Microwave spectra of dinitrotoluene isomers: a new step towards the detection of explosive vapors.

The spectroscopic characterization of explosive taggants used for TNT detection is a research topic of growing interest. We present a gas-phase rotational spectroscopic study of weakly volatile dinitrotoluene (DNT) isomers. The pure rotational spectra of 2,4-DNT and 2,6-DNT were recorded in the microwave range (2-20 GHz) using a Fabry-Perot Fourier-transform microwave (FP-FTMW) spectrometer coupled to a pulsed supersonic jet. Rotational transitions are split by hyperfine quadrupole coupling at the two 14N nuclei leading to up to 9 hyperfine components. The spectral analysis was supported by quantum chemical calculations carried out at the B98/cc-pVTZ and MP2/cc-pVTZ levels of theory. Based on 2D potential energy surfaces at the B98/cc-pVTZ level of theory, the methyl group internal rotation barriers were calculated to be V3 = 515 cm-1 and 698 cm-1 for 2,4- and 2,6-DNT, respectively. Although no splitting due to internal rotation was observed for 2,6-DNT, several splittings were observed for 2,4-DNT. The microwave spectra of both species were fitted using a semi-rigid Hamiltonian accounting for the quadrupole coupling hyperfine structure. Based on the internal axis method (IAM), an additional analysis was performed to retrieve an accurate value of the rotationless A-E tunneling splitting which could be extracted from the rotational dependence of the tunneling splitting. This yielded in the case of 2,4-DNT to an experimental value of 525 cm-1 for the barrier height V3 which agrees well with the DFT value. The coupled internal rotations of -CH3 and -NO2 are investigated in terms of 2-D surfaces, as already done in the case of 2-nitrotoluene [A. Roucou et al., Chem. Phys. Chem., 2020, 21, 2523-2538].

Formation of the methyl cation by photochemistry in a protoplanetary disk.

Forty years ago, it was proposed that gas-phase organic chemistry in the interstellar medium can be initiated by the methyl cation CH3+ (refs. 1-3), but so far it has not been observed outside the Solar System4,5. Alternative routes involving processes on grain surfaces have been invoked6,7. Here we report James Webb Space Telescope observations of CH3+ in a protoplanetary disk in the Orion star-forming region. We find that gas-phase organic chemistry is activated by ultraviolet irradiation.

[Physical activity and lung cancer: A synthesis of the literature]. / Activité physique et cancer broncho-pulmonaire : Synthèse de la littérature.

INTRODUCTION: Physical activity (PA) has its place in the continuum of care, the objective being to limit alterations associated with cancer and its treatments. This review of the literature collates the evidence and current data relating to PA carried out at different periods of treatment for lung cancer. STATE OF THE ART: PA is safe and feasible in patients with lung cancer throughout their oncologic treatment. The efficacy of multimodal programs is demonstrated regarding symptoms, exercise capacity, functional capacity, postoperative complications, length of hospital stay and quality of life. Nevertheless, this result remains to be confirmed with more robust upcoming trial, notably in the long term. PERSPECTIVES: Utilization of activity and energy expenditure sensors or PA questionnaires could help to increase the PA level of lung cancer patients during their continuum of care. For those not at ease with conventional training modalities, it may be judicious to offer intermittent high-intensity training or respiratory muscle strength training. Telerehabilitation could also be implemented. The targeting of populations at high risk should be investigated. CONCLUSION: Teams caring for patients with lung cancer during or after their oncologic treatment should develop innovative strategies designed to overcome difficulties of access or adherence to exercise programs, so that the PA be an integral part of the care of these patients. Physical therapists play an important role in supporting these patients during their assessment or treatment.

[Preparing for thoraco-abdominal surgery: What's in it for the physiotherapist?] / Préparation à une chirurgie thoraco-abdominale : Quelle place pour le masseur-kinésithérapeute ?

