The Role of Momentum Partitioning in Covariance Ion Imaging Analysis.

We present results from a covariance ion imaging study, which employs extensive filtering, on the relationship between fragment momenta to gain deeper insight into photofragmentation dynamics. A new data analysis approach is introduced that considers the momentum partitioning between the fragments of the breakup of a molecular polycation to disentangle concurrent fragmentation channels, which yield the same ion species. We exploit this approach to examine the momentum exchange relationship between the products, which provides direct insight into the dynamics of molecular fragmentation. We apply these techniques to extensively characterize the dissociation of 1-iodopropane and 2-iodopropane dications prepared by site-selective ionization of the iodine atom using extreme ultraviolet intense femtosecond laser pulses with a photon energy of 95 eV. Our assignments are supported by classical simulations, using parameters largely obtained directly from the experimental data.

Exploring the ultrafast and isomer-dependent photodissociation of iodothiophenes via site-selective ionization.

C-I bond extension and fission following ultraviolet (UV, 262 nm) photoexcitation of 2- and 3-iodothiophene is studied using ultrafast time-resolved extreme ultraviolet (XUV) ionization in conjunction with velocity map ion imaging. The photoexcited molecules and eventual I atom products are probed by site-selective ionization at the I 4d edge using intense XUV pulses, which induce multiple charges initially localized to the iodine atom. At C-I separations below the critical distance for charge transfer (CT), charge can redistribute around the molecule leading to Coulomb explosion and charged fragments with high kinetic energy. At greater C-I separations, beyond the critical distance, CT is no longer possible and the measured kinetic energies of the charged iodine atoms report on the neutral dissociation process. The time and momentum resolved measurements allow determination of the timescales and the respective product momentum and kinetic energy distributions for both isomers, which are interpreted in terms of rival 'direct' and 'indirect' dissociation pathways. The measurements are compared with a classical over the barrier model, which reveals that the onset of the indirect dissociation process is delayed by ∼1 ps relative to the direct process. The kinetics of the two processes show no discernible difference between the two parent isomers, but the branching between the direct and indirect dissociation channels and the respective product momentum distributions show isomer dependencies. The greater relative yield of indirect dissociation products from 262 nm photolysis of 3-iodothiophene (cf. 2-iodothiophene) is attributed to the different partial cross-sections for (ring-centred) π∗ ← π and (C-I bond localized) σ∗ ← (n/π) excitation in the respective parent isomers.

A case report and review of calcinosis cutis.

Commonly associated with autoimmune and renal disorders, calcinosis cutis is a disorder of systemic calcium deposition in soft tissues. The pathophysiology of such deposition varies based on subtype, therefore treatment options vary not only in terms of severity of disease but also with subtype. This case report describes a 52-year-old female with systemic sclerosis and an extensive past medical history who initially presented with complaints of worsening left lower leg pain, a negative workup for deep vein thrombosis, and an extensive palpable mass in the posterior thigh with erythema, drainage, and purulence. With multiple treatment options exhausted from her autoimmune disorders, she ultimately required surgical resection for her refractory infected calcinosis cutis. Identification of calcinosis cutis subtype in conjunction with appropriate history and physical is crucial to determining indications for treatment.

Local Anesthetic Systemic Toxicity During Transversus Abdominis Plane Block With Liposomal Bupivacaine.

Local anesthetic systemic toxicity (LAST) is a rare but potentially fatal outcome associated with local anesthetic administration. Liposomal bupivacaine (LB; EXPAREL®) is a widely used local anesthetic with extended-release and liposomal formulation that carries an improved cardiac and central nervous system safety profile. However, there is limited data regarding LAST associated with liposomal bupivacaine. Here is described a case of local anesthetic systemic toxicity in a 68-year-old male who presented with obstructing sigmoid adenocarcinoma and underwent open sigmoidectomy with end descending colostomy. The operation was complicated by LAST following transversus abdominis plane block injection with liposomal bupivacaine resulting in cardiac arrest. Return of spontaneous circulation was achieved following advanced cardiac life support and infusion of 20% I.V. fat emulsion. Given the widespread use of local anesthetics, providers must be aware of the pathophysiology, diagnosis, and immediate treatment of LAST.

Colorectal Adenocarcinoma in a 35-year-old Female with No Germline Mutations.

