Evidence for Superoxide-Initiated Oxidation of Aniline in Water by Pulsed, Atmospheric Pressure Plasma.

Plasma-driven solution electrochemistry (PDSE) uses plasma-generated reactive species to drive redox reactions in solution. Nonthermal, atmospheric pressure plasmas, when irradiating water, produce many redox species. While PDSE is a promising chemical tool, there is limited insight into the mechanisms of the reactions due to the variety of short-lived reagents produced. In this study, we use aniline as a model system for studying redox mechanisms of PDSE. We show that the plasma irradiation of aqueous aniline solutions drives the formation of polyaniline oligomer, which is suppressed under acidic starting conditions. The addition of (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO), a radical scavenger, decreases the formation of oligomer by 80%, and the addition of superoxide dismutase fully hinders oligomerization. These results lead us to conclude that the oligomerization of aniline by plasma irradiation is initiated by superoxide. This discovery provides novel insights into PDSE mechanisms and illustrates a potential method of harnessing superoxide for chemical reactions.

Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO2- as a plasma-derived reducing agent.

Many applications involving plasma-liquid interactions depend on the reactive processes occurring at the plasma-liquid interface. We report on a falling liquid film plasma reactor allowing for in situ optical absorption measurements of the time-dependence of the ferricyanide/ferrocyanide redox reactivity, complemented with ex situ measurement of the decomposition of formate. We found excellent agreement between the measured decomposition percentages and the diffusion-limited decomposition of formate by interfacial plasma-enabled reactions, except at high pH in thin liquid films, indicating the involvement of previously unexplored plasma-induced liquid phase chemistry enabled by long-lived reactive species. We also determined that high pH facilitates a reduction-favoring environment in ferricyanide/ferrocyanide redox solutions. In situ conversion measurements of a 1:1 ferricyanide/ferrocyanide redox mixture exceed the measured ex situ conversion and show that conversion of a 1:1 ferricyanide/ferrocyanide mixture is strongly dependent on film thickness. We identified three dominant processes: reduction faster than ms time scales for film thicknesses >100 µm, •OH-driven oxidation on time scales of <10 ms, and reduction on 15 ms time scales for film thickness <100 µm. We attribute the slow reduction and larger formate decomposition at high pH to HO2- formed from plasma-produced H2O2 enabled by the high pH at the plasma-liquid interface as confirmed experimentally and by computed reaction rates of HO2- with ferricyanide. Overall, this work demonstrates the utility of liquid film reactors in enabling the discovery of new plasma-interfacial chemistry and the utility of atmospheric plasmas for electrodeless electrochemistry.

Mastering Femtosecond Stimulated Raman Spectroscopy: A Practical Guide.

Femtosecond stimulated Raman spectroscopy (FSRS) is a powerful nonlinear spectroscopic technique that probes changes in molecular and material structure with high temporal and spectral resolution. With proper spectral interpretation, this is equivalent to mapping out reactive pathways on highly anharmonic excited-state potential energy surfaces with femtosecond to picosecond time resolution. FSRS has been used to examine structural dynamics in a wide range of samples, including photoactive proteins, photovoltaic materials, plasmonic nanostructures, polymers, and a range of others, with experiments performed in multiple groups around the world. As the FSRS technique grows in popularity and is increasingly implemented in user facilities, there is a need for a widespread understanding of the methodology and best practices. In this review, we present a practical guide to FSRS, including discussions of instrumentation, as well as data acquisition and analysis. First, we describe common methods of generating the three pulses required for FSRS: the probe, Raman pump, and actinic pump, including a discussion of the parameters to consider when selecting a beam generation method. We then outline approaches for effective and efficient FSRS data acquisition. We discuss common data analysis techniques for FSRS, as well as more advanced analyses aimed at extracting small signals on a large background. We conclude with a discussion of some of the new directions for FSRS research, including spectromicroscopy. Overall, this review provides researchers with a practical handbook for FSRS as a technique with the aim of encouraging many scientists and engineers to use it in their research.

