate ion trajectories. The computer code is multithreaded and designed to run on shared-memory architectures. CITA yields near real-time simulations with full propagation of 26 particles per second per core. As a consequence, a realistic numbers of trapped ions (100+ million) can be used and their trajectories modeled, yielding a representative prediction of mass spectrometer analysis of trace gas species. When the model is compared with experimental results conducted at low pressures using the conventional quadrupole and dipole excitation modes, there is an excellent agreement with the observed peak shapes. Owing to the program's efficiency, CITA has been used to explore regions of trapping stability that are of interest to experimental research. These results are expected to facilitate a fast and reliable modeling of ion dynamics in miniature quadrupole ion trap and improve the interpretation of observed mass spectra. Graphical Abstract ᅟ.

Accurate Xe isotope measurement using JPL ion trap.

We report an approach for the reproducible and accurate compositional analysis of different mixtures of Xe isotopes using miniature Jet Propulsion Laboratory Quadrupole Ion Trap (JPL-QIT). A major study objective was to validate the recent instrumental improvements to the long-term operational stability under different pressures, temperatures, and trapping conditions. We propose that the present device can be used in certification of trace amounts of isotopes in mixtures dominated by one or more isotopes. Measured isotopic compositions are verified against commercially available standards with accuracy better than 0.07%. To aid the analysis of experimental data, we developed a scalable replica fitting method and use peak areas as descriptors of relative isotopic abundances. This low-power and low-mass device is ideally suited for planetary explorations aimed to enhance quantitative analysis for major isotopes present in small amounts of atmospheric samples.

Two synchronous somatostatinomas of the duodenum and pancreatic head in one patient.

Somatostatinomas are extremely rare neuroendocrine tumors of the gastrointestinal tract, first described in the pancreas in 1977 and in the duodenum in 1979. They may be functional and cause somatostatinoma or inhibitory syndrome, but more frequently are non-functioning pancreatic endocrine tumors that produce somatostatin alone. They are usually single, malignant, large lesions, frequently associated with metastases, and generally with poor prognosis. We present the unique case of a 57-year-old woman with two synchronous non-functioning somatostatinomas, one solid duodenal lesion and one cystic lesion within the head of the pancreas, that were successfully resected with a pylorus-preserving Whipple's procedure. No secondaries were found in the liver, or in any of the removed regional lymph nodes. The patient had an uneventful recovery, and remains well and symptom-free at 18 mo postoperatively. This is an extremely rare case of a patient with two synchronous somatostatinomas of the duodenum and the pancreas. The condition is discussed with reference to the literature.

Perigastric extraskeletal Ewing's sarcoma: a case report.

Ewing's sarcoma (ES) is a neoplasm of undifferentiated small round cells, which occurs in the bones and deep soft tissues of children and adolescents. We present a rare case of a 44-year-old woman with gastric ES presenting with epigastric pain and weight loss. Ultrasound and computed tomography scans indicated a solid/cystic mass in the pancreatic tail. At laparotomy, the tumor was found attached to the posterior surface of the stomach, completely free from the pancreas, with no lymphadenopathy or local metastases. The polynodal, partly pseudocystic, dark-red soft tumor was excised. Histopathology revealed an anaplastic small-round-cell tumor with strong membranous CD99 immunoexpression. Additionally, there was patchy immunostaining for S-100 protein, vimentin, protein gene product (PGP) 9.5 and neuron-specific enolase, and weak focal CD117 cytoplasmic immunoreactivity. The patient had no adjuvant chemotherapy; her postoperative recovery was uneventful, and she remains symptom-free, and without any sign of recurrence at 20 mo. To the best of our knowledge, this is only the third ever case of gastric ES.

Sudden death of a 17-year-old boy due to suspected Williams syndrome.

In this article, we present a case of sudden death of a 17-year-old boy, in which diagnosis of Williams syndrome was firstly suspected after medicolegal autopsy, on the basis of typical macroscopical changes (facial appearance, dental status, supravalvular aortic stenosis with mild enlargement of the heart and significant thickening of the left ventricular myocardium) as well as heteroanamnestic data (slight mental retardation and nervousness). All other causes of sudden death were excluded. The definite diagnosis of this syndrome could not be corroborated as specific genetic analysis (fluorescent in situ hybridization test) could not be performed because of the lack of appropriate technical facilities.

Omphalocele associated with gastroschisis defect covered with skin.

Omphalocele and gastroschisis are distinct malformations in many aspects. Anatomical and pathologic findings in both conditions are usually typical and very frequent. Unusual clinical presentations of some cases may contribute to clearing up questions about the embryological origins of gastroschisis and omphalocele. We describe a rare case of omphalocele associated with gastroschisis defect covered with skin.

