Characterizing the multi-dimensional reaction dynamics of dihalomethanes using XUV-induced Coulomb explosion imaging.

Site-selective probing of iodine 4d orbitals at 13.1 nm was used to characterize the photolysis of CH2I2 and CH2BrI initiated at 202.5 nm. Time-dependent fragment ion momenta were recorded using Coulomb explosion imaging mass spectrometry and used to determine the structural dynamics of the dissociating molecules. Correlations between these fragment momenta, as well as the onset times of electron transfer reactions between them, indicate that each molecule can undergo neutral three-body photolysis. For CH2I2, the structural evolution of the neutral molecule was simultaneously characterized along the C-I and I-C-I coordinates, demonstrating the sensitivity of these measurements to nuclear motion along multiple degrees of freedom.

From 'OPAT' to 'COpAT': implications of the OVIVA study for ambulatory management of bone and joint infection.

Bone and joint infection contributes significantly to clinical activity within outpatient parenteral antimicrobial therapy (OPAT) services. The OVIVA (oral versus intravenous antibiotics for bone and joint infection) randomized study has challenged the practice of prolonged intravenous therapy, because non-inferiority of oral antibiotic therapy was demonstrated, thereby implying that early transition to oral therapy is an appropriate alternative to prolonged intravenous therapy. We examine the caveats to the study and discuss the implications for OPAT practice, highlighting the importance of careful oral antibiotic selection with attention to bioavailability, bone penetration, drug interactions, compliance and toxicity monitoring. We emphasize that ambulatory antibiotic therapy (whether intravenous or oral) in this patient group requires expert multidisciplinary management, monitoring and follow-up, and ideally should be undertaken within existing OPAT or, more accurately, complex outpatient antibiotic therapy (COpAT) services.

Ultraviolet photochemistry of 2-bromothiophene explored using universal ionization detection and multi-mass velocity-map imaging with a PImMS2 sensor.

The ultraviolet photochemistry of 2-bromothiophene (C4H3SBr) has been studied across the wavelength range 265-245 nm using a velocity-map imaging (VMI) apparatus recently modified for multi-mass imaging and vacuum ultraviolet (VUV, 118.2 nm) universal ionization. At all wavelengths, molecular products arising from the loss of atomic bromine were found to exhibit recoil velocities and anisotropies consistent with those reported elsewhere for the Br fragment [J. Chem. Phys. 142, 224303 (2015)]. Comparison between the momentum distributions of the Br and C4H3S fragments suggests that bromine is formed primarily in its ground (2P3/2) spin-orbit state. These distributions match well at high momentum, but relatively fewer slow moving molecular fragments were detected. This is explained by the observation of a second substantial ionic product, C3H3+. Analysis of ion images recorded simultaneously for several ion masses and the results of high-level ab initio calculations suggest that this fragment ion arises from dissociative ionization (by the VUV probe laser) of the most internally excited C4H3S fragments. This study provides an excellent benchmark for the recently modified VMI instrumentation and offers a powerful demonstration of the emerging field of multi-mass VMI using event-triggered, high frame-rate sensors, and universal ionization.

Nanoparticle Trapping and Characterization Using Open Microcavities.

Characterization and trapping of nanoparticles in solution is of great importance for lab-on-a-chip applications in biomedical, environmental, and materials sciences. Devices are now starting to emerge allowing such manipulations and investigations in real-time. Better insights into the interaction between the nanoparticle and the optical trap is therefore necessary in order to move forward in this field. In this work, we present a new kind of nanotweezers based on open microcavities. We show that by monitoring the cavity mode wavelength shift as the particle diffuses through the cavity, it is possible to establish both the nanoparticle polarizability and its coefficient of friction. Additionally, our experiment provides a deep insight in the interaction between the nanoparticle and the cavity mode. The technique has built-in calibration of the trap strength and spring constant, making it attractive for practical applications. This work illustrates the potential of such optical microcavities for future developments in nanoparticle sensors and lab-on-a-chip devices.

Modifications to a commercially available linear mass spectrometer for mass-resolved microscopy with the pixel imaging mass spectrometry (PImMS) camera.