Colorectal cancer (CRC) is the third most common cancer to cause death in the world. Despite the recent change in age from 50 to 45 in some societies' recommendations for CRC screening, its incidence is increasing in patients under 50 years. We present a case of a 35-year-old female with no family history of CRC who presented to the emergency department with abdominal pain, vomiting, and obstipation and was found to have sporadic obstructing transverse colon adenocarcinoma.

Time-Resolved X-ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge.

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.

Development of High Throughput Microscope Mode Secondary Ion Mass Spectrometry Imaging.

This paper describes the development and initial results from a secondary ion mass spectrometer coupled with microscope mode detection. Stigmatic ion microscope imaging enables us to decouple the primary ion (PI) beam focus from spatial resolution and is a promising route to attaining higher throughput for mass spectrometry imaging (MSI). Using a commercial C60+ PI beam source, we can defocus the PI beam to give uniform intensity across a 2.5 mm2 area. By coupling the beam with a position-sensitive spatial detector, we can achieve mass spectral imaging of positive and negative secondary ions (SIs), which we demonstrate using samples comprising metals and dyes. Our approach involves simultaneous desorption of ions across a large field of view, enabling mass spectral images to be recorded over an area of 2.5 mm2 in a matter of seconds. Our instrument can distinguish spatial features with a resolution of better than 20 µm, and has a mass resolution of >500 at 500 u. There is considerable scope to improve this, and through simulations we estimate the future performance of the instrument.

Management of High Grade Splenic Injuries in Rural America.

BACKGROUND: Rural surgeons face unique challenges when managing patients with high-grade (III-V) blunt splenic injury (BSI) given limited access to interventional radiology and blood products. Patients therefore may require transfer for splenic artery embolization (SAE) when resuscitation may still be ongoing. This study aims to evaluate current resource utilization in a rural trauma population with limited access to SAE and blood products. METHODS: Retrospective analysis of adult patients with high-grade BSI at one Level 1 trauma center and two Level 2 trauma centers was performed. Patients were evaluated for resources used after transfer to the regional trauma center. Primary outcomes measured were SAE, operative management (OM), and blood product utilization. Secondary outcomes measured included injury severity score (ISS) and mortality. RESULTS: Final analysis included 134 transferred patients. 16% underwent SAE, 16% underwent OM, and 69% were treated successfully with nonoperative and non-procedural management (NOM). 52% of the SAE patients had sustained a grade III splenic injury, 38% grade IV, and 10% grade V. 84% of patients required <3 units of packed red blood cells (PRBC) and 57% of patients required none. 80% of transferred patients required <3 total units of all combined blood products. DISCUSSION: The majority of patients with BSI transferred to a tertiary trauma center from a rural facility were successfully managed without SAE and required minimal transfusion of blood products. In the absence of other injuries necessitating transfer to a tertiary trauma center, rural surgeons should consider management of high grade splenic injuries at their home institution.

Photoionization and Photofragmentation Dynamics of I2 in Intense Laser Fields: A Velocity-Map Imaging Study.

The photoionization and photofragmentation dynamics of I2 in intense femtosecond near-infrared laser fields were studied using velocity-map imaging of cations, electrons, and anions. A series of photofragmentation pathways originating from different cationic electronic states were observed following single ionization, leading to I+ fragments with distinct kinetic energies, which could not be resolved in previous studies. Photoelectron spectra indicate that these high-lying dissociative states are primarily produced through nonresonant ionization from several molecular orbitals (MO) of the neutral. The photoelectron spectra also show clear signatures of resonant ionization pathways (Freeman resonances) to low-lying bound ionic states via Rydberg states of the neutral moiety. To investigate the role of these Rydberg states further, we imaged anionic products (I-) formed through ion-pair dissociations of neutral molecules excited to these Rydberg states by the intense femtosecond laser pulse. Collectively, these results shed significant new light on the complex dynamics of I2 molecules in intense laser fields and on the important role of neutral Rydberg states in a full description of strong-field phenomena in molecules.

Ion Microscope Imaging Mass Spectrometry Using a Timepix3-Based Optical Camera.