INTRODUCTION: Physiotherapy before thoraco-abdominal surgery aims to optimize the patient's cardiorespiratory fitness, in order to limit his alterations in the immediate postoperative period and to reduce postoperative morbidity. This support also aims to make eligible for surgery the patient who is not initially. This review of the literature addresses chest physiotherapy and exercise training that the patient can benefit. STATE OF ART: Scientific evidence remains relatively weak for physiotherapy before thoraco-abdominal surgery, especially for bronchial drainage and incentive spirometry techniques. However, inspiratory muscle training and prehabilitation seem interesting for increasing exercise capacity and reducing morbidity. These last two innovative modalities that can be carried out at home are particularly relevant for patients who present a high risk of complications or who cannot access conventional programs. Smoking cessation, nutritional care and educational support are areas that the physiotherapist must integrate into his practice. PERSPECTIVES: In a decisional algorithm, we suggest 4 types of programs ranging from a simple preoperative education to an intensive multimodal program. This remains to be evaluated in current practice. CONCLUSIONS: The physiotherapist must fully participate in assessing the risk of postoperative morbidity in the context of thoraco-abdominal surgery. He must also identify the most efficient modalities within the delay imposed by the date of surgery. It is also necessary that the latter learn to identify the patient at higher risk of postoperative complications in order to adapt the preoperative management according to the levels of scientific evidence.

In vitro assessment of the role of the nucleus pulposus in the mechanism of vertebral body fracture under dynamic compressive loading using high-speed cineradiography.

Traumatic Spinal Cord Injuries (TSCI) have a disastrous effect on the physical and mental health of both the patients and their relatives. Around 15 % of these injuries are caused by burst fractures, a sub-type of compressive fractures of the vertebral body. The transient dynamics of these fracture have been studied through in vitro experiments coupled with numerical simulations, but no direct observation have ever been made of their genesis and evolution and the behaviour of the nucleus pulposus under compressive loading has only been hypothesized. The purpose of this study was to evaluate the interactions between the vertebral body and the nucleus pulposus under dynamic compressive loading using high-speed cineradiography. A radiopaque agent was injected into the nuclei pulposi of 4 young porcine thoraco-lumbar and lumbar cadaveric segments, and a dynamic compressive load was applied to them using a servo-hydraulic bench-test. The compression process was filmed with a custom high-speed fluoroscope. The nucleus pulposus loaded the vertebral endplate up to 14,142 ± 486 N, before fracturing it and diffusing into the vertebral body. Then, internal pressure seemingly built up until an outward projection of the nucleus pulposus, at an antero-posterior velocity up to 2.9 m.s-1, or until retroprojection of bony fragments into the spinal canal. These results directly corroborate the hypotheses previously made by other studies and stress the unprecedented advantages of using high-speed cineradiography for the study of complex fractures genesis and evolution.Clinical Relevance- Methodology and results from this study would provide an unprecedented insight on the genesis and transient evolution of complex spinal fractures.

Extreme anomalous centrifugal distortion in methylene.

A new treatment is presented to account for the extreme anomalous centrifugal distortion displayed by the open-shell methylene radical. This new treatment is based on a four-dimensional approach in which both the overall rotation and the large amplitude bending mode are treated simultaneously. It accounts for the spin-rotation and spin-spin fine couplings, assumed to depend on the large amplitude bending coordinate, as well as for the hyperfine coupling. The new treatment is tested analyzing the available high-resolution data. 336 transitions, involving the ground and first excited vibrational states of the bending mode, are reproduced with a unitless standard deviation of 1.3, using 42 molecular constants. Compared to a previous analysis [S. Brünken et al., J. Chem. Phys. 123, 164315 (2005)], the present analysis is more satisfactory as it accounts for a larger dataset and the ratio of the number of data to the number of varied constants is larger. The present theoretical treatment also allows us to retrieve the bending potential and the main kinetic energy term.

Quasi-symmetry effects in the threshold photoelectron spectrum of methyl isocyanate.

