A Nationwide Survey of Educational Resource Utilization and Perception Among Internal Medicine Residents.

BACKGROUND: New virtual resources ("novel resources") have been incorporated into medical education. No recent large studies about their use and perception among internal medicine (IM) residents exist. OBJECTIVE: Characterize the use and perceived helpfulness of educational resources. DESIGN: Nationwide survey from December 2019 to March 2020. PARTICIPANTS: IM residents in the USA. MAIN MEASURES: Residents were surveyed on their use and their perceived helpfulness of resources for both attaining general medical knowledge and for point-of-care (POC) learning. Traditional resources included board review resources, clinical experience, digital clinical resources (e.g., UpToDate), journal articles, pocket references, professional guidelines, textbooks, and residency curricula. Novel resources included Twitter, video streaming platforms (e.g., YouTube), online blogs, podcasts, and Wikipedia. KEY RESULTS: We had 662 respondents from 55 residency programs across 26 states. On average, residents used 9 total resources (7 traditional and 2 novel). Digital clinical resources and clinical experience were used by all residents and found helpful by the highest percentage of residents (96% and 94%, respectively). Journal articles were next (used by 90%), followed by board review resources and residency curricula (both used by 85%). Their perceived helpfulness varied, from 90% for board review resources, to 66% for journal articles and 64% for residency curricula, the lowest perceived helpfulness of any traditional resource. Podcasts and video streaming platforms were used as frequently as textbooks (58-59%), but were rated as helpful more frequently (75% and 82% vs 66%, respectively). CONCLUSIONS: Digital clinical resources, video streaming platforms, and podcasts were perceived as helpful, underscoring the importance of ensuring their integration into medical education to complement clinical experience and other traditional resources which remain highly valued by residents. IMPORTANCE: Our findings can inform residency programs as they transition to virtual curricula in the wake of the COVID-19 pandemic.

Client and provider factors associated with integration of family planning services among maternal and reproductive health clients in Kigoma Region, Tanzania: a cross-sectional study, April-July 2016.

BACKGROUND: Integration of family planning (FP) services into non-FP care visits is an essential strategy for reducing maternal and neonatal mortality through reduction of short birth intervals and unplanned pregnancies. METHODS: Cross-sectional surveys were conducted across 61 facilities in Kigoma Region, Tanzania, April-July 2016. Multilevel, mixed effects logistic regression analyses were conducted on matched data from providers (n = 330) and clients seeking delivery (n = 935), well-baby (n = 272), pregnancy loss (PL; n = 229), and other routine (postnatal, HIV/STI, other; n = 69) services. Outcomes of interest included receipt of FP information and a modern FP method (significance level p < 0.05). RESULTS: Clients had significantly greater odds of receiving FP information if the primary reason for seeking care was for PL versus (vs) any other types of care (aOR 1.97), had four or more pregnancies vs fewer (aOR 1.78), and had had a FP discussion with their partner vs no FP discussion (aOR 1.73). Clients had lower odds of receiving FP information if they were aged 40-49 vs 15-19 (aOR 0.50) and reported attending religious services at least weekly vs less frequently (aOR 0.61). Clients of providers who perceived that in-service training had helped vs had not helped job performance (aOR 2.27), and clients of providers having high vs low recent FP training index scores (aOR 1.58) had greater odds of receiving FP information. Clients had greater odds of receiving a modern method when they received information on two or more vs fewer methods (aOR 7.13), had had a FP discussion with their partner vs no discussion (aOR 5.87), if the primary reason for seeking care was for PL vs any other types of care (aOR 4.08), had zero vs one or more live births (aOR 3.92), made their own FP decisions vs not made own FP decisions (aOR 3.17), received FP information from two or more vs fewer sources (aOR 3.12), and were in the middle or high vs the low wealth tercile (aOR 1.99 and 2.30, respectively). Well-baby care clients, Other routine services clients, and married clients had significantly lower odds of receiving a method (aOR 0.14; aOR 0.08; and aOR 0.41, respectively) compared to their counterparts. CONCLUSIONS: Strategies that better integrate FP into routine care visits, encourage women to have FP discussions with their partners and providers, increase FP training among providers, and expand FP options and sources of information may help reduce the unmet need for FP, and ultimately lower maternal and neonatal mortality.