Postmortem production of ethanol in different tissues under controlled experimental conditions.

The aim of this study was to follow the postmortem ethanol production phenomenon under controlled experimental conditions (temperature, time interval) in different tissues. Specimens of blood, liver, skeletal muscle and kidney were taken from 30 corpses and no chemical preservatives were used in the specimens collected. Ethanol concentrations were detected by gas chromatography. All specimens stored at -20 degrees C and 4 degrees C did not show any change in ethanol concentration in an eight-day time interval. At 20 degrees C and 30 degrees C, all tissues, except blood, showed statistically significant ethanol production over the time interval tested. However, blood sample kept at 30 degrees C, showed statistically significant increase in ethanol production on the 2nd and 4th day comparing to the controls. Thus, we can state that postmortem ethanol production occurs in different tissues, and is increased at higher temperatures and, in general, it is in accordance with the course of time.

Evaluation of body surface potential mapping changes after successful percutaneous transluminal coronary angioplasty.

OBJECTIVE: To assess the progress of chronic myocardial ischemia after successful percutaneous transluminal coronary angioplasty (PTCA) using body surface potential mapping (BSPM). DESIGN: For BSPM analysis the following kinds of maps were used: isopotential repolarization maps corresponding to 70% of ST-T interval's duration and isointegral maps corresponding to 0% to 20% of ST-T duration. BSPM measurements were taken before the PTCA and usually one to six days after this intervention. In 17 patients BSPM was carried out within two days after PTCA. Eleven to 14 BSPM examinations were usually carried out during six months of follow-up. Control coronary angiography was performed after six months in all but three patients. RESULTS: Substantial focal decrease of positive potential in repolarization caused by myocardial ischemia recovered gradually after successful PTCA. This appeared to be caused by the regression of "hibernating myocardium'. An increase of positive potential was statistically significant (P < 0.01) after the fifth week of PTCA intervention. There was a positive correlation between BSPM findings and chest discomfort of patients after PTCA. Chronic myocardial ischemia could be observed on isopotential and/or isointegral maps examined before the PTCA in 21 of 25 cases (sensitivity 84%).

Analysis of ventricular activation in patients with chronic non-Q wave myocardial infarction: comparison with left ventricular asynergy and myocardial perfusion defects.

In this report, we dealt with ventricular activation abnormalities in 30 patients with previous non-Q myocardial infarction (MI) by means of the CARDIAG 128.1 device, which enables analysis of ECGs, VCGs and body surface potential maps. The diagnosis was verified by left ventriculography, echocardiography and perfusion scintigraphy. Twenty-nine healthy subjects served as the control group. Morphological findings confirmed the presence of a significant subgroup with serious left ventricular asynergy. Seven electrocardiological variables, which significantly differed from control values, disclosed that non-Q MI is responsible for localized activation time prolongation, and that inferoposterior scars tend to delay the entire activation of ventricles, and to cause disturbances of the terminal depolarization phase together with a decrease in voltage production during QRS. Lesions of the anterior wall and the apicomesial part of the inferoposterior wall affect the distribution of the Q wave more often than the posterior basal ones. The probability of such abnormalities increases with the degree of asynergy. Some VCG criteria increase the sensitivity of electrocardiological analysis. These parameters will be used for evaluating the diagnostic value of electrocardiological analysis in the chronic non-Q MI. Non-Q myocardial infarctions represent a heterogeneous group of infarctions from both electrophysiological and morphological aspects.

The methodology of clinical analysis of electric heart field.

A brief description of the methodology of analysis of the electric heart field using electrocardiograms, vectorcardiograms, diagrams of potential maxima/minima and body surface potential maps is presented. The text is focused on the description of different kinds of isopotential and isointegral maps and their diagnostic possibilities. A detailed description of the diagram of potential maxima/minima and its place in diagnostic of different disturbances of the heart muscle and conduction defects is given.

[Diagnosis of conditions following myocardial infarct using complex analysis of electrical cardiac fields]. / Diagnostika stavu po srdecním infarktu komplexní analýzou elektrického srdecního pole.

In 22 patients with ischaemic heart disease and conditions after infarction and angina pectoris a coronarographic examination was made as well as other auxiliary examinations incl. a complex analysis of the electrical cardiac field (KAESP) (23), using a Cardiac apparatus (manufacturer ZPA Cakovice). Using the KAESP method fibroses in the heart muscle were found in all 22 patients, while a classical electrocardiogram revealed them only in 12 patients (54.5%). Post-infarction fibrous changes on the inferior cardiac wall were detected by ECG in 10 patients, KAESP revealed this localization of changes in 17 patients. The difference was particularly marked as regards localization on the anterior cardiac wall, according to ECG it was in 2 patients, according to KAESP in 17 patients. The authors investigated also on isopotential repolarization maps focal changes caused by cardiac ischaemia associated with organic affection of the appropriate coronary artery as revealed by coronarography. Identical sites were proved in 18 patients by the two methods, i. e. in 81.8%. In the discussion the authors analyse the causes which influence the accuracy of assessment of the coronary artery in KAESP. In KAESP in addition to isopotential maps also other maps were used such as isointegral, iso-areal, asynchronic potential maxima and minima, isochronic maps, maps of negative isodivergencies, profile sections etc. (20).