Feasibility and Morbidity of Magnetic Resonance Imaging-Guided Stereotactic Laser Ablation of Deep Cerebral Cavernous Malformations: A Report of 4 Cases.

BACKGROUND: Magnetic resonance imaging (MRI)-guided laser interstitial thermal therapy (MRgLITT) has been used successfully to treat epileptogenic cortical cerebral cavernous malformations (CCM). It is unclear whether MRgLITT would be as feasible or safe for deep CCMs. OBJECTIVE: To describe our experience with MRgLITT for symptomatic deep CCMs. METHODS: Patients' records were reviewed retrospectively. MRgLITT was carried out using a commercially available system in an interventional MRI suite with efforts to protect adjacent brain structures. Immediate postoperative imaging was used to judge ablation adequacy. Delayed postoperative MRI was used to measure lesion volume changes during follow-up. RESULTS: Four patients with CCM in the thalamus, putamen, midbrain, or subthalamus presented with persistent and disabling neurological symptoms. A total of 2 patients presented with disabling headaches and sensory disturbances and 2 with recurrent symptomatic hemorrhages, of which 1 had familial CCM. Patients were considered by vascular neurosurgeons to be poor candidates for open surgery or had refused it. Multiple trajectories were used in most cases. Adverse events included device malfunction with leakage of saline causing transient mass effect in one patient, and asymptomatic tract hemorrhage in another. One patient suffered an expected mild but persistent exacerbation of baseline deficits. All patients showed improvement from a previously aggressive clinical course with lesion volume decreased by 20% to 73% in follow-up. CONCLUSION: MRgLITT is feasible in the treatment of symptomatic deep CCM but may carry a high risk of complications without the benefit of definitive resection. We recommend cautious patient selection, low laser power settings, and conservative temperature monitoring in surrounding brain parenchyma.

MRI-guided stereotactic laser corpus callosotomy for epilepsy: distinct methods and outcomes.

OBJECTIVE: Several small series have described stereotactic MRI-guided laser interstitial thermal therapy for partial callosotomy of astatic and generalized tonic-clonic (GTC) seizures, especially in association with Lennox-Gastaut syndrome. Larger case series and comparison of distinct stereotactic methods for stereotactic laser corpus callosotomy (SLCC), however, are currently lacking. The objective of this study was to report seizure outcomes in a series of adult patients with epilepsy following anterior, posterior, and complete SLCC procedures and to compare the results achieved with a frameless stereotactic surgical robot versus direct MRI guidance frames. METHODS: The authors retrospectively reviewed sequential adult epilepsy surgery patients who underwent SLCC procedures at a single institution. They describe workflows, stereotactic errors, percentage disconnection, hospitalization durations, adverse events, and seizure outcomes after performing anterior, posterior, and complete SLCC procedures using a frameless stereotactic surgical robot versus direct MRI guidance platforms. RESULTS: Thirteen patients underwent 15 SLCC procedures. The median age at surgery was 29 years (range 20-49 years), the median duration of epilepsy was 21 years (range 9-48 years), and median postablation follow-up was 20 months (range 4-44 months). Ten patients underwent anterior SLCC with a median 73% (range 33%-80%) midsagittal length of callosum acutely ablated. Following anterior SLCC, 6 of 10 patients achieved meaningful (> 50%) reduction of target seizures. Four patients underwent posterior (completion) SLCC following prior anterior callosotomy, and 1 patient underwent complete SLCC as a single procedure; 3 of these 5 patients experienced meaningful reduction of target seizures. Overall, 8 of 10 patients in whom astatic seizures were targeted and treated by anterior and/or posterior SLCC experienced meaningful improvement. SLCC procedures with direct MRI guidance (n = 7) versus a frameless surgical robot (n = 8) yielded median radial accuracies of 1.1 mm (range 0.2-2.0 mm) versus 2.4 mm (range 0.6-6.1 mm; p = 0.0011). The most serious adverse event was a clinically significant intraparenchymal hemorrhage in a patient who underwent the robotic technique. CONCLUSIONS: This is the largest reported series of SLCC for epilepsy to date. SLCC provides seizure outcomes comparable to open surgery outcomes reported in the literature. Direct MRI guidance is more accurate, which has the potential to reduce the risks of SLCC. Methodological advancements and larger studies are needed.