Ultrasound curriculum taught by first-year medical students: A four-year experience in Tanzania / 世界急诊医学杂志（英文）

BACKGROUND:Diagnostic imaging is an integral aspect of care that is often insufficient, if not altogether absent, in rural and remote regions of low to middle income countries (LMICs) such as Tanzania. The introduction of ultrasound can significantly impact treatment in these countries due to its portability, low cost, safety, and usefulness in various medical assessments. This study reviews the implementation of a four-week ultrasound course administered annually from 2013–2016 in a healthcare professional school in Mwanza, Tanzania by first-year allopathic US medical students. METHODS:Participants (n=582, over 4 years) were recruited from the Tandabui Institute of Health Sciences and Technology to take the ultrasound course. Subjects were predominantly clinical officer students, but other participants included other healthcare professional students, practicing healthcare professionals, and school employees. Data collected includes pre-course examination scores, post-course examination scores, course quiz scores, demographic surveys, and post-course feedback surveys. Data was analyzed using two-tailed t-tests and the single factor analysis of variance (ANOVA). RESULTS:For all participants who completed both the pre- and post-course examinations (n=229, 39.1％ of the total recruited), there was a significant mean improvement in their ultrasound knowledge of 42.5％, P<0.01. CONCLUSION:Our data suggests that trained first-year medical students can effectively teach a point of care ultrasound course to healthcare professional students within four weeks in Tanzania. Future investigation into the level of long-term knowledge retention, impact of ultrasound training on knowledge of human anatomy and diagnostic capabilities, and how expansion of an ultrasound curriculum has impacted access to care in rural Tanzania is warranted.

Obesity, but not metabolic syndrome, negatively affects outcome in bipolar disorder.

OBJECTIVE: Examine the effects of obesity and metabolic syndrome on outcome in bipolar disorder. METHOD: The Comparative Effectiveness of a Second Generation Antipsychotic Mood Stabilizer and a Classic Mood Stabilizer for Bipolar Disorder (Bipolar CHOICE) study randomized 482 participants with bipolar disorder in a 6-month trial comparing lithium- and quetiapine-based treatment. Baseline variables were compared between groups with and without obesity, with and without abdominal obesity, and with and without metabolic syndrome respectively. The effects of baseline obesity, abdominal obesity, and metabolic syndrome on outcomes were examined using mixed effects linear regression models. RESULTS: At baseline, 44.4% of participants had obesity, 48.0% had abdominal obesity, and 27.3% had metabolic syndrome; neither obesity, nor abdominal obesity, nor metabolic syndrome were associated with increased global severity, mood symptoms, or suicidality, or with poorer functioning or life satisfaction. Treatment groups did not differ on prevalence of obesity, abdominal obesity, or metabolic syndrome. By contrast, among the entire cohort, obesity was associated with less global improvement and less improvement in total mood and depressive symptoms, suicidality, functioning, and life satisfaction after 6 months of treatment. Abdominal obesity was associated with similar findings. Metabolic syndrome had no effect on outcome. CONCLUSION: Obesity and abdominal obesity, but not metabolic syndrome, were associated with less improvement after 6 months of lithium- or quetiapine-based treatment.

Chromatin immunoprecipitation of adult murine cardiomyocytes.

This unit describes a streamlined two-step protocol for the isolation of adult murine cardiomyocytes with subsequent Chromatin ImmunoPrecipitation (ChIP). Isolation and culturing of cardiomyocytes is a delicate process and the protocol presented here optimizes the combination of cardiomyocyte isolation with ChIP. ChIP is an invaluable method for analyzing molecular interactions occurring between a specific protein (or its post-translationally modified form) and a region of genomic DNA. ChIP has become a widely used technique in the last decade since several groundbreaking studies have focused attention on epigenetics and have identified many epigenetic regulatory mechanisms. However, epigenetics within cardiovascular biology is a new area of focus for many investigators, and we have optimized a method for performing ChIP in adult murine cardiomyocytes, as we feel this will be an important aid to both the cardiovascular field and for the development of cell- and tissue-specific ChIP.

GlideScope® vs flexible fibreoptic scope for elective intubation in obese patients.