[Diagnosis of syndrome X using comprehensive analysis of the electrical field of the heart]. / Diagnostika syndromu X komplexní analýzou elektrického srdecního pole.

The authors describe the clinical picture and results of some auxiliary examinations in 18 patients with the X syndrome, i.e. with angina pectoris with a normal angiographic finding on the coronary arteries. For the diagnosis of ischemic cardiac changes, which are an integral part of this syndrome, the authors used a complex analysis of the electric cardiac field by means of a Cardiac 128.1 apparatus (manufactured by ZPA-Cakovice). In patients with the X syndrome they observed a significant reduction of some potential and integral values, as compared with an equally sized group of healthy subjects. On maps of the electric manifestation of cardiac activity on the chest surface ischemic changes were revealed on the antrior and lower cardiac wall but also in its lateral and posterior wall. These changes were older and were found in the subendocardial layer or concurrently in another area of the heart with affection of the subepicardial layer. Minor non-transmural fibroses, most frequently on the septum, in some instances spreading to the anterior and lower cardiac wall, were a surprising finding. At present it is not possible to differentiate merely by analysis of the electric cardiac field the X syndrome and ischemic heart disease. This should be made possible by further comparative studies. The present paper is the first description of ischemic and fibrous cardiac changes in X syndrome diagnosed by a complex analysis of the electric cardiac field in the professional literature published in Czechoslovakia and other countries.

[Extracellular and intracellular electrogram of the heart at the site of suction electrodes in frogs]. / Extracelulární a intracelulární elektrogram srdecní v míste prísavné elektrody u záby.

On biological model of current due to damage with the suction electrode on the frog heart atrium in situ was given the survey of epicardial, intracellular and membraneous leads. The following data were found out: 1. Monophase epicardial recording is gradually starting from underpressure values -13.3 kPa to -40.0 kPa in the suction electrode when it is already constant; 2. In the course of sucking the originating monophase recording in lead with the suction electrode is spontaneously disappearing after a longer period (6-10 hrs) and changing into original multiphase one; 3. Intracellular potential up to 0.5 mm round suction electrode is lowered and it thus corresponds to monophase deformation in unipolar extracellular leads in this particular region; 4. After the original fall of the intracellular potential under the suction electrode higher underpressure causes the increase of this potential. Under local loss of membraneous tension the intracellular electrode reaches the branch of demarcation current inbetween the internal and external sides of sound membranes as well as the extracellular electrode.

[The development and disappearance of electrical current in frog heart injuries induced by suction electrodes]. / Vznik a zánik proudu z poskození vyvolaného prísavnou elektrodou na zabím srdci.

Origin and extinction of current due to damage caused by suction electrode on frog heart was studied. By means of epicardial and intracellular leads it was found out that this demarcation current manifests itself only in a very limited space around the place of suction and does not differ from the current due to damage caused by restraint in the coronary bloodstream in hearts of warm-blooded or in myocardial infarction in man. Membrane depolarization degree is diminishing from the place of suction with all accompanying manifestations also in intracellular recordings. The main cause of these changes is the local raised concentration of extracellular potassium ions and the participation of sodium and calcium ions is also being considered. It was proved that this simple biological model of current due to damage is suitable for the study of some changes in electrical heart area and in this way depolarizing and repolarizing parts of the electrocardiogram also in the ischemic heart disease in man.

[Morphologic changes in the heart atrium in frogs after extinction of current due to suction electrode induced damage]. / Morfologické zmeny v zabím komorovém myokardu pod prísavnou elektrodou pri zániku proudu z poskození.

In biological model experiments in frog heart morphological substrate was observed in current extinction due to damage under suction electrode. After short-term suction discharge monophase recording disappeared without demonstrable myocyte ultrastructure changes by means of reparation ad integrum. Monophase recording spontaneously disappeared in distinct changes of monocyte structure with enlarged spaces in between myofibrils, with breakdown of cristae in mitochondria and with dilatation of tubules and cisternae of the endoplasmic reticulum. This tissue disintegration leads to demarcation and forming of new cellular surfaces on the border with the healthy tissue so that the damaged area turns into a mere electric conductor.