RATIONALE: Imaging mass spectrometry is a powerful analytical technique capable of accessing a large volume of spatially resolved, chemical data from two-dimensional samples. Probing the entire surface of a sample simultaneously requires a detector with high spatial and temporal resolutions, and the ability to observe events relating to different mass-to-charge ratios. METHODS: A commercially available time-of-flight mass spectrometer, designed for matrix-assisted laser desorption/ionization (MALDI) analysis, was combined with the novel pixel imaging mass spectrometry (PImMS) camera in order to perform multi-mass, microscope-mode imaging experiments. A number of minor modifications were made to the spectrometer hardware and ion optics so that spatial imaging was achieved for a number of small molecules. RESULTS: It was shown that a peak width of Δm50 % < 1 m/z unit across the range 200 ≤ m/z ≤ 800 can be obtained while also achieving an optimum spatial resolution of 25 µm. It was further shown that these data were obtained simultaneously for all analytes present without the need to scan the experimental parameters. CONCLUSIONS: This work demonstrates the capability of multi-mass, microscope-mode imaging to reduce the acquisition time of spatially distributed analytes such as multi-arrays or biological tissue sections. It also shows that such an instrument can be commissioned by effecting relatively minor modifications to a conventional commercial machine.

Time-resolved relaxation and fragmentation of polycyclic aromatic hydrocarbons investigated in the ultrafast XUV-IR regime.

Polycyclic aromatic hydrocarbons (PAHs) play an important role in interstellar chemistry and are subject to high energy photons that can induce excitation, ionization, and fragmentation. Previous studies have demonstrated electronic relaxation of parent PAH monocations over 10-100 femtoseconds as a result of beyond-Born-Oppenheimer coupling between the electronic and nuclear dynamics. Here, we investigate three PAH molecules: fluorene, phenanthrene, and pyrene, using ultrafast XUV and IR laser pulses. Simultaneous measurements of the ion yields, ion momenta, and electron momenta as a function of laser pulse delay allow a detailed insight into the various molecular processes. We report relaxation times for the electronically excited PAH*, PAH+* and PAH2+* states, and show the time-dependent conversion between fragmentation pathways. Additionally, using recoil-frame covariance analysis between ion images, we demonstrate that the dissociation of the PAH2+ ions favors reaction pathways involving two-body breakup and/or loss of neutral fragments totaling an even number of carbon atoms.

Evaluation of predictors of the development of azotemia in cats.

BACKGROUND: Chronic kidney disease (CKD) is a common condition in geriatric cats. Diagnosis is based on the development of persistent azotemia with inadequate urine concentrating ability. Biomarkers are sought for early identification. HYPOTHESIS: Clinical variables, urine concentrating ability, proteinuria, and N-acetyl-beta-D-glucosaminidase (NAG) index will be predictive of cats at risk of developing azotemia within 12 months. ANIMALS: Client-owned nonazotemic geriatric (>or=9 years) cats. METHODS: Prospective longitudinal cohort study monitoring a population of healthy nonazotemic geriatric cats every 6 months until development of azotemia, death, or the study end point (September 30, 2007). Multivariable logistic regression analysis was used to assess baseline clinical, biochemical, and urinalysis variables, urine protein to creatinine ratio (UP/C), urine albumin to creatinine (UA/C) ratio, and urinary NAG index as predictors of development of azotemia. RESULTS: One hundred and eighteen cats were recruited with a median age of 13 years. Ninety-five cats (80.5%) had been followed or reached the study end point by 12 months of which 30.5% (29/95) developed azotemia. Age, systolic blood pressure, plasma creatinine concentration, urine specific gravity, UP/C, UA/C, and NAG index were significantly associated with development of azotemia in the univariable analysis (P

Quality of life of living kidney donors: a single-center experience.

Renal transplantation improves the quality of life (QoL) of patients with end-stage renal disease. The preservation of QoL of living kidney donors is paramount. The aim of this study was to assess the QoL pre- and postdonation using Medical Outcome Survey Short Form-36 (SF-36) and to compare with a control group of potential donors who did not proceed with donation. Over a period of 28 years (1978 to 2006), 82 living donor renal transplantations were performed. Of the 78 eligible donors, 66 (85%) participated in the survey. The median postdonation period was 4.6 years (range, 3 months to 27 years). Thirty eight individuals were assessed in the control group. The postdonation SF-36 scores of the donors were not statistically significantly different from those of the control group except in one out of eight dimensions, which was physical role. However, in 44/66 (66%) donors, the postdonation scores were significantly lower compared to their predonation scores because of development of comorbidities such as musculoskeletal pain, migraine, myocardial infarction, diabetes, and peptic ulcers as the time progressed since kidney donation. The age, sex, time since donation, and relationship to recipient did not affect QoL. Eighty three percentage of the donors would have donated again if possible, and 90.9% wished to encourage living kidney donation. We conclude that the QoL of living kidney donors was not different from the healthy controls, although with the passage of time, there was some deterioration of QoL due to development of comorbidities.