We hypothesised that in obese patients, tracheal intubation with the GlideScope® would be advantageous compared with flexible fibreoptic intubation. Seventy-five anaesthetised obese patients were randomly assigned to oral intubation by either GlideScope or flexible fibreoptic bronchoscope. We compared the two devices for time to intubate (p = 0.19), difficulty of intubation (p = 0.58), successful intubation on first attempt (p = 0.29), number of attempts (p = 0.24), incidence of hypoxaemia (p = 0.57), amount of post-intubation bleeding (p = 0.79) and sore throat (p = 0.82). None differed significantly. Median (IQR [range]) time to intubation was 37 (25-48 [19-81]) s and 95% of the first attempts were successful with the GlideScope, vs 43 (35-58 [26-96]) s and an 86% first-attempt success rate with the flexible fibreoptic bronchoscope. For experienced users, the time required to intubate the trachea in anaesthetised obese patients is similar with the GlideScope and a flexible bronchoscope.

Nonadiabatic decomposition of gas-phase RDX through conical intersections: an ONIOM-CASSCF study.

Topographical exploration of nonadiabatically coupled ground- and excited-electronic-state potential energy surfaces (PESs) of the isolated RDX molecule was performed using the ONIOM methodology: Computational results were compared and contrasted with the previous experimental results for the decomposition of this nitramine energetic material following electronic excitation. One of the N-NO(2) moieties of the RDX molecule was considered to be an active site. Electronic excitation of RDX was assumed to be localized in the active site, which was treated with the CASSCF algorithm. The influence of the remainder of the molecule on the chosen active site was calculated by either a UFF MM or RHF QM method. Nitro-nitrite isomerization was predicted to be a major excited-electronic-state decomposition channel for the RDX molecule. This prediction directly corroborates previous experimental results obtained through photofragmentation-fragment detection techniques. Nitro-nitrite isomerization of RDX was found to occur through a series of conical intersections (CIs) and was finally predicted to produce rotationally cold but vibrationally hot distributions of NO products, also in good agreement with the experimental observation of rovibrational distributions of the NO product. The ONIOM (CASSCF:UFF) methodology predicts that the final step in the RDX dissociation occurs on its S(0) ground-electronic-state potential energy surface (PES). Thus, the present work clearly indicates that the ONIOM method, coupled with a suitable CASSCF method for the active site of the molecule, at which electronic excitation is assumed to be localized, can predict hitherto unexplored excited-electronic-state PESs of large energetic molecules such as RDX, HMX, and CL-20. A comparison of the decomposition mechanism for excited-electronic-state dimethylnitramine (DMNA), a simple analogue molecule of nitramine energetic materials, with that for RDX, an energetic material, was also performed. CASSCF pure QM calculations showed that, following electronic excitation of DMNA to its S(2) surface, decomposition of this molecule occurs on its S(1) surface through a nitro-nitrite isomerization producing rotationally hot and vibrationally cold distributions of the NO product.

Experimental and theoretical studies of reactions of neutral vanadium and tantalum oxide clusters with NO and NH3.

Reactions of neutral vanadium and tantalum oxide clusters with NO, NH(3), and an NO/NH(3) mixture in a fast flow reactor are investigated by time of flight mass spectrometry and density functional theory (DFT) calculations. Single photon ionization through a 46.9 nm (26.5 eV) extreme ultraviolet (EUV) laser is employed to detect both neutral cluster distributions and reaction products. Association products VO(3)NO and V(2)O(5)NO are detected for V(m)O(n) clusters reacting with pure NO, and reaction products, TaO(3,4)(NO)(1,2), Ta(2)O(5)NO, Ta(2)O(6)(NO)(1-3), and Ta(3)O(8)(NO)(1,2) are generated for Ta(m)O(n) clusters reacting with NO. In both instances, oxygen-rich clusters are the active metal oxide species for the reaction M(m)O(n)+NO→M(m)O(n)(NO)(x). Both V(m)O(n) and Ta(m)O(n) cluster systems are very active with NH(3). The main products of the reactions with NH(3) result from the adsorption of one or two NH(3) molecules on the respective clusters. A gas mixture of NO:NH(3) (9:1) is also added into the fast flow reactor: the V(m)O(n) cluster system forms stable, observable clusters with only NH(3) and no V(m)O(n)(NO)(x)(NH(3))(y) species are detected; the Ta(m)O(n) cluster system forms stable, observable mixed clusters, Ta(m)O(n)(NO)(x)(NH(3))(y), as well as Ta(m)O(n)(NO)(x) and Ta(m)O(n)(NH(3))(y) individual clusters, under similar conditions. The mechanisms for the reactions of neutral V(m)O(n) and Ta(m)O(n) clusters with NO/NH(3) are explored via DFT calculations. Ta(m)O(n) clusters form stable complexes based on the coadsorption of NO and NH(3). V(m)O(n) clusters form weakly bound complexes following the reaction pathway toward end products N(2)+H(2)O without barrier. The calculations give an interpretation of the experimental data that is consistent with the condensed phase reactivity of V(m)O(n) catalyst and suggest the formation of intermediates in the catalytic chemistry.