Uncovering the Functional Role of Coherent Phonons during the Photoinduced Phase Transition in a Molecular Crystal.

The atomic motions that make up phonons and molecular vibrations in molecular crystals influence their photophysical and electronic properties, including polaron formation, carrier mobility, and phase transitions. Discriminating between spectator and driving motions is a significant challenge hindering optimization. Unlocking this information and developing fine-tuned controls over actively participating phonon modes would not only lead to a stronger understanding of photochemistry but also provide a significant new tool in controlling solid state chemistry. We present a strategy using rationally designed double pulses to unveil the unique function of specific excited state phonon modes. Using ultrafast spectroscopy, we identified 50 and 90 cm-1 phonons involved in modulating the photoinduced spin-Peierls melting of potassium tetracyanoquinodimethane crystals. We show that the 50 cm-1 phonon specifically corresponds to the coherent nuclear wavepacket involved in the charge transfer component of the overall spin-Peierls phase melting process, while the 90 cm-1 phonon facilitates the phase transition component.

Stereotactic MRI-guided laser interstitial thermal therapy for extratemporal lobe epilepsy.

OBJECTIVE: Magnetic resonance imaging (MRI)-guided laser interstitial thermal therapy (MRg-LITT) is an alternative to open epilepsy surgery. We assess safety and effectiveness of MRg-LITT for extratemporal lobe epilepsy (ETLE) in patients who are considered less favorable for open resection. METHODS: We retrospectively reviewed sequential cases of patients with focal ETLE who underwent MRg-LITT between 2012 and 2019. Epileptogenic zones were determined from standard clinical and imaging data ± stereoelectroencephalography (SEEG). Standard stereotactic techniques, MRI thermometry, and a commercial laser thermal therapy system were used for ablations. Anatomic MRI was used to calculate ablation volumes. Clinical outcomes were determined longitudinally. RESULTS: Thirty-five patients with mean epilepsy duration of 21.3 ± 12.2 years underwent MRg-LITT for focal ETLE at a mean age 36.4 ± 12.7 years. A mean 2.59 ± 1.45 trajectories per patient were used to obtain ablation volumes of 8.8 ± 7.5 cm3 . Mean follow-up was 27.3 ± 19.5 months. Of 32 patients with >12 months of follow-up, 17 (53%) achieved good outcomes (Engel class I + II) of whom 14 (44%) were Engel class I. Subgroup analysis revealed better outcomes for patients with lesional ETLE than for those who were nonlesional, multifocal, or who had failed prior interventions (P = .02). Of 13 patients showing favorable seizure-onset patterns (localized low voltage fast activity or rhythmic spiking on SEEG) prior to ablation, 9 (69%) achieved good outcomes, whereas only 3 of 11 (27%) who show other slower onset patterns achieved good outcomes. Minor adverse events included six patients with transient sensorimotor neurologic deficits and four patients with asymptomatic hemorrhages along the fiber tract. Major adverse events included one patient with a brain abscess that required stereotactic drainage and one patient with persistent hypothalamic obesity. Three deaths-two seizure-associated and one suicide-were unrelated to surgical procedures. SIGNIFICANCE: MRI-guided laser interstitial thermal therapy (or MRg-LITT) was well-tolerated and yielded good outcomes in a heterogeneous group of ETLE patients. Lesional epilepsy and favorable seizure-onset patterns on SEEG predicted higher likelihoods of success.