Plasma asymmetric dimethylarginine, symmetric dimethylarginine, l-arginine, and nitrite/nitrate concentrations in cats with chronic kidney disease and hypertension.

BACKGROUND: Chronic kidney disease (CKD) and hypertension have been associated with decreased bioavailability of nitric oxide (NO) and endothelial dysfunction. Increased concentrations of the endothelial nitric oxide synthase (eNOS) inhibitor asymmetric dimethylarginine (ADMA) are implicated. HYPOTHESIS: Plasma ADMA concentration is increased in cats with CKD and systemic hypertension corresponding to a decrease in total plasma nitrate/nitrite (NOx) availability. Decrease in systolic blood pressure (SBP) and proteinuria during treatment of hypertension with amlodipine besylate may be associated with increased NOx availability. ANIMALS: Sixty-nine client-owned normotensive and hypertensive cats with variable azotemia. METHODS: Plasma ADMA, symmetric dimethylarginine (SDMA), and l-arginine were measured simultaneously by hydrophilic-interaction liquid chromatography-electrospray tandem mass spectrometry in cats from 6 groups: normotensive nonazotemic (n = 10), normotensive mildly azotemic (n = 10), hypertensive mildly azotemic with hypertensive retinopathy (n = 20), hypertensive mildly azotemic without hypertensive retinopathy (n = 10), normotensive moderately azotemic cats (n = 10), and hypertensive nonazotemic cats (n = 9). Plasma NOx concentrations were measured. RESULTS: A moderate correlation between plasma creatinine and ADMA (n = 69, r= .608, P < .001), SDMA (n = 69, r= .741, P < .001), and NOx concentrations (n = 69, r= .589, P < .001) was observed. There was no association among plasma ADMA, SDMA, and NOx concentrations and SBP. CONCLUSIONS AND CLINICAL IMPORTANCE: Plasma ADMA and SDMA concentrations are increased in cats with CKD and correlate with plasma creatinine concentration. This may imply the presence of endothelial dysfunction in cats with CKD. Plasma ADMA concentrations were not associated with systemic hypertension. Treatment of systemic hypertension with amlodipine besylate did not affect plasma ADMA or NOx concentrations.

A pharmacological action of vitamin E unrelated to its antioxidant capacity.

The pharmacological action of vitamin E on the mechanical activity of isolated guinea pig colonic smooth muscle was examined in normoxic and hypoxic conditions. In hypoxia, but not normoxia, alpha-tocopherol (1-160 microM) evoked rapid concentration-dependent contractions from the colon. This was also seen with other members of the vitamin E family, and potency measurements gave EC(50) values (microM) of 10.6 +/- 0.9 for D-alpha-tocopherol, 6.0 +/- 1.2 for D-beta-tocopherol, 7.5 +/- 0.7 for D-gamma-tocopherol, and 6.1 +/- 1.5 for D-delta-tocopherol. This order of potency for the components of the vitamin differs from previously studied bioassay systems and from their antioxidant activity. A range of potent natural and synthetic antioxidants was not active in this system. Compounds with structural similarities to the side chain of vitamin E produced similar stimulatory responses and some, like phytol, were more potent than the vitamin (EC(50): 1.0 +/- 0.2 microM), whereas ring structures related to the vitamin, like Trolox C, antagonized the stimulant responses in a concentration-dependent manner. Therefore, this model system measures, directly, vitamin E-induced responses through a mechanism that does not appear to be related to the known antioxidant capacity of these agents.

Three-dimensional imaging of carbonyl sulfide and ethyl iodide photodissociation using the pixel imaging mass spectrometry camera.

The Pixel Imaging Mass Spectrometry (PImMS) camera is used in proof-of-principle three-dimensional imaging experiments on the photodissociation of carbonyl sulfide and ethyl iodide at wavelengths around 230 nm and 245 nm, respectively. Coupling the PImMS camera with DC-sliced velocity-map imaging allows the complete three-dimensional Newton sphere of photofragment ions to be recorded on each laser pump-probe cycle with a timing precision of 12.5 ns, yielding velocity resolutions along the time-of-flight axis of around 6%-9% in the applications presented.

A fast microchannel plate-scintillator detector for velocity map imaging and imaging mass spectrometry.