The vacuum-ultraviolet threshold photoelectron spectrum of methyl isocyanate CH3NCO has been recorded from 10.4 eV to 12 eV using synchrotron radiation and a coincidence technique allowing for a mass-discrimination of the photoelectron signal. A significant improvement is achieved over previous investigations as this experimental setup leads to a much more resolved spectrum. Ten sharp peaks and a broad feature spanning 1.2 eV were recorded. This spectrum consists of X̃+ 2A″←X̃ 1A' and Ã+ 2A'←X̃ 1A' ionizing transitions. For the former, the adiabatic ionization energy was determined experimentally to be 10.596(6) eV; for the latter, its value was estimated to be 10.759(50) eV. Seven sharp peaks could be assigned to vibrational modes of the cation X̃+ 2A″ and neutral X̃ 1A' ground electronic states involving only the NCO group atoms. Theoretical modeling of the threshold photoelectron spectrum has proven difficult as methyl isocyanate is a non-rigid molecule displaying large amplitude internal rotation of the methyl group and ∠CNC bending mode, leading to the quasi-symmetry. With the help of ab initio calculations, a theoretical model in which these two large amplitude motions are included in addition to the five small amplitude vibrational modes involving NCO group atoms is proposed. Comparison with the experimental spectrum shows that the broad feature and the strongest peak line positions are well accounted for; their intensities are also fairly well reproduced after adjusting a few parameters.

Protection against Borreliella burgdorferi infection mediated by a synthetically engineered DNA vaccine.

Lyme disease is the most common vector-borne disease in North America. The etiological agent is the spirochete Borreliella burgdorferi, transmitted to mammalian hosts by the Ixodes tick. In recent years there has been an increase in the number of cases of Lyme disease. Currently, there is no vaccine on the market for human use. We describe the development of a novel synthetically engineered DNA vaccine, pLD1 targeting the outer-surface protein A (OspA) of Borreliella burgdorferi. Immunization of C3 H/HeN mice with pLD1 elicits robust humoral and cellular immune responses that confer complete protection against a live Borreliella burgdorferi bacterial challenge. We also assessed intradermal (ID) delivery of pLD1 in Hartley guinea pigs, demonstrating the induction of robust and durable humoral immunity that lasts at least 1 year. We provide evidence of the potency of pLD1 by showing that antibodies targeting the OspA epitopes which have been associated with protection are prominently raised in the immunized guinea pigs. The described study provides the basis for the advancement of pDL1 as a potential vaccine for Lyme disease control.

The Pentose Phosphate Pathway Dynamics in Cancer and Its Dependency on Intracellular pH.

The Pentose Phosphate Pathway (PPP) is one of the key metabolic pathways occurring in living cells to produce energy and maintain cellular homeostasis. Cancer cells have higher cytoplasmic utilization of glucose (glycolysis), even in the presence of oxygen; this is known as the "Warburg Effect". However, cytoplasmic glucose utilization can also occur in cancer through the PPP. This pathway contributes to cancer cells by operating in many different ways: (i) as a defense mechanism via the reduced form of nicotinamide adenine dinucleotide phosphate (NADPH) to prevent apoptosis, (ii) as a provision for the maintenance of energy by intermediate glycolysis, (iii) by increasing genomic material to the cellular pool of nucleic acid bases, (iv) by promoting survival through increasing glycolysis, and so increasing acid production, and (v) by inducing cellular proliferation by the synthesis of nucleic acid, fatty acid, and amino acid. Each step of the PPP can be upregulated in some types of cancer but not in others. An interesting aspect of this metabolic pathway is the shared regulation of the glycolytic and PPP pathways by intracellular pH (pHi). Indeed, as with glycolysis, the optimum activity of the enzymes driving the PPP occurs at an alkaline pHi, which is compatible with the cytoplasmic pH of cancer cells. Here, we outline each step of the PPP and discuss its possible correlation with cancer.

Renner-Teller effects in the photoelectron spectra of CNC, CCN, and HCCN.

The line intensity of photoelectron spectra when either the neutral or cationic species display a Renner-Teller coupling is derived and applied to the modeling of the photoelectron spectra of CNC, CCN, and HCCN. The rovibronic energy levels of these three radicals and of their cations are investigated starting from ab initio results. A model treating simultaneously the bending mode and the overall rotation is developed to deal with the quasilinearity problem in CNC+, CCN+, and HCCN and accounts for the large amplitude nature of their bending mode. This model is extended to treat the Renner-Teller coupling in CNC, CCN, and HCCN+. Based on the derived photoelectron line intensity, the photoelectron spectra of all three molecules are calculated and compared to the experimental ones.

