Tropospheric Emissions: Monitoring of Pollution (TEMPO).

TEMPO was selected in 2012 by NASA as the first Earth Venture Instrument, for launch between 2018 and 2021. It will measure atmospheric pollution for greater North America from space using ultraviolet and visible spectroscopy. TEMPO observes from Mexico City, Cuba, and the Bahamas to the Canadian oil sands, and from the Atlantic to the Pacific, hourly and at high spatial resolution (~2.1 km N/S×4.4 km E/W at 36.5°N, 100°W). TEMPO provides a tropospheric measurement suite that includes the key elements of tropospheric air pollution chemistry, as well as contributing to carbon cycle knowledge. Measurements are made hourly from geostationary (GEO) orbit, to capture the high variability present in the diurnal cycle of emissions and chemistry that are unobservable from current low-Earth orbit (LEO) satellites that measure once per day. The small product spatial footprint resolves pollution sources at sub-urban scale. Together, this temporal and spatial resolution improves emission inventories, monitors population exposure, and enables effective emission-control strategies. TEMPO takes advantage of a commercial GEO host spacecraft to provide a modest cost mission that measures the spectra required to retrieve ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), formaldehyde (H2CO), glyoxal (C2H2O2), bromine monoxide (BrO), IO (iodine monoxide),water vapor, aerosols, cloud parameters, ultraviolet radiation, and foliage properties. TEMPO thus measures the major elements, directly or by proxy, in the tropospheric O3 chemistry cycle. Multi-spectral observations provide sensitivity to O3 in the lowermost troposphere, substantially reducing uncertainty in air quality predictions. TEMPO quantifies and tracks the evolution of aerosol loading. It provides these near-real-time air quality products that will be made publicly available. TEMPO will launch at a prime time to be the North American component of the global geostationary constellation of pollution monitoring together with the European Sentinel-4 (S4) and Korean Geostationary Environment Monitoring Spectrometer (GEMS) instruments.

High knee valgus in female subjects does not yield higher knee translations during drop landings: a biplane fluoroscopic study.

The goal of this study was to determine the effects of peak knee valgus angle and peak knee abductor moment on the anterior, medial, and lateral tibial translations (ATT, MTT, LTT) in the "at risk" female knee during drop landing. Fifteen female subjects performed drop landings from 40 cm. Three-dimension knee motion was simultaneously recorded using a high speed, biplane fluoroscopy system, and a video-based motion analysis system. Valgus knee angles and knee abduction moments were stratified into low, intermediate, and high groups and peak ATT, MTT, and LTT were compared between these groups with ANOVA (α = 0.05). Significant differences were observed between stratified groups in peak knee valgus angle (p < 0.0001) and peak knee abduction moment (p < 0.0001). However, no corresponding differences in peak ATT, LTT, and MTT between groups exhibiting low to high-peak knee valgus angles (ATT: p = 0.80; LTT: p = 0.25; MTT: p = 0.72); or, in peak ATT (p = 0.61), LTT (p = 0.26) and MTT (p = 0.96) translations when stratified according to low to high knee abduction moments, were found. We conclude that the healthy female knee is tightly regulated with regard to translations even when motion analysis derived knee valgus angles and abduction moments are high.

Accuracy of a contour-based biplane fluoroscopy technique for tracking knee joint kinematics of different speeds.

While measuring knee motion in all six degrees of freedom is important for understanding and treating orthopaedic knee pathologies, traditional motion capture techniques lack the required accuracy. A variety of model-based biplane fluoroscopy techniques have been developed with sub-millimeter accuracy. However, no studies have statistically evaluated the consistency of the accuracy across motions of varying intensity or between degrees of freedom. Therefore, this study evaluated the bias and precision of a contour-based tracking technique by comparing it to a marker-based method (gold standard) during three movements with increasing intensity. Six cadaveric knees with implanted tantalum markers were used to simulate knee extension, walking and drop landings, while motion was recorded by a custom biplane fluoroscopy system. The 3D geometries of the bones were reconstructed from CT scans and anatomical coordinate systems were assigned. The position and orientation of the bone and marker models were determined for an average of 27 frames for each trial and knee joint kinematics were compared. The average bias and precision was 0.01 ± 0.65° for rotations and 0.01 ± 0.59 mm for joint translations. Rotational precision was affected by motion (p=0.04) and depended on the axis of rotation (p=0.02). However, the difference in average precision among motions or axes was small (≤ 0.13°) and not likely of consequence for kinematic measurements. No other differences were found. The contour-based technique demonstrated sub-millimeter and sub-degree accuracy, indicating it is a highly accurate tool for measuring complex three dimensional knee movements of any intensity.

