Near-thermo-neutral electron recombination of titanium oxide ions.

While the dissociative recombination (DR) of ground-state molecular ions with low-energy free electrons is generally known to be exothermic, it has been predicted to be endothermic for a class of transition-metal oxide ions. To understand this unusual case, the electron recombination of titanium oxide ions (TiO+) with electrons has been experimentally investigated using the Cryogenic Storage Ring. In its low radiation field, the TiO+ ions relax internally to low rotational excitation (≲100 K). Under controlled collision energies down to ∼2 meV within the merged electron and ion beam configuration, fragment imaging has been applied to determine the kinetic energy released to Ti and O neutral reaction products. Detailed analysis of the fragment imaging data considering the reactant and product excitation channels reveals an endothermicity for the TiO+ dissociative electron recombination of (+4 ± 10) meV. This result improves the accuracy of the energy balance by a factor of 7 compared to that found indirectly from hitherto known molecular properties. Conversely, the present endothermicity yields improved dissociation energy values for D0(TiO) = (6.824 ± 0.010) eV and D0(TiO+) = (6.832 ± 0.010) eV. All thermochemistry values were compared to new coupled-cluster calculations and found to be in good agreement. Moreover, absolute rate coefficients for the electron recombination of rotationally relaxed ions have been measured, yielding an upper limit of 1 × 10-7 cm3 s-1 for typical conditions of cold astrophysical media. Strong variation of the DR rate with the TiO+ internal excitation is predicted. Furthermore, potential energy curves for TiO+ and TiO have been calculated using a multi-reference configuration interaction method to constrain quantum-dynamical paths driving the observed TiO+ electron recombination.

Isochronous mass spectrometry in an electrostatic storage ring.

For sensitive studies of molecular ions in electrostatic storage rings, the exact knowledge of the isobaric composition of stored beams from a variety of ion sources is essential. Conventional mass-filtering techniques are often inefficient to resolve the beam components. Here, we report the first isochronous mass spectrometry in an electrostatic storage ring, which offers a high mass resolution of Δm/m < 1 × 10-5 even for heavy molecular species with m > 100 u and uncooled ion beams. Mass contaminations can be resolved and identified at relative fractions down to 0.02%.

Laser Probing of the Rotational Cooling of Molecular Ions by Electron Collisions.

We present state-selected measurements of rotational cooling and excitation rates of CH^{+} molecular ions by inelastic electron collisions. The experiments are carried out at a cryogenic storage ring, making use of a monoenergetic electron beam at matched velocity in combination with state-sensitive laser dissociation of the CH^{+} ions for simultaneous monitoring of the rotational level populations. Employing storage times of up to 600 s, we create conditions where electron-induced cooling to the J=0 ground state dominates over radiative relaxation, allowing for the experimental determination of inelastic electron collision rates to benchmark state-of-the-art theoretical calculations. On a broader scale, our experiments pave the way to probe inelastic electron collisions for a variety of molecular ions relevant in various plasma environments.

Quantum-state-selective electron recombination studies suggest enhanced abundance of primordial HeH.

The epoch of first star formation in the early Universe was dominated by simple atomic and molecular species consisting mainly of two elements: hydrogen and helium. Gaining insight into this constitutive era requires a thorough understanding of molecular reactivity under primordial conditions. We used a cryogenic ion storage ring combined with a merged electron beam to measure state-specific rate coefficients of dissociative recombination, a process by which electrons destroy molecular ions. We found a pronounced decrease of the electron recombination rates for the lowest rotational states of the helium hydride ion (HeH+), compared with previous measurements at room temperature. The reduced destruction of cold HeH+ translates into an enhanced abundance of this primordial molecule at redshifts of first star and galaxy formation.

An efficient, movable single-particle detector for use in cryogenic ultra-high vacuum environments.

A compact, highly efficient single-particle counting detector for ions of keV/u kinetic energy, movable by a long-stroke mechanical translation stage, has been developed at the Max-Planck-Institut für Kernphysik (Max Planck Institute for Nuclear Physics, MPIK). Both, detector and translation mechanics, can operate at ambient temperatures down to ∼10 K and consist fully of ultra-high vacuum compatible, high-temperature bakeable, and non-magnetic materials. The set-up is designed to meet the technical demands of MPIK's Cryogenic Storage Ring. We present a series of functional tests that demonstrate full suitability for this application and characterise the set-up with regard to its particle detection efficiency.