Experimental and theoretical investigations of H2O-Ar.

We have used continuous-wave cavity ring-down spectroscopy to record the spectrum of H2O-Ar in the 2OH excitation range of H2O. 24 sub-bands have been observed. Their rotational structure (Trot = 12 K) is analyzed and the lines are fitted separately for ortho and para species together with microwave and far infrared data from the literature, with a unitless standard deviation σ=0.98 and 1.31, respectively. Their vibrational analysis is supported by a theoretical input based on an intramolecular potential energy surface obtained through ab initio calculations and computation of the rotational energy of sub-states of the complex with the water monomer in excited vibrational states up to the first hexad. For the ground and (010) vibrational states, the theoretical results agree well with experimental energies and rotational constants in the literature. For the excited vibrational states of the first hexad, they guided the assignment of the observed sub-bands. The upper state vibrational predissociation lifetime is estimated to be 3 ns from observed spectral linewidths.

Valence shell threshold photoelectron spectroscopy of the CHxCN (x = 0-2) and CNC radicals.

We present the photoelectron spectroscopy of four radical species, CHxCN (x = 0-2) and CNC, formed in a microwave discharge flow-tube reactor by consecutive H abstractions from CH3CN (CHxCN + F → CHx-1CN + HF (x = 1-3)). The spectra were obtained combining tunable vacuum ultraviolet synchrotron radiation with double imaging electron/ion coincidence techniques, which yielded mass-selected threshold photoelectron spectra. The results obtained for H2CCN complement existing ones while for the other radicals the data represent the first observation of their (single-photon) ionizing transitions. In the case of H2CCN, Franck-Condon calculations have been performed in order to assign the vibrational structure of the X+ 1A1←X 2B1 ionizing transition. A similar treatment for the HCCN, CCN, and CNC radicals appeared to be more complicated mainly because a Renner-Teller effect strongly affects the vibrational levels of the ground electronic state of the HCCN+, CCN, and CNC species. Nevertheless, the first adiabatic ionization energies of these radicals are reported and compared to our ab initio calculated values, leading to new values for enthalpies of formation (ΔfH2980(HCCN+(X2A'))=1517±12kJmol-1,ΔfH2980(CCN(X2Π))=682±13kJmol-1, and ΔfH2980(CNC(X2Πg))=676±12kJmol-1), which are of fundamental importance for astrochemistry.

Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2═CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene.

The ground-state rotational spectrum of propene-3-d1, CH2═CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.

Ab initio intermolecular potential of Ar-C2H2 refined using high-resolution spectroscopic data.

The high-resolution infrared spectra of the ν1 + ν3 (2CH) band of the Ar-C2H2 complex has been recorded from 6544 to 6566 cm(-1). The previously reported K(a) = 1 ← 0, 2 ← 1, and 0 ← 1 subbands were observed and the K(a) = 1 ← 2, 2 ← 3, and 3 ← 2 subbands were assigned for the first time. The intermolecular potential energy surface of this complex has been calculated ab initio and optimized by fitting the new high-resolution data. Refined intermolecular potential energy surfaces have been obtained for the ground vibrational state and for the excited v1 = v3 = 1 stretching state. For the former state, the results of the analysis are satisfactory and the microwave transitions of the complex are reproduced with a root-mean-square deviation of 5 MHz. For the latter state, systematic discrepancies arise in the analysis.

Impact of arachidonic acid enrichment of live rotifer prey on bacterial communities in rotifer and larval fish cultures.