Femtosecond stimulated Raman spectro-microscopy for probing chemical reaction dynamics in solid-state materials.

Femtosecond stimulated Raman spectroscopy (FSRS) is a chemically specific vibrational technique that has the ability to follow structural dynamics during photoinduced processes such as charge transfer on the ultrafast timescale. FSRS has a strong background in following structural dynamics and elucidating chemical mechanisms; however, its use with solid-state materials has been limited. As photovoltaic and electronic devices rely on solid-state materials, having the ability to track the evolving dynamics during their charge transfer and transport processes is crucial. Following the structural dynamics in these solid-state materials will lead to the identification of specific chemical structures responsible for various photoinduced charge transfer reactions, leading to a greater understanding of the structure-function relationships needed to improve upon current technologies. Isolating the specific nuclear motions and molecular structures that drive a desired physical process will provide a chemical blueprint, leading to the rational design and fabrication of efficient electronic and photovoltaic devices. In this perspective, we discuss technical challenges and experimental developments that have facilitated the use of FSRS with solid-state samples, explore previous studies that have identified structure-function relationships in charge transfer reactions, and analyze the future developments that will broaden and advance the field.

Minimally Invasive Resection of Intracerebral Amyloidoma: Case Report and Systematic Review of the Literature.

BACKGROUND: Management of cerebral amyloidomas has lacked consensus owing to their rarity. We present a case and review 39 reported cases of amyloidomas in the literature, comparing their initial presentation, imaging characteristics, treatment, and progression. CASE DESCRIPTION: A 56-year-old woman presented with a history of intractable headaches and progressive speech difficulty. Imaging demonstrated a 1.7 × 2.6 cm left frontal subcortical hemorrhagic mass with an associated developmental venous anomaly, characteristics initially suggestive of a cavernous malformation. Diffusion tractography imaging was employed to avoid interference with the intact arcuate fasciculus and corticospinal tracts to minimize neurologic deficits. CONCLUSIONS: To our knowledge, this is the first documented case of the use of diffusion tractography in preoperative planning for cerebral amyloidoma resection. Our systematic review of 39 reported cases of amyloidomas in the literature provided insight regarding how these rare lesions have manifested and progressed and further understanding of current theories regarding their etiology and pathophysiology. Cerebral amyloidomas are rare, localized, proteinaceous aggregates with variable presentation and prognosis and no apparent relationship to systemic amyloidosis. Biopsy may be useful in determination of progression. Diffusion tractography is a valuable tool for minimizing complications associated with resection.

Facile Background Discrimination in Femtosecond Stimulated Raman Spectroscopy Using a Dual-Frequency Raman Pump Technique.

Femtosecond stimulated Raman spectroscopy (FSRS) is a useful technique for uncovering chemical reaction dynamics by acquiring high-resolution Raman spectra with ultrafast time resolution. However, in FSRS, it can be challenging to discern Raman features from signals arising from transient absorption and other four-wave mixing pathways. To overcome this difficulty, we combine the principles of shifted excitation Raman difference spectroscopy with a simple fixed frequency comb to perform dual-frequency Raman pump FSRS. Through the addition of only two mirrors and a slit to the standard FSRS setup, this method provides Raman spectra at two different excitation wavelengths that can be processed by an automated algorithm to reconstruct the Raman spectrum. Here, we demonstrate the utility of dual-frequency Raman pump FSRS to easily identify Raman signatures by visual inspection for excited-state and ground-state spectra, both on- and off-resonance. We show that previously assigned short-lived vibrations of photoexcited ß-carotene are actually not vibrational in nature. We also use crystalline betaine-30 as a challenging test case for this method, as the FSRS spectra contain a number of narrow transient vibronic and non-SRS features. By reliably reducing interference from background signals, the interpretation is substantially more quantitative and enables the future study of new systems, particularly those with small Raman cross-sections or solid-state samples with narrow vibronic features.