Coulomb explosion imaged cryptochiral (R,R)-2,3-dideuterooxirane: unambiguous access to the absolute configuration of (+)-glyceraldehyde.

The absolute configuration of (R,R)-2,3-dideuterooxirane, which has been independently determined using Coulomb explosion imaging, has been unambiguously chemically correlated with the stereochemical key reference (+)-glyceraldehyde. This puts the absolute configuration of D(+)-glyceraldehyde on firm experimental grounds.

Imaging the absolute configuration of a chiral epoxide in the gas phase.

In chemistry and biology, chirality, or handedness, refers to molecules that exist in two spatial configurations that are incongruent mirror images of one another. Almost all biologically active molecules are chiral, and the correct determination of their absolute configuration is essential for the understanding and the development of processes involving chiral molecules. Anomalous x-ray diffraction and vibrational optical activity measurements are broadly used to determine absolute configurations of solid or liquid samples. Determining absolute configurations of chiral molecules in the gas phase is still a formidable challenge. Here we demonstrate the determination of the absolute configuration of isotopically labeled (R,R)-2,3-dideuterooxirane by foil-induced Coulomb explosion imaging of individual molecules. Our technique provides unambiguous and direct access to the absolute configuration of small gas-phase species, including ions and molecular fragments.

Storage ring measurements of the dissociative recombination of H3+.

The dissociative recombination (DR) of H(3)(+) is a key process in interstellar chemistry. More than 30 experimental studies of the DR process have been published in the literature. The H(3)(+) DR rate coefficient results obtained from these measurements, however, have not always been consistent. The outcome seems to depend on the experimental method, on the exact measurement procedure and sometimes even on the interpretation of the experimental data. In the past two decades, heavy-ion storage rings have become the working horse for DR measurements, as they provide a direct measurement of the DR products. Furthermore, storage ring measurements yield energy-resolved rate coefficients with unprecedented resolution that allow for detailed comparison with theory. DR results from different storage ring facilities have shown a remarkable consistency throughout the years and they provide additional information on break-up dynamics and internal excitation. In this study, we will review the storage ring DR measurements that have been carried out for H(3)(+).

Cervical spondylotic myelopathy: conservative versus surgical treatment after 10 years.

It is not known whether the results of decompressive surgery to treat the mild and moderate forms of spondylotic cervical myelopathy (CSM) are any better than those of a conservative approach. A 10-year prospective randomised study was performed. The objective of the study was to compare conservative and operative treatments of mild and moderate, non-progressive, or slowly progressive, forms of CSM. Sixty-four patients were randomised into two groups of 32. Group A was treated conservatively while group B was treated surgically. The clinical outcome was evaluated by modified JOA score, timed 10-m walk, score of daily activities recorded by video and evaluated by two observers blinded to the type of therapy, and by subjective assessment by the patients themselves. Seventeen patents died of natural, unrelated causes, during the follow-up. A total of 25 patients in the conservatively and 22 in the surgically treated group were used for the final evaluation. There was no statistically significant difference between both groups in mJOA score, in subjective evaluation by the patients themselves and in evaluation of video-recordings of daily living activities by two observers blinded to treatment mode. There was neither any difference found in the percentage of patients losing the ability to walk nor in the time taken to cover the 10-m track from a standing start. Comparison of conservative and surgical treatment in mild and moderate forms of CSM in a 10-year follow-up has not shown, on average, a significant difference in results. In both groups, patients get better and worse. According to the power analysis it is necessary admit that these results possess the low ability to answer definitely the question which treatment is better for the patients with a mild and moderate non-progressive CSM because of the low number of patients for the final evaluation and for clinically negligible differences between two compared arms. These findings can serve as a worthy odds-on hypothesis which needs the confirmation.

Are subjects with spondylotic cervical cord encroachment at increased risk of cervical spinal cord injury after minor trauma?