Rotifers (Brachionus plicatilis), commonly used at first feeding in commercial fish hatcheries, carry a large bacteria load. Because they are relatively poor in essential fatty acids, it is common practice to enrich them with fatty acids, including arachidonic acid (AA). This study aims to determine whether prey enrichment with AA may act as a prebiotic and modify the microbial community composition either in AA-enriched rotifer cultures or in larval-rearing water using winter flounder (Pseudopleuronectes americanus) as a larval fish model. AA enrichment modified the bacterial community composition in both the rotifer culture tanks and the larval-rearing tanks. We observed an increase in the number of cultivable bacteria on TCBS (thiosulfate-citrate-bile salts-sucrose) agar, used as a proxy for the abundance of Vibrio sp. The results suggest that AA may also play an indirect role in larval health.

The plant TPX2 protein regulates prospindle assembly before nuclear envelope breakdown.

The Targeting Protein for Xklp2 (TPX2) is a central regulator of spindle assembly in vertebrate cells. The absence or excess of TPX2 inhibits spindle formation. We have defined a TPX2 signature motif that is present once in vertebrate sequences but twice in plants. Plant TPX2 is predominantly nuclear during interphase and is actively exported before nuclear envelope breakdown to initiate prospindle assembly. It localizes to the spindle microtubules but not to the interdigitating polar microtubules during anaphase or to the phragmoplast as it is rapidly degraded during telophase. We characterized the Arabidopsis thaliana TPX2-targeting domains and show that the protein is able to rescue microtubule assembly in TPX2-depleted Xenopus laevis egg extracts. Injection of antibodies to TPX2 into living plant cells inhibits the onset of mitosis. These results demonstrate that plant TPX2 already functions before nuclear envelope breakdown. Thus, plants have adapted nuclear-cytoplasmic shuttling of TPX2 to maintain proper spindle assembly without centrosomes.

Ab initio and experimental studies of the large-amplitude motion in BF2OH.

The ground state rotational spectrum of BF2OH was measured under high resolution by microwave Fourier transform spectroscopy (FTMW), and the small torsional splitting could be resolved for several lines. This splitting was analyzed using a phenomenological model previously developed for HNO3 [Coudert and Perrin, J. Mol. Spectrosc. 1995, 172, 352] and with the help of the geometries of the stationary points calculated ab initio. The torsional splitting was also calculated using the results of the calculations for the ground vibrational state, for the excited OH torsional states 91 and 92, and for the excited BOH bending state 41, and a satisfactory agreement with available experimental data was found.

Myasthenia gravis exacerbation or unmasking associated with telithromycin treatment.

Telithromycin, a new ketolide antibiotic, has been implicated in the exacerbation or unmasking of myasthenia gravis. This retrospective study presents two clinical reports and summarizes eight other suspected cases notified to the French pharmacovigilance system, highlighting a potentially life-threatening risk of telithromycin treatment in myasthenic patients. An important common feature was that, in seven cases, symptomatology occurred within 2 hours of first telithromycin intake--notably in cases of severe exacerbation.

Quantitative SUMO-1 modification of a vaccinia virus protein is required for its specific localization and prevents its self-association.

Vaccinia virus (VV), the prototype member of the Poxviridae, a family of large DNA viruses, carries out DNA replication in specialized cytoplasmic sites that are enclosed by the rough endoplasmic reticulum (ER). We show that the VV gene product of A40R is quantitatively modified by SUMO-1, which is required for its localization to the ER-enclosed replication sites. Expression of A40R lacking SUMO-1 induced the formation of rod-shaped cytoplasmic aggregates. The latter likely consisted of polymers of nonsumoylated protein, because unmodified A40R interacted with itself, but not with the SUMO-1-conjugated protein. Using a bacterial sumoylation system, we furthermore show that unmodified A40R is mostly insoluble, whereas the modified form is completely soluble. By electron microscopy, the A40R rods seen in cells were associated with the cytosolic side of the ER and induced the apposition of several ER cisternae. A40R is the first example of a poxvirus protein to acquire SUMO-1. Its quantitative SUMO-1 modification is required for its proper localization to the viral "mini-nuclei" and prevents its self-association. The ability of the nonsumoylated A40R to bring ER membranes close together could suggest a role in the fusion of ER cisternae when these coalesce to enclose the VV replication sites.