The time resolution achievable using standard position-sensitive ion detectors, consisting of a chevron pair of microchannel plates coupled to a phosphor screen, is primarily limited by the emission lifetime of the phosphor, around 70 ns for the most commonly used P47 phosphor. We demonstrate that poly-para-phenylene laser dyes may be employed extremely effectively as scintillators, exhibiting higher brightness and much shorter decay lifetimes than P47. We provide an extensive characterisation of the properties of such scintillators, with a particular emphasis on applications in velocity-map imaging and microscope-mode imaging mass spectrometry. The most promising of the new scintillators exhibits an electron-to-photon conversion efficiency double that of P47, with an emission lifetime an order of magnitude shorter. The new scintillator screens are vacuum stable and show no signs of signal degradation even over longer periods of operation.

Open-access optical microcavities for lab-on-a-chip refractive index sensing.

Open-access optical microcavities provide a novel approach to label-free lab-on-a-chip optofluidic sensing. They offer direct access to a highly confined electromagnetic field, and yield a femtoliter detection volume. This article describes the characteristics of these devices for refractive index sensing. We show that most of the ambient noise can be removed from the refractive index data by simultaneous tracking of resonances across an array of cavities. A sensitivity of 3.5 × 10(-4) RIU is demonstrated which corresponds to detecting the refractive index change caused by the presence of 500,000 glucose molecules in aqueous solution.

The application of the fast, multi-hit, pixel imaging mass spectrometry sensor to spatial imaging mass spectrometry.

Imaging mass spectrometry is a powerful technique that allows chemical information to be correlated to a spatial coordinate on a sample. By using stigmatic ion microscopy, in conjunction with fast cameras, multiple ion masses can be imaged within a single experimental cycle. This means that fewer laser shots and acquisition cycles are required to obtain a full data set, and samples suffer less degradation as overall collection time is reduced. We present the first spatial imaging mass spectrometry results obtained with a new time-stamping detector, named the pixel imaging mass spectrometry (PImMS) sensor. The sensor is capable of storing multiple time stamps in each pixel for each time-of-flight cycle, which gives it multi-mass imaging capabilities within each pixel. A standard velocity-map ion imaging apparatus was modified to allow for microscope mode spatial imaging of a large sample area (approximately 5 × 5 mm(2)). A variety of samples were imaged using PImMS and a conventional camera to determine the specifications and possible applications of the spectrometer and the PImMS camera.

Velocity map imaging in time of flight mass spectrometry.

A new variation on time of flight mass spectrometry is presented, which uses a fast framing charge coupled device camera to velocity map image multiple product masses in a single acquisition. The technique is demonstrated on two photofragmentation processes, those of CS(2) and CH(3)S(2)CH(3) (dimethyldisulfide) at a photolysis wavelength of 193 nm. In both cases, several mass fragments are imaged simultaneously, and speed distributions and anisotropy parameters are extracted that are comparable to those obtained by imaging each fragment separately in conventional velocity map imaging studies.

The photodissociation dynamics of OCS at 248 nm: the S((3)P(J)) atomic angular momentum polarization.

The dissociation of OCS has been investigated subsequent to excitation at 248 nm using velocity map ion imaging. Speed distributions, speed dependent translational anisotropy parameters, and the atomic angular momentum orientation and alignment are reported for the channel leading to S((3)P(J)). The speed distributions and beta parameters are in broad agreement with previous work and show behavior that is highly sensitive to the S-atom spin-orbit state. The data are shown to be consistent with the operation of at least two triplet production mechanisms. Interpretation of the angular momentum polarization data in terms of an adiabatic picture has been used to help identify a likely dissociation pathway for the majority of the S((3)P(J)) products, which strongly favors production of J=2 fragment atoms, correlated, it is proposed, with rotationally hot and vibrationally cold CO cofragments. For these fragments, optical excitation to the 2 (1)A(') surface is thought to constitute the first step, as for the singlet dissociation channel. This is followed by crossing, via a conical intersection, to the ground 1 (1)A(') state, from where intersystem crossing occurs, populating the 1 (3)A(')1 (3)A(")((3)Pi) states. The proposed mechanism provides a qualitative rationale for the observed spin-orbit populations, as well as the S((3)P(J)) quantum yield and angular momentum polarization. At least one other production mechanism, leading to a more statistical S-atom spin-orbit state distribution and rotationally cold, vibrationally hot CO cofragments, is thought to involve direct excitation to either the (3)Sigma(-) or (3)Pi states.

Photodissociation dynamics of OCS at 248 nm: the S((1)D(2)) atomic angular momentum polarization.