Relationship of knee shear force and extensor moment on knee translations in females performing drop landings: a biplane fluoroscopy study.

BACKGROUND: Research has linked knee extensor moment and knee shear force to the non-contact anterior cruciate ligament injury during the landing motion. However, how these biomechanical performance factors relate to knee translations in vivo is not known as knee translations cannot be obtained with traditional motion capture techniques. The purpose of this study was to combine traditional motion capture with high-speed, biplane fluoroscopy imaging to determine relationships between knee extensor moment and knee shear force profiles with anterior and lateral tibial translations occurring during drop landing in female athletes. METHODS: 15 females performed drop landings from a height of 40 cm while being recorded using a high speed, biplane fluoroscopy system and simultaneously being recorded using surface marker motion capture techniques to estimate knee joint angle, reaction force and moment profiles. FINDINGS: No significant statistical relationships were observed between peak anterior or posterior knee shear force and peak anterior and lateral tibial translations; or, between peak knee extensor moment and peak anterior and lateral tibial translations. Although differences were noted in peak shear force (P=0.02) and peak knee extensor moment (P<0.001) after stratification into low and high shear force and moment cohorts, no differences were noted in anterior and lateral tibial translations (all P ≥ 0.18). INTERPRETATION: Females exhibiting high knee extensor moment and knee shear force during drop landings do not yield correspondingly high anterior and lateral tibial translations.

Role of the acetabular labrum and the iliofemoral ligament in hip stability: an in vitro biplane fluoroscopy study.

BACKGROUND: Recent biomechanical reports have described the function of the acetabular labrum and iliofemoral ligament in providing hip stability, but the relative stability provided by each structure has not been well described. HYPOTHESIS: Both the iliofemoral ligament and acetabular labrum are important for hip stability by limiting external rotation and anterior translation, with increased stability provided by the iliofemoral ligament compared with the acetabular labrum. STUDY DESIGN: Controlled laboratory study. METHODS: Fifteen fresh-frozen male cadaveric hips were utilized for this study. Each specimen was selectively skeletonized down to the hip capsule. Four tantalum beads were embedded into each femur and pelvis to accurately measure hip translations and rotations using biplane fluoroscopy while either a standardized 5 N·m external or internal rotation torque was applied. The hips were tested in 4 hip flexion angles (10° of extension, neutral, and 10° and 40° of flexion) in the intact state and then by sectioning and later repairing the acetabular labrum and iliofemoral ligament in a randomized order. RESULTS: External rotation significantly increased from the intact condition (41.5° ± 7.4°) to the sectioned iliofemoral ligament condition (54.4° ± 6.6°) and both-sectioned condition (61.5° ± 5.7°; P < .01), but there was no significant increase in external rotation when the labrum alone was sectioned (45.6° ± 5.9°). The intact and fully repaired conditions were not significantly different. External rotation and internal rotation significantly decreased when the hip flexion angle decreased from 40° of flexion to 10° of extension (P < .01) regardless of sectioned condition. Anterior translation varied significantly across sectioned conditions but not across flexion angles (P < .001). The ligament-sectioned (1.4 ± 0.5 mm), both-sectioned (2.2 ± 0.2 mm), and labrum-repaired (1.1 ± 0.2 mm) conditions all resulted in significantly greater anterior translation than the intact condition (-0.4 ± 0.1 mm) (P < .001). CONCLUSION: The iliofemoral ligament had a significant role in limiting external rotation and anterior translation of the femur, while the acetabular labrum provided a secondary stabilizing role for these motions. CLINICAL RELEVANCE: These results suggest that, if injured, both the acetabular labrum and iliofemoral ligament should be surgically repaired to restore native hip rotation and translation. In addition, a careful repair of an arthroscopic capsulotomy should be performed to avoid increased external hip rotation and anterior translation after arthroscopy.

The influence of arm and shoulder position on the bear-hug, belly-press, and lift-off tests: an electromyographic study.