Unimolecular decomposition of tetrazine-N-oxide based high nitrogen content energetic materials from excited electronic states.

Unimolecular excited electronic state decomposition of novel high nitrogen content energetic molecules, such as 3,3(')-azobis(6-amino-1,2,4,5-tetrazine)-mixed N-oxides (DAATO(3.5)), 3-amino-6-chloro-1,2,4,5-tetrazine-2,4-dioxide (ACTO), and 3,6-diamino-1,2,4,5-tetrazine-1,4-dioxde (DATO), is investigated. Although these molecules are based on N-oxides of a tetrazine aromatic heterocyclic ring, their decomposition behavior distinctly differs from that of bare tetrazine, in which N(2) and HCN are produced as decomposition products through a concerted dissociation mechanism. NO is observed to be an initial decomposition product from all tetrazine-N-oxide based molecules from their low lying excited electronic states. The NO product from DAATO(3.5) and ACTO is rotationally cold (20 K) and vibrationally hot (1200 K), while the NO product from DATO is rotationally hot (50 K) and vibrationally cold [only the (0-0) vibronic transition of NO is observed]. DAATO(3.5) and ACTO primarily differ from DATO with regard to molecular structure, by the relative position of oxygen atom attachment to the tetrazine ring. Therefore, the relative position of oxygen in tetrazine-N-oxides is proposed to play an important role in their energetic behavior. N(2)O is ruled out as an intermediate precursor of the NO product observed from all three molecules. Theoretical calculations at CASMP2/CASSCF level of theory predict a ring contraction mechanism for generation of the initial NO product from these molecules. The ring contraction occurs through an (S(1)/S(0))(CI) conical intersection.

The pulsed-dye laser for treatment of cutaneous conditions.

The concept of selective photothermolysis simply states that if one heats target tissue with a laser that is selectively absorbed by that tissue, heat should last sufficiently enough to cause damage to the target tissue, but not so long for the heat to spread to the surrounding tissue. The pulsed-dye laser (PDL) was the first laser to utilize the concept of selective photothermolysis to treat dermatologic conditions. The first application of this concept was directed at treating port-wine stain birthmarks (PWSs). A myriad of conditions that were previously only marginally treated by earlier-generation PDLs could be addressed, increasing by a factor of many thousand the number of potential patients for PDL treatment. Rosacea, scars, red striae, some lower-extremity spider veins, and photodamage could now be easily treated in addition to PWSs, nevus araneuses, cherry hemangioma, and verrucae. Finally, the latest advances in PDL technology have maximized the ability to treat linear vessels such as lower-extremity spider veins, and linear facial vessels associated with rosacea, photodamage or simply heredity, as well as improving the ability to treat diffuse erythema such as the facial redness of rosacea, PWSs, scars and striae with less risk of epidermal damage and hyperpigmentation. Final advances aim to reduce side-effects of both types of vascular lasers while potentially increasing benefits by allowing the delivery of higher fluencies. Cooling the surface of the skin protects melanin pigment while allowing the delivery of light to the dermis to remove unwanted blood vessels and potentially stimulate dermal remodeling.

Photodissociation dynamics of nitromethane at 226 and 271 nm at both nanosecond and femtosecond time scales.