The dissociation of OCS has been investigated subsequent to excitation at 248 nm. Speed distributions, speed dependent translational anisotropy parameters, angular momentum alignment, and orientation are reported for the channel leading to S((1)D(2)). In agreement with previous experiments, two product speed regimes have been identified, correlating with differing degrees of rotational excitation in the CO coproducts. The velocity dependence of the translational anisotropy is also shown to be in agreement with previous work. However, contrary to previous interpretations, the speed dependence is shown to primarily reflect the effects of nonaxial recoil and to be consistent with predominant excitation to the 2 (1)A(') electronic state. It is proposed that the associated electronic transition moment is polarized in the molecular plane, at an angle greater than approximately 60 degrees to the initial linear OCS axis. The atomic angular momentum polarization data are interpreted in terms of a simple long-range interaction model to help identify likely surfaces populated during dissociation. Although the model neglects coherence between surfaces, the polarization data are shown to be consistent with the proposed dissociation mechanisms for the two product speed regimes. Large values for the low and high rank in-plane orientation parameters are reported. These are believed to be the first example of a polyatomic system where these effects are found to be of the same order of magnitude as the angular momentum alignment.

Atomic polarization in the photodissociation of diatomic molecules.

The angular momentum polarization of atomic photofragments provides a detailed insight into the dynamics of the photodissociation process. In this article, the origins of electronic angular momentum polarization are introduced and experimental and theoretical methods for the measurement or calculation of atomic orientation and alignment parameters described. Many diatomic photodissociation systems are surveyed, in order to provide an overview both of the historical development of the field and of the most state-of-the-art contemporary studies.

The photodissociation dynamics of O2 at 193 nm: an O3PJ angular momentum polarization study.

In the following paper we present translational anisotropy and angular momentum polarization data for O((3)P(1)) and O((3)P(2)) products of the photodissociation of molecular oxygen at 193 nm. The data were obtained using polarized laser photodissociation coupled with resonantly enhanced multiphoton ionization and velocity-map ion imaging. Under the jet-cooled conditions employed, absorption is believed to be dominated by excitation into the Herzberg continuum. The experimental data are compared with previous experiments and theoretical calculations at this and other wavelengths. Semi-classical calculations performed by Groenenboom and van Vroonhoven [J. Chem. Phys, 2002, 116, 1965] are used to estimate the alignment parameters arising from incoherent excitation and dissociation and these are shown to agree qualitatively well with the available experimental data. Following the work of Alexander et al. [J. Chem. Phys, 2003, 118, 10566], orientation and alignment parameters arising from coherent excitation and dissociation are modelled more approximately by estimating phase differences generated subsequent to dissociation via competing adiabatic pathways leading to the same asymptotic products. These calculations lend support to the view that large values of the coherent alignment moments, but small values of the corresponding orientation moments, could arise from coherent excitation of (and subsequent dissociation via) parallel and perpendicular components of the Herzberg I, II and III transitions.

The photodissociation dynamics of NO2 at 308 nm and of NO2 and N2O4 at 226 nm.

Velocity-map ion imaging has been applied to the photodissociation of NO(2) via the first absorption band at 308 nm using (2 + 1) resonantly enhanced multiphoton ionization detection of the atomic O((3)P(J)) products. The resulting ion images have been analyzed to provide information about the speed distribution of the O((3)P(J)) products, the translational anisotropy, and the electronic angular momentum alignment. The atomic speed distributions were used to provide information about the internal quantum-state distribution in the NO coproducts. The data were found to be consistent with an inverted NO vibrational quantum-state distribution, and thereby point to a dynamical, as opposed to a statistical dissociation mechanism subsequent to photodissociation at 308 nm. Surprisingly, at this wavelength the O-atom electronic angular momentum alignment was found to be small. Probe-only ion images obtained under a variety of molecular-beam backing-pressure conditions, and corresponding to O atoms generated in the photodissociation of either the monomer, NO(2), or the dimer, N(2)O(4), at 226 nm, are also reported. For the monomer, where 226 nm corresponds to excitation into the second absorption band, the kinetic-energy release distributions are also found to indicate a strong population inversion in the NO cofragment, and are shown to be remarkably similar to those previously observed in the wavelength range of 193-248 nm. Mechanistic implications of this result are discussed. At 226 nm it has also been possible to observe directly O atoms from the photodissociation of the dimer. The O-atom velocity distribution has been analyzed to provide information about its production mechanism.