Orientation effects in inelastic collisions of OH(X 2Π)+Ar at an energy of 746 cm−1 have been studied in a crossed molecular beam experiment. The OH(X 2Π) radicals were prepared in the v=0, Ω=32, J=32, f state by hexapole state selection and oriented with their O-end or H-end towards the Ar atom by a static electric field in the collision zone. The orientation-dependent probability density function has been determined by laser induced fluorescence spectroscopy using a narrow band dye laser and the Stark mixing induced P1′(1) transition. A degree of orientation of 〈cos θ〉=0.55 has been obtained. The steric asymmetry factor has been determined for rotational excitation up to the Ω=32, J=92 and Ω=12, J=52 states. Differences up to a factor of 8 in cross section were found between O-end and H-end impact. In general a slight preference for O-end impact was found for low rotational excitation, while a strong preference for H-end impact was found for excitation to high rotational states. The experimental results are compared to quantum scattering calculations on ab initio potential energy surfaces developed by Degli-Esposti and Werner [J. Chem. Phys. 93, 3351 (1990)] and Klos et al. [J. Chem. Phys. 112, 4952 (2000)]. The agreement between experiment and calculations based on the Klos and Chalasinski potential is excellent for transitions to states of A″ symmetry and good for transitions to states of A′ symmetry.

ObjectivesIn rheumatoid arthritis (RA), treat-to-target strategies require instruments for valid detection of joint inflammation. Therefore, imaging modalities are increasingly used in clinical practice. Optical spectral transmission (OST) measurements are non-invasive and fast and may therefore have benefits over existing imaging modalities. We tested whether OST could measure disease activity validly in patients with RA.MethodsIn 59 patients with RA and 10 patients with arthralgia, OST, joint counts, Disease Activity Score (DAS) 28 and ultrasonography (US) were performed. Additionally, MRI was performed in patients with DAS28<2.6. We developed and validated within the same cohort an algorithm for detection of joint inflammation by OST with US as reference.ResultsAt the joint level, OST and US performed similarly inproximal interphalangeal-joints (area under the receiver-operating curve (AUC) of 0.79, p<0.0001) andmetacarpophalangeal joints (AUC 0.78, p<0.0001). Performance was less similar in wrists (AUC 0.62, p=0.006). On the patient level, OST correlated moderately with clinical examination (DAS28 r=0.42, p=0.001), and US scores (r=0.64, p<0.0001). Furthermore, in patients with subclinical and low disease activity, there was a correlation between OST and MRI synovitis score (RAMRIS (Rheumatoid Arthritis MRI Scoring) synovitis), r=0.52, p=0.005.ConclusionsIn this pilot study, OST performed moderately in the detection of joint inflammation in patients with RA. Further studies are needed to determine the diagnostic performance in a new cohort of patients with RA.

Inelastic collisions of OH(X 2Π)+Ar at an energy of 746 cm−1 have been studied in a crossed molecular beam experiment. The OH(X 2Π) radicals were prepared in the v=0, Ω=32, J=32, f state by hexapole state selection. Parity-resolved integral state-to-state cross sections for rotational excitation have been determined up to the Ω=32, J=92 and Ω=12, J=52 states. A strong preference is found for spin–orbit manifold conserving transitions to final states of e symmetry. The experimental results are compared to quantum scattering calculations on ab initio potential energy surfaces developed by Degli-Esposti and Werner [J. Chem. Phys. 93, 3351 (1990)] and by Klos et al. [J. Chem. Phys. 112, 4952 (2000)]. The overall agreement between experiment and theory is very good; however, the calculated cross sections for spin–orbit changing transitions are a bit larger than the experimental values. The results are also compared to previous experiments at a collision energy of 451 cm−1.

Orientational effects in rotationally elastic collisions of OH with Ar were studied in a crossed molecular beam setup. A static electric field was applied to orient the molecules before the collision. After the collision the orientation was measured by using a narrow-band laser system to probe the Stark-split states corresponding to different orientations. Differential and integral cross sections for reorientation of the molecular axis have been determined as a function of the initial orientation. The cross section for reorientation by one quantum is 25 A2 with a preference for O-end collisions.

Parity resolved state-to-state cross sections for inelastic scattering of OH (X2Pi) by HCl were measured in a crossed molecular beam experiment at the collision energy of 920 cm(-1). The OH (X2Pi) radicals were prepared in a single quantum state, Omega=3/2, J=3/2, MJ=3/2, f, by means of electrostatic state selection in a hexapole field. The rotational distribution of the scattered OH radicals by HCl was probed by saturated LIF spectroscopy of the 0-0 band of the A 2Sigma+ - X 2Pi transition. Relative state-to-state cross sections were measured for rotational excitations up to J=9/2 within the Omega=3/2 spin-orbit manifold and up to J=7/2 within the Omega=1/2 spin-orbit manifold. A propensity for spin-orbit conserving transitions was found, but no propensity for excitation into a particular Lambda-doublet component of the same rotational state was evident. The data are presented and discussed in comparison with results previously obtained for collisions of OH with CO (Ecoll=450 cm(-1)) and N2 (Ecoll=410 cm(-1)) and with new data we have measured for the OH+CO system at a comparable collision energy (Ecoll=985 cm(-1)). This comparison suggests that the potential energy surface (PES) governing the interaction between OH and HCl is more anisotropic than the PES's governing the intermolecular interaction of OH with CO and N2.

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The effect of OH orientation on rotationally inelastic collisions of OH(X2Π) with CO and N2 has been studied in a crossed molecular beam setup at translational energies of 750 and 690 cm−1, respectively. The OH molecules were prepared in the v=0,Ω=32,J=32,f state by hexapole state selection and oriented with their O end or H end toward the collision partner by a static electric field in the collision zone. A degree of orientation of 〈cosθ〉=0.46 has been obtained. In general the cross sections are larger for collisions at the O end in excitation to low rotational states, whereas the cross sections are larger for H end excitation to higher rotational states. OH+CO and OH+N2 behave quite similarly when compared to OH+Ar. Systematic differences between OH+CO and OH+N2 may be attributed to the influence of complex formation on the inelastic collision process. Reanalysis of state-to-state scattering experiments on unoriented OH+CO and OH+N2 indicate that the interaction potential is more head–tail symmetric with respect to OH for OH+N2 compared to OH+CO.

X-linked adrenoleukodystrophy (ALD), a progressive neurodegenerative disease, is caused by mutations in ABCD1 and characterized by very-long-chain fatty acids (VLCFA) accumulation. Virtually all males develop progressive myelopathy (AMN). A subset of patients, however, develops a fatal cerebral demyelinating disease (cerebral ALD). Hematopoietic stem cell transplantation is curative for cerebral ALD provided the procedure is performed in an early stage of the disease. Unfortunately, this narrow therapeutic window is often missed. Therefore, an increasing number of newborn screening programs are including ALD. To identify new biomarkers for ALD, we developed an Abcd1 knockout mouse with enhanced VLCFA synthesis either ubiquitous or restricted to oligodendrocytes. Biochemical analysis revealed VLCFA accumulation in different lipid classes and acylcarnitines. Both C26:0-lysoPC and C26:0-carnitine were highly elevated in brain, spinal cord, but also in bloodspots. We extended the analysis to patients and confirmed that C26:0-carnitine is also elevated in bloodspots from ALD patients. We anticipate that validation of C26:0-carnitine for the diagnosis of ALD in newborn bloodspots may lead to a faster inclusion of ALD in newborn screening programs in countries that already screen for other inborn errors of metabolism.