Photodissociation of nitromethane has been investigated for decades both theoretically and experimentally; however, as a whole picture, the dissociation dynamics for nitromethane are still not clear, although many different mechanisms have been proposed. To make a complete interpretation of these different mechanisms, photolysis of nitromethane at 226 and 271 nm under both collisional and collisionless conditions is investigated at nanosecond and femtosecond time scales. These two laser wavelengths correspond to the pi* <-- pi and pi* <-- n excitations of nitromethane, respectively. In nanosecond 226 nm (pi* <-- pi) photolysis experiments, CH(3) and NO radicals are observed as major products employing resonance enhanced multiphoton ionization techniques and time-of-flight mass spectrometry. Additionally, OH and CH(3)O radicals are weakly observed as dissociation products employing laser induced fluorescence spectroscopy; the CH(3)O product is only observed under collisional conditions. In femtosecond 226 nm experiments, CH(3), NO(2), and NO products are observed. These results confirm that rupture of C-N bond should be the main primary process for the photolysis of nitromethane after the pi* <-- pi excitation at 226 nm, and the NO(2) molecule should be the precursor of the observed NO product. Formation of the CH(3)O radical after the recombination of CH(3) and NO(2) species under collisional conditions rules out a nitro-nitrite isomerization mechanism for the generation of CH(3)O and NO from pi pi* CH(3)NO(2). The OH radical formation for pi pi* CH(3)NO(2) should be a minor dissociation channel because of the weak OH signal in both nanosecond and femtosecond (nonobservable) experiments. Single color femtosecond pump-probe experiments at 226 nm are also employed to monitor the dynamics of the dissociation of nitromethane after the pi* <-- pi excitation. Because of the ultrafast dynamics of product formation at 226 nm, the pump-probe transients for the three dissociation products are measured as an autocorrelation of the laser pulse, indicating the dissociation of nitromethane in the pi pi* excited state is faster than the laser pulse duration (180 fs). In nanosecond 271 nm (pi* <-- n) photolysis experiments, pump-probe experiments are performed to detect potential dissociation products, such as CH(3), NO(2), CH(3)O, and OH; however, none of them is observed. In femtosecond 271 nm laser experiments, the nitromethane parent ion is observed with major intensity, together with CH(3), NO(2), and NO fragment ions with only minor intensities. Pump-probe transients for both nitromethane parent and fragment ions at 271 nm excitation and 406.5 nm ionization display a fast exponential decay with a constant time of 36 fs, which we suggest to be the lifetime of the excited n pi* state of nitromethane. Combined with the 271 nm nanosecond pump-probe experiments, in which none of the CH(3), NO(2), CH(3)O, or OH fragment is observed, we suggest that all the fragment ions generated in 271 nm femtosecond laser experiments are derived from the parent ion, and dissociation of nitromethane from the n pi* excited electronic state does not occur in a supersonic molecular beam under collisionless conditions.

Experimental and theoretical exploration of the initial steps in the decomposition of a model nitramine energetic material: dimethylnitramine.

Decomposition of dimethylnitramine (DMNA, (CH(3))(2)NNO(2)) has been studied extensively over the past decades. Although several different mechanisms have been proposed for the initial decomposition of DMNA, the dominant decomposition channel is still far from fully understood. In this report, we collect all the results reported in the literature, along with our new experimental and theoretical results, into a single reference for a sensible comparison in order to reach a general conclusion on DMNA decomposition. In this effort, nanosecond laser, energy resolved spectroscopy and complete active space self-consistent field (CASSCF) calculations are employed. The parent DMNA molecule is electronically excited using two different UV excitation wavelengths, 226 and 193 nm, to initiate the decomposition process. The NO molecule is observed as a major decomposition product with relatively hot (120 K) rotational and cold vibrational distributions by both time-of-flight mass spectrometry and laser induced fluorescence spectroscopy. On the basis of the experimental observations, a nitro-nitrite isomerization mechanism is predicted to be the major channel of decomposition of DMNA in the excited electronic state with a minor contribution from the HONO elimination mechanism. The branching ratio between nitro-nitrite isomerization and HONO elimination channels is estimated to be approximately 1:0.04. CASSCF calculations show that surface crossing (conical intersection) between upper and lower electronic states along the nitro-nitrite isomerization reaction coordinate plays an important role in the overall decomposition of DMNA. Presence of such an (S(2)/S(1))(CI) conical intersection in the nitro-nitrite isomerization reaction coordinate provides a direct nonadiabatic decomposition pathway from the Franck-Condon point of the S(2) surface, which is experimentally accessed by 226 nm photoexcitation. This excited state isomerization takes place through a loose geometry for which the NO(2) moiety interacts with the (CH(3))(2)N moiety from a long distance (approximately 2.8 A); however, in the ground electronic state, a similar (S(1)/S(0))(CI) conical intersection in this nitro-nitrite isomerization reaction coordinate hinders the isomerization exit channel, rendering NO(2) elimination as the major thermal decomposition channel of DMNA.

Reaction of carbon monoxide and hydrogen on neutral Nb8 clusters in the gas phase.