Ion microscopy allows for high-throughput mass spectrometry imaging. In order to resolve congested mass spectra, a high degree of timing precision is required from the microscope detector. In this paper we present an ion microscope mass spectrometer that uses a Timepix3 hybrid pixel readout with an optimal 1.56 ns resolution. A novel triggering technique is also employed to remove the need for an external time-to-digital converter (TDC) and allow the experiment to be performed using a low-cost and commercially available readout system. Results obtained from samples of rhodamine B demonstrate the application of multimass imaging sensors for microscope mass spectrometry imaging with high mass resolution.

Disentangling sequential and concerted fragmentations of molecular polycations with covariant native frame analysis.

We present results from an experimental ion imaging study into the fragmentation dynamics of 1-iodopropane and 2-iodopropane following interaction with extreme ultraviolet intense femtosecond laser pulses with a photon energy of 95 eV. Using covariance imaging analysis, a range of observed fragmentation pathways of the resulting polycations can be isolated and interrogated in detail at relatively high ion count rates (∼12 ions shot-1). By incorporating the recently developed native frames analysis approach into the three-dimensional covariance imaging procedure, contributions from three-body concerted and sequential fragmentation mechanisms can be isolated. The angular distribution of the fragment ions is much more complex than in previously reported studies for triatomic polycations, and differs substantially between the two isomeric species. With support of simple simulations of the dissociation channels of interest, detailed physical insights into the fragmentation dynamics are obtained, including how the initial dissociation step in a sequential mechanism influences rovibrational dynamics in the metastable intermediate ion and how signatures of this nuclear motion manifest in the measured signals.

The kinetic energy of PAH dication and trication dissociation determined by recoil-frame covariance map imaging.

We investigated the dissociation of dications and trications of three polycyclic aromatic hydrocarbons (PAHs), fluorene, phenanthrene, and pyrene. PAHs are a family of molecules ubiquitous in space and involved in much of the chemistry of the interstellar medium. In our experiments, ions are formed by interaction with 30.3 nm extreme ultraviolet (XUV) photons, and their velocity map images are recorded using a PImMS2 multi-mass imaging sensor. Application of recoil-frame covariance analysis allows the total kinetic energy release (TKER) associated with multiple fragmentation channels to be determined to high precision, ranging 1.94-2.60 eV and 2.95-5.29 eV for the dications and trications, respectively. Experimental measurements are supported by Born-Oppenheimer molecular dynamics (BOMD) simulations.

Predicting Coulomb explosion fragment angular distributions using molecular ground-state vibrational motion.

Laser-induced Coulomb explosions can be used to identify gas-phase molecular structures through correlations between fragment ion trajectories. This report presents a model for predicting these outcomes, which first establishes the neutral equilibrium geometry of a target molecule using electronic structure calculations, and then samples a probability distribution of potential ground-state configurations by allowing for zero-point vibrational motion. Candidate structures are assumed to explode instantaneously into charged fragments, and the simulated ion trajectories are correlated using recoil-frame covariance analysis. The effects of detection efficiency and fluctuating experimental conditions are also considered. The results were found to match experimental data, indicating that Coulomb explosion fragment angular distributions produced from highly-charged ions depend largely on the internal motion of the target molecule.

A localized view on molecular dissociation via electron-ion partial covariance.

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

Multi-channel photodissociation and XUV-induced charge transfer dynamics in strong-field-ionized methyl iodide studied with time-resolved recoil-frame covariance imaging.

The photodissociation dynamics of strong-field ionized methyl iodide (CH3I) were probed using intense extreme ultraviolet (XUV) radiation produced by the SPring-8 Angstrom Compact free electron LAser (SACLA). Strong-field ionization and subsequent fragmentation of CH3I was initiated by an intense femtosecond infrared (IR) pulse. The ensuing fragmentation and charge transfer processes following multiple ionization by the XUV pulse at a range of pump-probe delays were followed in a multi-mass ion velocity-map imaging (VMI) experiment. Simultaneous imaging of a wide range of resultant ions allowed for additional insight into the complex dynamics by elucidating correlations between the momenta of different fragment ions using time-resolved recoil-frame covariance imaging analysis. The comprehensive picture of the photodynamics that can be extracted provides promising evidence that the techniques described here could be applied to study ultrafast photochemistry in a range of molecular systems at high count rates using state-of-the-art advanced light sources.