BACKGROUND: Clinical testing for the integrity of the subscapularis muscle includes the belly-press, lift-off, and bear-hug examinations. While these tests have been widely applied in clinical practice, there is considerable variation in arm positioning within each clinical examination. HYPOTHESIS: To determine the ideal arm and shoulder positions for isolating the subscapularis muscle while performing the bear-hug, belly-press, and lift-off tests. STUDY DESIGN: Controlled laboratory study. METHODS: The activity of 7 muscles was monitored in 20 healthy participants: upper and lower divisions of the subscapularis, supraspinatus, infraspinatus, latissimus dorsi, teres major, triceps, pectoralis major. Electromyogram data were collected and compared across each clinical test at varying arm positions: bear-hug (ideal position, 10° superior, 10° inferior to the shoulder line), belly-press (ideal position, maximum shoulder external rotation, and maximal shoulder internal rotation), and lift-off (ideal position, hand position 5 in. [12.7 cm] superior and 5 in. [12.7 cm] inferior to the midlumbar spine). RESULTS: Regardless of arm and shoulder position, the upper and lower subscapularis muscle activities were significantly greater than all other muscles while performing each test. No significant differences were observed between the upper and lower subscapularis divisions at any position within and across the 3 tests. There were no significant differences in subscapularis electromyogram activities across the 3 tests. CONCLUSION: The level of subscapularis muscle activation was similar among the bear-hug, belly-press, and lift-off tests. The 3 tests activated the subscapularis significantly more than all other muscles tested but were not different from one another when compared across tests and positions. Although the bear-hug and lift-off tests have been described to activate differential portions of the subscapularis, the findings of this study do not support the preferential testing of a specific subscapular division across the 3 tests. As such, all 3 tests are effective in testing the integrity of the entire subscapularis muscle, although there does not appear to be an ideal position for selectively testing its divisions. CLINICAL RELEVANCE: Clinicians may feel comfortable in using any of the 3 tests, depending on the patient, to isolate the function of the subscapularis as a single muscle. Furthermore, clinicians should not solely focus on a patient's arm position when administering an examination but also compare the affected arm to the contralateral shoulder when appropriate.

Relationship of anterior knee laxity to knee translations during drop landings: a bi-plane fluoroscopy study.

PURPOSE: Passive anterior knee laxity has been linked to non-contact ACL injury risk. High deceleration movements have been implicated in the non-contact ACL injury mechanism, and evidence suggests that greater anterior tibial translations (ATT) may occur in healthy knees that are lax compared to a tight knee. The purpose of this study was to determine the relationship between anterior knee laxity scores and ATT during drop landings using biplane fluoroscopy. METHODS: Sixteen healthy adults (10 women; 6 men) performed stiff drop landings (40 cm) while being filmed using a high-speed, biplane fluoroscopy system. Initial, peak and excursions for rotations and translations were calculated and regression analysis used to determine the 6DoF kinematic relationships with KT1000 scores with peak ATT occurring during the landing. RESULTS: KT1000 values were (+) correlated with peak ATT values for group (r = 0.89; P < 0.0001) and both genders (males, r = 0.97; P = 0.0003; females, r = 0.93; P = < 0.0001). Regression analysis yielded a significant linear fit for the group (r (2) = 0.80; Y (ATT-group) = - 0.516 + 1.2 × X (KT1000-group)) and for each gender (females: r(2) = 0.86; Y (ATT-females) = 0.074 + 1.2 × X (KT1000-females) and males: r (2) = 0.94; Y (ATT-males) = - 0.79 + 1.2 × X (KT1000-males)). CONCLUSION: A strong relationship was observed between passive anterior knee laxity measured via KT1000 and peak ATT experienced during dynamic activity in otherwise healthy persons performing a stiff drop-landing motion.

Structural and oxo-transfer reactivity differences of hexacoordinate and pentacoordinate (nitro)(tetraphenylporphinato)cobalt(III) derivatives.

The oxo-transfer catalyst (nitro)(pyridyl)cobalt(III) tetraphenylporphyrin has been reinvestigated by substitution of the distal pyridine ligand with 4-N,N-dimethylaminopyridine and 3,5-dichloropyridine. Differences in their structures and in the reactivity of the compounds toward catalytic secondary oxo transfer were investigated by FT-IR and UV-visible spectroscopy, cyclic voltammetry, X-ray diffraction, semiempirical calculations, and reactions with alkenes in dichloromethane solution. Very modest differences in the hexacoordinate compounds' structures were predicted and observed, but the secondary oxo-transfer reactivity at the nitro ligand varies markedly with the basicity of the pyridine ligand and the position of the coordination equilibrium. Oxo transfer occurs rapidly through the pentacoordinate species (nitro)cobalt(III) tetraphenylporphyrin that is generated by dissociation of the pyridine ligand and therefore is strongly related to the Hammett parameters of these nitrogenous bases. The reactive pentacoordinate species CoTPP(NO(2)) can be generated in solution by addition of lithium perchlorate to (py)CoTPP(NO(2)) by Lewis acid-base interactions or more simply by using the weaker Lewis base Cl(2)py instead of py as the distal ligand. In contrast to pentacoordinate (nitro)iron porphyrins, disproportionation reactions of CoTPP(NO(2)) compound are not evident. This pentacoordinate derivative, CoTPP(NO(2)), is reactive enough to stoichiometrically oxidize allyl bromide in minutes. Preliminary catalytic oxidation reaction studies of alkenes also indicate the involvement of both radical and nonradical oxo-transfer steps in the mechanism, suggesting formation of a peroxynitro intermediate in the reaction of the reduced CoTPP(NO) with O(2).

