A clear and positive correlation between the CO2 concentration and the blood-sugar level has been observed via a non-invasive and time-dependent monitoring of CO2 concentration from human breath, ...which is carried out by using a home-made gas chromatography (GC)/milli-whistle compact analyzer. The time-dependent sampling of the CO2 concentration correlated between 5.0 to 5.6% (1% = 104 ppm) in accordance with blood-sugar level variations of 80 to 110 mg/dL. The analytical method results in a rapid, continuous and non-invasive determination of blood-sugar level via measurement of the CO2 concentration exhaled from the lungs.
Recent experimental and theoretical advances in the study of the dissociation of excited molecules are revealing unexpected mechanisms, when their outcomes are tackled by combining (i) space-time ion ...imaging of translational features, with (ii) spectroscopic probing of rotational and vibrational distributions; crucial is the assistance of (iii) the quantum chemistry of structural investigations of rearrangements of chemical bonds, and of (iv) the simulations of molecular dynamics to follow the evolution of selective bond stretching and breaking. Here we present results of such an integrated approach to methyl formate, HCOOCH3, the simplest of esters; the main focus is on the rotovibrationally excited CO (v=1) product and in general on the energy distribution in the fragments. Previous laser studies of dissociation into CO and CH3OH at a sequence of various wavelengths discovered signatures of a roaming mechanism by the late arrival of CO (v=0) products in time-of-flight ion imaging. Subsequent detailed investigations as a function of excitation energy provided the assessment of the threshold, which opens for triple breakdown into CO and further fragments H and CH3O, as spectroscopically characterized by ion imaging and FTIR respectively. Accompanying quantum mechanical electronic structure calculations and classical molecular dynamics simulations clarify the origin of these fragments through "roaming" pathways involving incipient radical intermediates at energies below the triple fragmentation threshold: a specific role is played by nonadiabatic transitions at a conical intersection between ground and excited states; alternative pathways focalize our attention to regions of the potential energy surfaces other than those in the neighbourhoods of saddle points along minimum energy paths: eventually this leads us to look for avenues in reaction kinetics beyond those of venerable transition state theories.
Orientation of the chiral molecule propylene oxide with respect to the direction of the orienting field F. The principal axes a, b, and c, the dipole moment μ and the angle θ, given by the ...intersection of the component of the dipole moment with respect to the axis b and the orienting field F, are shown. Display omitted
► Supersonic beams of chiral molecule propylene oxide are selected by electrostatic hexapole. ► Pure and He or Ar seeded beams are investigated by time of flight and mass spectrometric detection. ► Focusing curves are analyzed to provide alignment and rotational distributions. ► Simulations involve full diagonalization of Stark matrices and account of avoided crossings. ► Orientational distributions for photochemical and scattering experiments are exhibited.
This theoretical study is complementary to previous experimental work (see D.-C. Che, F. Palazzetti, Y. Okuno, V. Aquilanti, T. Kasai, J. Phys. Chem. A 114 (2010) 3280) on the orientation and rotational state-selection of supersonic molecular beams of the asymmetric-top molecule propylene oxide, both pure and seeded (in He and in Ar) by using an 85-cm length hexapole state-selector. One objective is to obtain an accurate distribution of the rotational states after hexapole selection for the three molecular beams, the most relevant feature consisting in the evaluation of the variation in energy of the manifold of rotational states when an electric field is applied (the Stark forces). Previously, the Stark effect on the effective dipole moment was considered through second order for all rotational states, while in this work the energy derivatives of the rotational states with respect to the applied electric field, are obtained accurately by diagonalizing the very large Stark matrices, whose elements depend on the dipole moment components of the molecule. The Stark energies and the corresponding forces were calculated for values of the electric field between 0 and 80kVcm−1 in steps of 0.5kVcm−1 and then linearly interpolated, covering the whole experimental range of the hexapole. A treatment is given for the intricate pattern of avoided crossings among derivatives of the rotational levels and two limiting cases were considered, corresponding to transitions occurring either adiabatically or diabatically. The two treatments lead to slightly different distributions of the rotational states for the pure and Ar seeded molecular beams, while for the He seeded molecular beam the two distributions are substantially the same. This experimental arrangement is a perspective tool for experiments of photochemistry and scattering of oriented molecules and clusters, and therefore we calculated the orientational distributions in a configuration where a uniform electric field is placed between the hexapole field and the detector.
Patients with malignant diseases may develop symptoms of superior vena cava syndrome (SVCS) quickly because rapid tumor growth does not allow adequate time to develop collateral blood flow. ...Therefore, malignant SVCS is a medical emergency associated with neurological or pharyngeal-laryngeal signs. Recently, interventional endovascular treatment (EVT) has achieved acceptable results. We describe the case of a 55-year-old woman with pulmonary adenocarcinoma and laryngeal edema. In the first EVT, bare-metal-stent was implanted into the SVCS with intravascular ultrasound (IVUS) guidance. The IVUS showed insufficient stent-mid expansion. We did not use additional ballooning because of the risk of superior vena cava (SVC) rupture. Three months later, the SVCS recurred. A second EVT was performed, and IVUS imaging suggested tumor ingrowth into the SVC through the stent struts. We considered that the tumor ingrowth could be covered in the SVC using stent-graft. The patient showed no recurrence of SVCS for about 12 months. IVUS-guided implantation of stent for the treatment of malignant SVCS has not been reported. This case report revealed that stent therapy using IVUS for SVCS is useful.