High-Resolution Ion Microscope Imaging over Wide Mass Ranges Using Electrodynamic Postextraction Differential Acceleration.

A time-dependent postextraction differential acceleration (PEDA) potential was used to temporally focus increasingly heavy ions in a stigmatic imaging mass spectrometer, allowing them to be imaged with high mass and spatial resolutions over a broad mass-to-charge (m/z) range. By applying a linearly rising potential to the ion extraction electrode, sequential m/z ratios were subjected to a changing electric field, allowing their foci to coincide at the detector. Using this approach, at least 75% of the maximum mass resolution was obtained over a 300-600 Da range when the ion microscope was focused around 450 Da, representing more than a 10-fold increase over the conventional single-field PEDA method.

Microscope imaging mass spectrometry with a reflectron.

A time-of-flight microscope imaging mass spectrometer incorporating a reflectron was used to image mass-resolved ions generated from a 270 µm diameter surface. Mass and spatial resolutions of 8100 ± 700 m/Δm and 18 µm ± 6 µm, respectively, were obtained simultaneously by using pulsed extraction differential acceleration ion optical focusing to create a pseudo-source plane for a single-stage gridless reflectron. The obtainable mass resolution was limited only by the response time of the position-sensitive detector and, according to simulations, could potentially reach 30 200 ± 2900 m/Δm. The spatial resolution can be further improved at the expense of the mass resolution to at least 6 µm by increasing the applied extraction field. An event-triggered fast imaging sensor was additionally used to record ion images for each time-of-flight peak resolved during an experimental cycle, demonstrating the high-throughput capability of the instrument.

Coulomb explosion imaging of CH3I and CH2ClI photodissociation dynamics.

The photodissociation dynamics of CH3I and CH2ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH2ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

Practical Strategies for Optimizing and Integrating Palliative Care in Cancer.

PURPOSE OF REVIEW: Recent reforms in medical payment coupled with a rapidly evolving pharmacotherapeutic armamentarium is creating a transition in the field of oncology. This transition represents a key period for conceptual reevaluation, providing an opportunity for furthered strategic integration of palliative care within the realm of oncology. RECENT FINDINGS: Historically, oncologists have relied upon prognostic assessments to gauge appropriateness for referrals to specialty palliative care. Recent literature has elucidated on the early palliative burdens of cancer, demonstrated the importance of complexity-based palliative referrals, and begun the conversation to define provider-specific roles. Herein, we describe a model that overlaps complexity with oncology capacity, to target specialty services to those who could benefit most. This article will review the role of palliative care as a care philosophy, the enduring and important role of the oncologist in providing palliative care, and the important areas for integration of specialty services when needed.

What They May Not Tell You and You May Not Know to Ask: What is Expected of Surgeons in Their First Year of Independent Practice.

OBJECTIVE: The objective of this study was to explore the views and expectations that practicing general surgeons have of their junior colleagues who have recently finished training. DESIGN: This is a qualitative study performed using focus group data consisting of open-ended questions concentrating on essential qualities and attributes of surgeons, behaviors observed in newly-graduated surgeons, and appropriate oversight of junior partners. Qualitative analysis was performed using grounded theory methodology with transcripts coded by 3 independent reviewers. SETTING: Focus groups were conducted with surgeons practicing in rural and urban community settings. PARTICIPANTS: Focus groups consisted of practicing general surgeons throughout the state of Oregon. RESULTS: Focus groups were comprised of 31 practicing surgeons (10 female, 21 male) with varying ages and levels of experience practicing in both rural and urban environments. Qualitative analysis revealed the need for surgeons with strong interpersonal skills, teamwork, judgment, and broad technical skills who possess the appropriate amount of confidence and know when to ask for help. Frequently noted themes identified, included not knowing when to ask for help, overconfidence or underconfidence, as well as lack of judgment and lack of either quality or breadth of technical skill. Current oversight included direct observation, subjective evaluations from staff and colleagues, analysis of outcomes/quality, and either formal or informal mentorship arrangements. CONCLUSIONS: This study highlights the need for graduating surgeons to be competent in multiple domains. The importance of knowing when to ask for help was stressed by practicing surgeons in both the rural and urban community setting, but is underemphasized in residency training, possibly due to less indirect resident supervision. Surgeons also emphasized the importance of mentorship, as professional growth continues long after completion of training.