The aim of the study was to analyse the risk of symptomatic myelopathy after minor trauma in patients with asymptomatic spondylotic cervical spinal cord encroachment (ASCCE). In a cohort of 199 patients with ASCCE, previously followed prospectively in a study investigating progression into symptomatic myelopathy, the authors looked retrospectively for traumatic episodes that may have involved injury to the cervical spine. A questionnaire and data file analysis were employed to highlight whatever hypothetical relationship might emerge with the development of symptomatic myelopathy. Fourteen traumatic episodes in the course of a follow-up of 44 months (median) were recorded in our group (who had been instructed to avoid risky activities), with no significant association with the development of symptomatic myelopathy (found in 45 cases). Only three minor traumatic events without fracture of the cervical spine were found among the symptomatic myelopathy cases, with no chronological relationship between trauma and myelopathy. Furthermore, 56 traumatic spinal cord events were found before the diagnosis of cervical cord encroachment was established, with no correlation to either type of compression (discogenic vs osteophytic). In conclusion, the risk of spinal cord injury after minor trauma of the cervical spine in patients with ASCCE appeared to be low in our cohort provided risky activities in these individuals are restricted. Implementation of preventive surgical decompression surgery into clinical practice in these individuals should be postponed until better-designed studies provide proof enough for it to take precedence over a conservative approach.

Fragmentation channels in dissociative electron recombination with hydronium and other astrophysically important species.

We report on our recent studies of dissociative recombination (DR) employing two different fragment imaging detection techniques at the TSR storage ring in Heidelberg, Germany. Principles of an upgraded 3D optical system and the new energy-sensitive multistrip detector (EMU) are explained together with possible applications in reaction dynamics studies. With the EMU imaging detector we succeeded to observe the branching ratios after DR of deuterated hydronium ions D(3)O(+) at energies of 0-0.5 and 4-21 eV. The branching ratios are almost constant at low energies while above 6 eV both oxygen-producing channels O + D + D + D and O + D(2) + D strongly increase and dominate by about 85% at 11 eV. To demonstrate further capabilities of our fragment imaging detectors, we also summarize some of our additional recent studies on DR of molecular ions important for astrophysics as well as for fundamental unimolecular dynamics.

Presymptomatic spondylotic cervical myelopathy: an updated predictive model.

Spondylotic cervical cord compression detected by imaging methods is a prerequisite for the clinical diagnosis of spondylotic cervical myelopathy (SCM). Little is known about the spontaneous course and prognosis of clinically "silent" presymptomatic spondylotic cervical cord compression (P-SCCC). The aim of the present study was to update a previously published model predictive for the development of clinically symptomatic SCM, and to assess the early and late risks of this event in a larger cohort of P-SCCC subjects. A group of 199 patients (94 women, 105 men, median age 51 years) with magnetic resonance signs of spondylotic cervical cord compression, but without clear clinical signs of myelopathy, was followed prospectively for at least 2 years (range 2-12 years). Various demographic, clinical, imaging, and electrophysiological parameters were correlated with the time for the development of symptomatic SCM. Clinical evidence of the first signs and symptoms of SCM within the follow-up period was found in 45 patients (22.6%). The 25th percentile time to clinically manifested myelopathy was 48.4 months, and symptomatic SCM developed within 12 months in 16 patients (35.5%). The presence of symptomatic cervical radiculopathy and electrophysiological abnormalities of cervical cord dysfunction detected by somatosensory or motor-evoked potentials were associated with time-to-SCM development and early development (< or =12 months) of SCM, while MRI hyperintensity predicted later (>12 months) progression to symptomatic SCM. The multivariate predictive model based on these variables correctly predicted early progression into SCM in 81.4% of the cases. In conclusion, electrophysiological abnormalities of cervical cord dysfunction together with clinical signs of cervical radiculopathy and MRI hyperintensity are useful predictors of early progression into symptomatic SCM in patients with P-SCCC. Electrophysiological evaluation of cervical cord dysfunction in patients with cervical radiculopathy or back pain is valuable. Meticulous follow-up is justified in high-risk P-SCCC cases.