Reactions of neutral V(n), Nb(n), and Ta(n) metal clusters (n< or =11) with CO+H(2) mixed gases and CH(3)OH in a flow tube reactor (1-50 Torr) are studied by time of flight mass spectroscopy and density functional theory calculations. Metal clusters are generated by laser ablation, and reactants and products are ionized by low fluence (approximately 200 microJ/cm(2)) 193 nm excimer laser light. Nb(n) clusters exhibit strong size dependent reactivity in reactions both with CO+H(2) and CH(3)OH compared with V(n) and Ta(n) clusters. A "magic number" (relatively intense) mass peak at Nb(8)COH(4) is observed in the reaction of Nb(n) clusters with CO+H(2), and CH(3)OH is suggested to be formed. This feature at Nb(8)COH(4) remains the most intense peak independent of the relative concentrations of CO and H(2) in the flow tube reactor. No other Nb(n), Ta(n), or V(n) feature behaves in this manner. In reactions of CH(3)OH with metal clusters M(n) (M=V, Nb, and Ta, n=3-11), nondehydrogenated products M(n)COH(4)/M(n)CH(3)OH are only observed on Nb(8) and Nb(10), whereas dehydrogenated products M(n)CO/CM(n)O are observed for all other clusters. These observations support the suggestion that CH(3)OH can be formed on Nb(8) in the reaction of Nb(n) with CO+H(2). A reaction mechanism is suggested based on the experimental results and theoretical calculations of this work and of those in the literature. Methanol formation from CO+H(2) on Nb(8) is overall barrierless and thermodynamically and kinetically favorable.

A histopathologic evaluation of the Plasma Skin Regeneration System (PSR) versus a standard carbon dioxide resurfacing laser in an animal model.

BACKGROUND AND OBJECTIVES: A variety of high energy, pulsed, and scanned carbon dioxide lasers are available to perform cutaneous resurfacing. Rhytec has developed a device for skin regeneration that utilizes energy delivered via a burst of nitrogen plasma. This study was undertaken to benchmark the energy outputs of the plasma skin regeneration device as compared to an ultra-short pulsed carbon dioxide laser (the control device). The two systems were compared for time to complete healing, and the healing response post-treatment. MATERIALS AND METHODS: Three Yucatan mini-pigs were utilized for this study. Following anesthesia, five experimental sites were marked along the skin atop the psoas muscle on each side of the spine. Treatment was applied using either the plasma skin regeneration system or the carbon dioxide laser, with one site remaining untreated as a control. Biopsies were taken from all treatment sites 0, 2, 7, 14, 30, and 60 days following treatment and processed to hematoxylin-eosin staining. Histopathologic examination was performed by observers blinded as to the treatment conditions. RESULTS: Skin treated with the plasma skin regeneration device showed a wider range of tissue effects across the energy settings used as compared to the laser treatment. All treatment sites had clinically regenerated epidermis by 7 days after treatment, with active cellular response below the D/E junction noted at the day 30 time-point at energies ranging from 2 to 4 J. CONCLUSION: The Rhytec PSR system provides an attractive alternative to standard CO2 laser with good remodeling of tissue architecture. Epidermis regenerated after PSR treatment shows a smoother surface profile than adjacent untreated tissue.

Excited electronic state decomposition of furazan based energetic materials: 3,3'-diamino-4,4'-azoxyfurazan and its model systems, diaminofurazan and furazan.

We report the first experimental and theoretical study of gas phase excited electronic state decomposition of a furazan based, high nitrogen content energetic material, 3,3'-diamino-4,4'-azoxyfurazan (DAAF), and its model systems, diaminofurazan (DAF) and furazan (C2H2N2O). DAAF has received major attention as an insensitive high energy explosive; however, the mechanism and dynamics of the decomposition of this material are not clear yet. In order to understand the initial decomposition mechanism of DAAF and those of its model systems, nanosecond energy resolved and femtosecond time resolved spectroscopies and complete active space self-consistent field (CASSCF) calculations have been employed to investigate the excited electronic state decomposition of these materials. The NO molecule is observed as an initial decomposition product from DAAF and its model systems at three UV excitation wavelengths (226, 236, and 248 nm) with a pulse duration of 8 ns. Energies of the three excitation wavelengths coincide with the (0-0), (0-1), and (0-2) vibronic bands of the NO A 2Sigma+<--X 2Pi electronic transition, respectively. A unique excitation wavelength independent dissociation channel is observed for DAAF, which generates the NO product with a rotationally cold (20 K) and a vibrationally hot (1265 K) distribution. On the contrary, excitation wavelength dependent dissociation channels are observed for the model systems, which generate the NO product with both rotationally cold and hot distributions depending on the excitation wavelengths. Potential energy surface calculations at the CASSCF level of theory illustrates that two conical intersections between the excited and ground electronic states are involved in two different excitation wavelength dependent dissociation channels for the model systems. Femtosecond pump-probe experiments at 226 nm reveal that the NO molecule is still the main observed decomposition product from the materials of interest and that the formation dynamics of the NO product is faster than 180 fs. Two additional fragments are observed from furazan with mass of 40 amu (C2H2N) and 28 amu (CH2N) employing femtosecond laser ionization. This observation suggests a five-membered heterocyclic furazan ring opening mechanism with rupture of a CN and a NO bond, yielding NO as a major decomposition product. NH2 is not observed as a secondary decomposition product of DAAF and DAF.