Arthroscopic reconstruction for acromioclavicular joint dislocation.

We describe an arthroscopic reconstruction technique for acromioclavicular joint dislocation. Subsequent to Baum's first repair of the coracoclavicular complex in 1886, over 60 operative procedures have been described in the literature. This procedure is the first described arthroscopic approach used in reconstruction for acromioclavicular dislocation. It provides an anatomically correct and structurally sound reconstruction of the coracoclavicular ligament complex. This arthroscopic technique is also a cosmetically pleasing alternative to previously described open procedures for reconstruction of acromioclavicular joint dislocations. As with most arthroscopic procedures, this technique achieves its goals with minimal morbidity and violation of the surrounding soft tissues.

The 1,2,4-triazolyl cation: thermolytic and photolytic studies.

The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.

Redetermination of CaMn2O4.

The title compound, calcium dimanganese tetraoxide, CaMn(2)O(4), was synthesized hydrothermally and is made up of edge-sharing Mn(3+) distorted octahedral layers and eight-coordinate Ca(2+) centered polyhedral layers.

Is tracheotomy decannulation possible in oxygen-dependent children?

OBJECTIVE: The goal was to determine whether decannulation can be safely achieved in children with persistent oxygen requirements. DESIGN: The study was a prospective evaluation of 12 oxygen-dependent children at a tertiary care academic children's medical center. METHODS: Twelve tracheotomy-dependent children with persistent oxygen requirements were evaluated for decannulation. Patients requiring more than 35% FiO(2) were not considered. Direct laryngoscopy and bronchoscopy were performed in all patients. Two required single-stage laryngotracheoplasty to correct subglottic stenosis, 1 required tracheal resection, and 7 required removal of suprastomal granulation tissue. Oxygen was administered after decannulation through a nasal cannula. RESULTS: Decannulation was successful in 92% (11 of 12) of patients. At final follow-up, oxygen requirements decreased in 58% of patients after decannulation. CONCLUSIONS: Decannulation can be successful in children who remain oxygen dependent; conversion to a more physiologic airway may be an adjunct to reducing or eliminating their oxygen demand.

Complexes of acridine and 9-chloroacridine with I2: formation of unusual I6 chains through charge-transfer interactions involving amphoteric I2.

Acridine and 9-chloroacridine form charge-transfer complexes with iodine in which the nitrogen-bound I2 molecule is amphoteric; one end serves as a Lewis acid to the heterocyclic donor, while the other end acts as a Lewis base to a second I2 molecule that bridges two acridine.I2 units. In the acridine derivative [(acridine.I2)2.I2, 1], the dimer has a "zigzag" conformation, while in the 9-chloroacridine derivative [(9-Cl-acridine.I2)2.I2, 2], the dimer is "C-shaped". The thermal decomposition of the two complexes is very different. Compound 1 loses one molecule of I2 to form an acridine.I2 intermediate, which has not been isolated. Further decomposition gives acridine as the form II polymorph, exclusively. Decomposition of 2 involves the loss of two molecules of I2 to form a relatively stable intermediate [(9-Cl-acridine)2.I2, 3]. Compound 3 consists of two 9-Cl-acridine molecules bridged through N...I charge-transfer interactions by a single I2 molecule. This compound represents the first known example, in which both ends of an I2 molecule form interactions in a complex that is not stabilized by the extended interactions of an infinite chain structure. The ability of the terminal iodine of an N-bound I2 to act either as an electron donor (complexes 1 and 2) or as an electron acceptor (complex 3) can be understood through a quantum mechanical analysis of the systems. Both electrostatic interactions and the overlap of frontier molecular orbitals contribute to the observed behavior.