Superior vena cava syndrome (SVCS) due to malignancy is not rare. Recently, endovascular treatment for SVCS has achieved acceptable results. However, SVC stenting in SVCS as having primary patency rate varies for each report. Intravascular ultrasound (IVUS) guided implantation of stent for malignant SVCS treatment has not been reported. In this case, we suspected insufficient stent expansion and tumor ingrowth as the possible cause of in-stent restenosis. Therefore, stent therapy using IVUS for malignant SVCS can be helpful.
An alternative to the transition state (TS) pathway, the roaming route, which bypasses the minimum energy path but produces the same molecular products, was recently found in photodissociation ...dynamics. This account describes signatures of roaming in photodissociation of the carbonyl compounds, specifically methyl formate and aliphatic aldehydes. Methyl formate was promoted to the excited state, followed by internal conversion via a conical intersection. Then, the energetic precursor dissociated to fragments which proceeded along either TS or roaming path. In contrast to the lack of a roaming saddle point found in methyl formate, the structure of the roaming saddle point for each of a series of aliphatic aldehydes comprises two moieties that are weakly bound at a distance. As its size increases, the energy difference between the TS barrier and the roaming saddle point increases and the roaming pathway becomes increasingly dominant. Experimentally, the rotational-level dependence of the roaming route was measured with ion imaging, while the vibrational-state dependence was observed with time-resolved Fourier-transform infrared emission spectroscopy. The roaming signature was verified theoretically by quasi-classical trajectory (QCT) calculations. As an alternative to the QCT method, a multi-center impulsive model was developed to simulate the roaming scalar and vector properties.
Since the advent of the pneumococcal vaccine, cases of infective endocarditis (IE) from Streptococcus pneumoniae have become rare. Pneumococcal endocarditis (PE) may be the initial presentation in ...Austrian syndrome, which is very lethal. PE needs early detection and treatment and more commonly develops from pneumonia. To our knowledge, this is the first report of PE caused by sinusitis after pneumococcal vaccination. Here, a 71-year-old male presented with low back pain and right ankle joint pain. He had no dental history or pneumonia and received a pneumococcal vaccine 2 years prior. Blood tests showed high inflammatory response. We suspected IE due to the high inflammatory response and oligoarthritis. Transthoracic echocardiography showed vegetation at the aortic valve. As IE was probable, empiric antibiotic therapy was promptly initiated. Blood cultures detected S. pneumoniae. IE was diagnosed based on Duke's diagnostic criteria. After starting antibiotic treatment, lumbar magnetic resonance imaging (MRI) showed an abscess in the right erector spinae. Cranial MRI showed bilateral maxillary sinusitis. Sinusitis was considered the possible initial focus of infection. IE should be considered a differential in patients with S. pneumoniae detected in blood cultures without pneumonia even after pneumococcal vaccination as PE sometimes follows a fatal course.
<Learning objective: Pneumococcal endocarditis (PE) is rare and can be fatal when there is diagnostic delay. It may be less likely to exhibit characteristic skin lesions of infective endocarditis (IE). Clinicians should include IE in the differential diagnoses for cases of Streptococcus pneumoniae detected in blood cultures without pneumonia. Transthoracic echocardiography is also useful for early detection and treatment of PE.>
A 45-year-old man with a history of bronchial asthma had fever and elevated eosinophils on the day of surgery for sinusitis, resulting in cancellation of the surgery. Two days later, he was referred ...to our department for electrocardiographic abnormalities. We suspected eosinophilic myocarditis (EM) since he presented with fever, left ventricular hypokinesis, and hypertrophy on echocardiography, and eosinophilia with elevated cardiac enzymes. We immediately performed an endomyocardial biopsy that showed eosinophilic infiltration of the myocardium. He was diagnosed with eosinophilic granulomatosis with polyangiitis (EGPA) since he suffered from asthma, eosinophilia, sinusitis, and EM. Methylprednisolone pulse therapy followed by oral prednisolone and intravenous cyclophosphamide pulse therapy decreased his eosinophils to within the normal range, and his symptoms subsequently improved. In EGPA, cardiac involvement is less commonly seen compared to other organ involvement. Moreover, patients with EGPA who have cardiac involvement generally have other organ involvement as well. In this report, the patient had only cardiac involvement as organ damage associated with EGPA, except for asthma and sinusitis in the prodromal phase, making it clear that patients with EGPA could present with cardiac involvement alone. Therefore, it is recommended to thoroughly examine for cardiac involvement in patients with suspected EGPA.
We report a case of eosinophilic granulomatosis with polyangiitis (EGPA) presenting with cardiac involvement alone as organ damage, subsequently diagnosed with eosinophilic myocarditis as confirmed by an endomyocardial biopsy. EGPA usually involves other organs in addition to the cardiovascular system; however, patients with EGPA could present with cardiac involvement alone, as in this case. Thus, we should thoroughly investigate for cardiac involvement in patients with suspected EGPA.
Production, characterization and control of polarization states of molecules (specifically, alignment and/or orientation) are of importance for investigating in detail the stereodynamics of ...elementary processes involving elastic, inelastic and reactive events and also to prepare targets for selective photodynamical investigations. The focus here is on those molecular beam techniques which show perspectives in the applications offering appealing features for "duty cycle" and intensity characteristics. After a review of the basic experimental advances, mainly obtained in the last ten years, the attention will be addressed to recent studies carried out on the collisional alignment of hydrocarbon molecules and on orientation of symmetric top molecules by exploiting honeycomb hexapole fields. The first case is a prototype of "natural" polarization techniques, the second one of those where polarization is "forced" by external fields.
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