On the excited electronic state dissociation of nitramine energetic materials and model systems.

In order to elucidate the difference between nitramine energetic materials, such as RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), and their nonenergetic model systems, including 1,4-dinitropiperazine, nitropiperidine, nitropyrrolidine, and dimethylnitramine, both nanosecond mass resolved excitation spectroscopy and femtosecond pump-probe spectroscopy in the UV spectral region have been employed to investigate the mechanisms and dynamics of the excited electronic state photodissociation of these materials. The NO molecule is an initial decomposition product of all systems. The NO molecule from the decomposition of energetic materials displays cold rotational and hot vibrational spectral structures. Conversely, the NO molecule from the decomposition of model systems shows relatively hot rotational and cold vibrational spectra. In addition, the intensity of the NO ion signal from energetic materials is proportional to the number of nitramine functional groups in the molecule. Based upon experimental observations and theoretical calculations of the potential energy surface for these systems, we suggest that energetic materials dissociate from ground electronic states after internal conversion from their first excited states, and model systems dissociate from their first excited states. In both cases a nitro-nitrite isomerization is suggested to be part of the decomposition mechanism. Parent ions of dimethylnitramine and nitropyrrolidine are observed in femtosecond experiments. All the other molecules generate NO as a decomposition product even in the femtosecond time regime. The dynamics of the formation of the NO product is faster than 180 fs, which is equivalent to the time duration of our laser pulse.

Single photon ionization of hydrogen bonded clusters with a soft x-ray laser: (HCOOH)x and (HCOOH)y(H2O)z.

Pure, neutral formic acid (HCOOH)n+1 clusters and mixed (HCOOH)(H2O) clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV using a very compact, capillary discharge, soft x-ray laser. During the ionization process, neutral clusters suffer little fragmentation because almost all excess energy above the vertical ionization energy is taken away by the photoelectron, leaving only a small part of the photon energy deposited into the (HCOOH)n+1+ cluster. The vertical ionization energy minus the adiabatic ionization energy is enough excess energy in the clusters to surmount the proton transfer energy barrier and induce the reaction (HCOOH)n+1+-->(HCOOH)nH+ +HCOO making the protonated (HCOOH)nH+ series dominant in all data obtained. The distribution of pure (HCOOH)nH+ clusters is dependent on experimental conditions. Under certain conditions, a magic number is found at n=5. Metastable dissociation rate constants of (HCOOH)nH+ are measured in the range (0.1-0.8)x10(4) s(-1) for cluster sizes 4

First Report of Sudden Death Syndrome of Soybean in Wisconsin.