Observation of topological phenomena in a programmable lattice of 1,800 qubits.

The work of Berezinskii, Kosterlitz and Thouless in the 1970s1,2 revealed exotic phases of matter governed by the topological properties of low-dimensional materials such as thin films of superfluids and superconductors. A hallmark of this phenomenon is the appearance and interaction of vortices and antivortices in an angular degree of freedom-typified by the classical XY model-owing to thermal fluctuations. In the two-dimensional Ising model this angular degree of freedom is absent in the classical case, but with the addition of a transverse field it can emerge from the interplay between frustration and quantum fluctuations. Consequently, a Kosterlitz-Thouless phase transition has been predicted in the quantum system-the two-dimensional transverse-field Ising model-by theory and simulation3-5. Here we demonstrate a large-scale quantum simulation of this phenomenon in a network of 1,800 in situ programmable superconducting niobium flux qubits whose pairwise couplings are arranged in a fully frustrated square-octagonal lattice. Essential to the critical behaviour, we observe the emergence of a complex order parameter with continuous rotational symmetry, and the onset of quasi-long-range order as the system approaches a critical temperature. We describe and use a simple approach to statistical estimation with an annealing-based quantum processor that performs Monte Carlo sampling in a chain of reverse quantum annealing protocols. Observations are consistent with classical simulations across a range of Hamiltonian parameters. We anticipate that our approach of using a quantum processor as a programmable magnetic lattice will find widespread use in the simulation and development of exotic materials.

Phase Acrobatics: The Influence of Excitonic Resonance and Gold Nonresonant Background on Heterodyne-Detected Vibrational Sum Frequency Generation Emission.

We show how heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy can discriminate between the excitonic and monomeric properties of a helical, nanotube molecular aggregate by monitoring the phase of the VSFG emission associated with different polarization configurations. By keeping track of the "phase acrobatics" associated with the added phase of the nonresonant SFG emission of gold as well as that of the double-resonance conditions achieved when the SF frequency is resonant with an electronic exciton transition, we discover that for aggregates of tetra(sulfonatophenyl)porphyrin (TSPP) the PPP-polarized spectra exhibit double-resonance conditions while SSP-polarized spectra exhibit resonance only with the ground-state vibration. Along with observed shifts in the vibrational frequency, intensity differences, and sign flips in the imaginary second-order susceptibility, χs,Im(2), we conclude that PPP-polarized HD-VSFG spectra reflect the delocalized, excitonic nature of the molecular aggregate, while the SSP-polarized HD-VSFG spectra measure the localized, monomeric nature of the molecular subunits. It is implied from this study that HD-VSFG spectroscopy can be uniquely utilized to measure the excitonic and monomeric properties associated with molecular assemblies for a single sample.

Reversal of Gastric Bypass Resolves Hyperoxaluria and Improves Oxalate Nephropathy Secondary to Roux-en-Y Gastric Bypass.

Hyperoxaluria after Roux-en-Y gastric bypass (RYGB) increases the risk for kidney injury. Medical therapies for hyperoxaluria have limited efficacy. A 65-year-old female was evaluated for acute kidney injury [AKI, serum creatinine (Cr) 2.1 mg/dl, baseline Cr 1.0 mg/dl]. She did not have any urinary or gastrointestinal symptoms or exposure to nephrotoxic agents. Sixteen months prior to this evaluation, she underwent RYGB for morbid obesity. Her examination was unremarkable for hypertension or edema and there was no protein or blood on urine dipstick. Kidney biopsy revealed acute tubulointerstitial nephritis with oxalate crystals in tubules. The concurrent finding of severe hyperoxaluria (urine oxalate 150 mg/day) confirmed the diagnosis of oxalate nephropathy. Despite medical management of hyperoxaluria, her AKI worsened. Laparoscopic reversal of RYGB was performed and within 1 month, her hyperoxaluria resolved (urine oxalate 20 mg/day) and AKI improved (Cr 1.7 mg/dl). Surgical reversal of RYGB may be considered in patients with oxalate nephropathy at high risk of progression who fail medical therapy. Physicians need to be aware of the possibility of oxalate nephropathy after RYGB and promptly treat the hyperoxaluria to halt further kidney damage.