Laboratory measurements of the recombination of PAH ions with electrons: implications for the PAH charge state in interstellar clouds.

Laboratory measurements of the recombination of polycyclic aromatic hydrocarbon (PAH) ions with electrons are presented. Experimental data have been obtained at room temperature for azulene (C10H8) and acenaphthene (C12H10) cations by the Flowing Afterglow with PhotoIons method. The results confirm that the recombination of PAH ions is fast although well below the geometrical limit. The set of our recent and present measurements reveal a definite trend of increasing rate with the number of carbon atoms of the PAH. This behaviour that needs further characterization is potentially of great interest for charge state models as recombination is a dominant mechanism of PAH ion destruction in the interstellar medium. The design of experiments to measure the recombination of larger PAHs and their temperature dependence is discussed.

Presymptomatic spondylotic cervical cord compression.

STUDY DESIGN: We conducted a cohort study of clinically asymptomatic spondylotic cervical cord compression cases with the primary end point of the development of clinical signs of cervical myelopathy. OBJECTIVES: To investigate whether various demographic, clinical, radiologic, and electrophysiological parameters could predict progression from clinically asymptomatic (preclinical) spondylotic cervical cord compression to symptomatic myelopathy. SUMMARY OF BACKGROUND DATA: The data available on the prediction of the outcome in surgical and conservative treatment of spondylotic cervical myelopathy are controversial. Little is known about the clinical natural history of asymptomatic magnetic resonance image-detected spondylotic cervical cord compression and/or changes of signal intensity. METHODS: A group of 66 patients (32 women, 34 men, median age 50 years) with magnetic resonance signs of spondylotic cervical cord compression but without clear clinical signs of myelopathy was followed prospectively for at least 2 years (range, 2-8 years; median, 4 years). Various demographic, clinical, imaging, and electrophysiological parameters were correlated with clinical outcome. RESULTS: Clinical signs of myelopathy during the follow-up period were detected in 13 patients (19.7%). The only variables significantly associated with the development of clinically symptomatic spondylotic cervical myelopathy (SCM) were the presence of symptomatic cervical radiculopathy, electromyographic signs of anterior horn lesion, and abnormal somatosensory-evoked potentials. A multivariate logistic regression model based on these variables correctly classified 90% of cases into 2 subgroups: a group with development of symptomatic SCM and that without clinical manifestation of subclinical cervical cord compression. CONCLUSIONS: Electrophysiological abnormalities together with clinical signs of cervical radiculopathy could predict clinical manifestation of preclinical spondylotic cervical cord compression.

Approaches to spondylotic cervical myelopathy: conservative versus surgical results in a 3-year follow-up study.

STUDY DESIGN: A 3-year prospective randomized study was conducted. OBJECTIVE: To compare conservative and operative treatments of mild and moderate, nonprogressive, and slowly progressive forms of spondylotic cervical myelopathy. SUMMARY OF BACKGROUND: DATA It is not known whether the results of decompressive surgery for the mild and moderate forms of spondylotic cervical myelopathy are any better than those of the conservative approach. METHODS: For this study, 68 patients were randomized into two groups. Group A, treated conservatively, consisted of 35 subjects, whereas Group B, treated surgically, was composed of 33 patients. The clinical outcome was evaluated by modified JOA score, timed 10-m walk, the score for daily activities recorded by video and evaluated by two observers blinded to the type of therapy, and subjective assessment by the patients themselves at months 6, 12, 24, and 36 of the follow-up period. RESULTS: There was, on the average, no significant deterioration in mJOA score in the two groups over the 3-year follow-up period, but there was a slightly expressed decrease in the self-evaluation score in Group B, and a slight deterioration of the score for daily activities in Group A. Comparison of the two groups showed a significant difference in the timed 10-m walk test favoring group A, but no difference in mJOA score or self-evaluation by the patients themselves, with the exception of a better score at month 6 in favor of Group B. CONCLUSIONS: The 3-year follow-up study did not show, on the average, that the surgery is superior to conservative treatment for mild and moderate forms of spondylotic cervical myelopathy.