In August of 2006, soybean (Glycine max (L.) Merr.) plants collected from Columbia, Dane, Green Lake, Walworth, Jefferson, and Waushara counties in southern Wisconsin exhibited symptoms typical of sudden death syndrome (SDS) caused by Fusarium virguliforme O'Donnell & Aoki [synonym F. solani (Mart.) Sacc. f. sp. glycines] (1). Foliar symptoms ranged from chlorotic spots to severe interveinal chlorosis and necrosis. Taproots of symptomatic plants were necrotic and stunted and stems exhibited a light tan discoloration, but never the dark brown discoloration typical for brown stem rot, a disease with similar foliar symptoms. Isolations from root and crown tissue of symptomatic plants were made using one-quarter-strength potato dextrose agar (PDA) amended with 100 ppm of streptomycin. Slow-growing, white-to-cream fungal colonies with blue and turquoise sporodochia were observed. Spores produced in sporodochia grown on PDA ranged in size from 32.5 to 70 µm long (average 53.1 µm) and 3 to 6 µm wide (average 4.4 µm) and with 3-5 septa (mode of 3). Isolates were characteristic of F. virguliforme based on colony morphology, spore morphology and size, and the absence of microconidia (3). The identity of F. virguliforme was confirmed by PCR amplification and DNA sequencing of the ITS, BT1, Act, and EF1B regions. All isolate sequences exhibited single nucleotide polymorphisms that matched the sequences of these regions of F. virguliforme. Koch's postulates were conducted to confirm that the causal agent of the observed symptoms was F. virguliforme. Inoculum of single-spore isolates was produced on sterilized sorghum seed. After 14 days of incubation at 20 to 22°C and a 12-h photoperiod, the sorghum seed was assayed to determine colonization incidence by transferring seeds to PDA. In all trials, sorghum seed was 100% infested. Infested sorghum seeds (35) were placed in potting soil at 2 cm beneath each seed of the susceptible soybean cv. Williams 82 (4). Noninfested sorghum seed was used for a noninoculated control. Three trials were performed, each using 15 replicates of several fungal isolates and 15 replicates of the noninoculated control. Plants were grown in water baths located in a greenhouse (trial 1) and in a growth chamber (trial 2) and both maintained at an average temperature of 25°C with a 14-h photoperiod (2). The third trial was conducted in the growth chamber without a water bath with the same temperature and light regimen. In all environments, inoculated plants developed chlorotic spots 14 days after planting. After 21 days, symptoms progressed to a range of chlorotic mottling to interveinal chlorosis and necrosis. Foliar and root symptoms that resembled those on the original plant samples infected with F. virguliforme appeared on 88% of inoculated plants. Isolates that resembled the original F. virguliforme were recovered from 75% of inoculated plants and from 88% of plants showing symptoms. No symptoms were observed and no isolates were recovered from noninoculated plants. There was a statistically significant difference between inoculated and control plants (P < 0.001) based on the presence of symptoms and isolation success using the Goodman χ2 analysis. The confirmation of the presence of SDS in five counties suggests that the disease is widespread in Wisconsin and could become a serious threat to soybean production in the future. References: (1) T. Akoi et al. Mycoscience 46:162, 2005. (2) R. Y. Hashmi et al. Online publication. doi:10.1094/PHP-2005-0906-01-RS. Plant Health Progress, 2005. (3) K. W. Roy et al. Plant Dis. 81:259, 1997. (4) J. C. Rupe et al. Can. J. Bot. 79:829, 2001.

IR plus vacuum ultraviolet spectroscopy of neutral and ionic organic acid molecules and clusters: acetic acid.

Infrared (IR) vibrational spectroscopy of acetic acid (A) neutral and ionic monomers and clusters, employing vacuum ultraviolet (VUV), 10.5 eV single photon ionization of supersonically expanded and cooled acetic acid samples, is presented and discussed. Molecular and cluster species are identified by time of flight mass spectroscopy: the major mass features observed are A(n)H(+) (n=1-9), ACOOH(+) (VUV ionization) without IR radiation present, and A(+) with both IR and VUV radiation present. The intense feature ACOOH(+) arises from the cleavage of (A)(2) at the beta-CC bond to generate ACOOH(+)+CH(3) following ionization. The vibrational spectrum of monomeric acetic acid (2500-7500 cm(-1)) is measured by nonresonant ionization detected infrared (NRID-IR) spectroscopy. The fundamentals and overtones of the CH and OH stretches and some combination bands are identified in the spectrum. Mass selected IR spectra of neutral and cationic acetic acid clusters are measured in the 2500-3800 cm(-1) range employing nonresonant ionization dip-IR and IR photodissociation (IRPD) spectroscopies, respectively. Characteristic bands observed at approximately 2500-2900 cm(-1) for the cyclic ring dimer are identified and tentatively assigned. For large neutral acetic acid clusters A(n)(n>2), spectra display only hydrogen bonded OH stretch features, while the CH modes (2500-2900 cm(-1)) do not change with cluster size n. The IRPD spectra of protonated (cationic) acetic acid clusters A(n)H(+) (n=1-7) exhibit a blueshift of the free OH stretch with increasing n. These bands finally disappear for n> or =6, and one broad and weak band due to hydrogen bonded OH stretch vibrations at approximately 3350 cm(-1) is detected. These results indicate that at least one OH group is not involved in the hydrogen bonding network for the smaller (n< or =5) A(n)H(+) species. The disappearance of the free OH stretch feature at n> or =6 suggests that closed cyclic structures form for A(n)H(+) for the larger clusters (n> or =6).