Coordination polymers of copper(I) halides.

A total of 21 complexes of CuX (X = Cl, Br, I) with bridging ligand (B = 4,4'-dipyridyl (Bpy), pyrazine (Pyz), quinoxaline (Quin), phenazine (Phz), 1,4-diazabicyclo[2.2.2]octane (DABCO), and hexamethylenetetramine (HMTA)) have been synthesized. The products show two stoichiometries: [CuXB] (type 1) and [(CuX)2B] (type 2). Both types can be obtained for B = Bpy, depending on the conditions of preparation. In these cases, the type 2 stoichiometry is the kinetic product. Type 2 complexes only are found for B = Pyz (X = I), Quin, Phz, DABCO, and HMTA. Type 1 complexes form for Pyz (X = Cl, Br). Thermogravimetic analyses of the complexes reveal the general decomposition trend: 1 --> 2 --> [(CuX)2B(1/2)] --> CuX. The X-ray crystal structure of [CuBr(Pyz)] (type 1) features copper atoms bridged by Br and Pyz, forming 2D sheets of fused rectangular Cu4Br2(Pyz)2 units. The X-ray structure of [(CuI)2(Quin)] (type 2) shows 2D layers composed of [Cu2I2]infinity "stair step" chains which are cross-linked by Quin ligands. A total of 16 complexes of CuXL (L = P(OPh)3) with bridging ligand (B = those above and 1,4-dimethylpiperazine (DMP)) have also been prepared. All of these products, except those of HMTA, are of type 3 formulation, [(CuXL)2B]. The HMTA products have the formula [CuX(HMTA)], type 4. Thermal decomposition of the type 3 and 4 complexes occurs with initial loss of B, L, or both. The X-ray structures of [(CuBrL)2(Bpy)] and [(CuBrL)2(Pyz)] (type 3) reveal 1D chains formed from rhomboidal (LCu)2Br2 units linked by the B ligand. The type 4 structure of [CuBrL(HMTA)] is shown by X-ray to be a simple halide-bridged dimer.

Photopenic bone scan osteomyelitis: a clinical perspective.

Eighty-one pediatric patients had nuclear bone-imaging studies confirmatory of osteomyelitis during the past 10 years. Seven (8.6%) of 81 had "cold" osteomyelitis. These seven patients were all toxic [mean temperature (T), 39.9 degrees C; heart rate (HR), 145 beats/min], all had markedly elevated erythrocyte sedimentation rates (mean ESR, 76 mm/h), and six of seven had both confirmatory bone and blood cultures. All patients required surgical intervention. The average length of hospital stay for these seven patients was 32 days (range, 8-65 days). A control group of matched patients with "hot" osteomyelitis was constructed for statistical evaluation. This analysis confirmed significantly increased temperature, resting pulse rate, ESR, length of hospital stay, and rate of surgical intervention in patients with cold versus hot osteomyelitis. Patients with osteomyelitis presenting as a cold defect on bone imaging appeared to have a more aggressive type of bone infection, often requiring aggressive medical and surgical intervention adequately to control this infectious process.

Relationship between oral alveolar bone loss and aging among African-American and Caucasian individuals.

BACKGROUND: The periodontal attachment apparatus consists of the periodontal ligament, alveolar bone, cementum and supra-crestal connective tissue. They are interdependent and provide protection and support to the dentition. It is theorized that the integrity of the periodontal apparatus can be maintained throughout life by exercising comprehensive oral hygiene practices and routine dental care. Additionally, it appears to be unaffected by aging. As a consequence, the investigators performed a study to determine the effects of chronological aging on alveolar bone loss. OBJECTIVE: The present study was conducted to determine the relationship between oral alveolar bone loss, oral hygiene, and aging among African-American and Caucasian populations. METHODS: The population consisted of 229 individuals. There were 131 men and 98 women. With respect to race there were 89 African-Americans and 140 Caucasians. Oral examinations, oral hygiene and missing teeth determinations and bitewing radiographs were performed on all the individuals. Radiographs were digitized and measurements were made from the cementum/enamel junction to the alveolar bone crest. Measurements were made for both the maxillary and mandibular jaws. RESULTS: The results of the study showed a significant multiple linear regression model relationship between oral bone loss and aging. Oral hygiene was a factor, but contributed only slightly to the overall model. Race, gender and the number of missing teeth were not significant variables in the overall model. CONCLUSION: The results of this study suggest age-related alveolar bone loss.