Influence of hydrogen bonding on excitonic coupling and hierarchal structure of a light-harvesting porphyrin aggregate.

Helical porphyrin nanotubes of tetrakis(4-sulfonatophenyl)porphyrin (TSPP) were examined in DCl/D(2)O solution using resonance Raman and resonance light scattering spectroscopy to probe the influence of hydrogen bonding on the excitonic states. Atomic force microscopy reveals similar morphology for aggregates deposited from DCl/D(2)O and from HCl/H(2)O solution. Deuteration results in subtle changes to the aggregate absorption spectrum but large changes in the relative intensities of Raman modes in the J-band excited resonance Raman spectra, revealing relatively more reorganization along lower-frequency vibrational modes in the protiated aggregate. Depolarization ratio dispersion and changes in the relative Raman intensities for excitation wavelengths spanning the J-band demonstrate interference from overlapping excitonic transitions. Distinctly different Raman excitation profiles for the protiated and deuterated aggregates reveal that isotopic substitution influences the excitonic structure of the J-band. The deuterated aggregate exhibits a nearly two-fold increase in intensity of resonance light scattering as a result of an increase in the coherence number, attributed to decreased exciton-phonon scattering. We propose that strongly coupled cyclic N-mers, roughly independent of isotopic substitution, largely decide the optical absorption spectrum, while water-mediated hydrogen bonding influences the further coherent coupling among them when they are assembled into nanotubes. The results show that, similar to natural light-harvesting complexes such as chlorosomes, hydrogen bonding can have a critical influence on exciton dynamics.

Use of propofol and emergence agitation in children: a literature review.

Emergence agitation (EA) is an important issue in pediatric anesthesia. This phenomenon arises more frequently with the use of inhalational agents. Three commonly used general anesthesia techniques in children were evaluated as to the associated incidence of emergence reactions. An extensive literature review was performed to evaluate these anesthetic practices and the occurrence of EA in young children. Relevant literature was obtained from multiple sources, including professional journals, professional websites, and textbooks. Three categories of anesthesia techniques were reviewed: sevoflurane inhalational general anesthetic, Emerpropofol as an adjunct to sevoflurane general anesthetic, and propofol total intravenous anesthesia (TIVA) techniques. Several variables within each category were evaluated with respect to the outcome of EA: prevention, intraoperative adjuncts, type of surgery, and patient-related factors. According to the literature evidence base, there is an advantage to either propofol TIVA or adjunctive propofol with sevoflurane (compared with sevoflurane alone). We conclude, based on the current evidence, that the use of propofol is associated with a reduction in the incidence of emergence agitation.

Effect of disorder on the optical properties of colloidal crystals.

Colloidal crystals offer a promising route for the formation of three-dimensional photonic crystals. The primary constraint in working with these materials is the disorder present in these self-assembled materials. Sphere vacancies, line dislocations, and random position errors all lead to a degradation in the optical properties. It is important to characterize these effects so as to guide further developments in colloidal crystal optics. Here, we report a systematic and quantitative study of disorder in colloidal crystals with visible diffractive properties. Using optical spectroscopy and digital imaging we have correlated several measures of structural disorder with variations in the transmissive and reflective optical properties. We observe a critical size distribution above which rapid deterioration of the lowest stop band is observed. Below this critical size distribution, we observe excellent optical quality, nearly independent of the size distribution. Single sphere vacancies also increase in crystals formed from more polydisperse spheres. The primary effect of this type of defect is to increase the broadband diffuse scattering.