Anionic migration reactions in aromatic systems effected by collisional activation : Deprotonated anilides containing methoxycarbonyl substituents

Long-range cross-ring reactions are of minor importance in the collision-induced mass spectra (MS/MS) of [M - H]- ions of CH2OCO-C6H4-NHCOR systems: e.g. the loss of 'CD3CO2CH3' from CH3OCO-C6H4-(N) over bar COCD3. Major processes involve (i) losses of radicals to form stable radical anions, e.g. loss of a ring hydrogen atom and losses from the ester (CH3 ., CH3O . and . CO2CH3), (ii) losses of neutral molecules from the amide moiety [e.g. CO (R = H) and CH2CO (R = CH3), and proximity effects when the two substituents are ortho [e.g. loss of (CH3OD+CO2) from o-CH3OCO-C6H4 (N) over bar COCD3].

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

Interstellar molecules. Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Ability of recombinant human bone morphogenetic protein 2 to enhance bone healing in the presence of tobramycin : evaluation in a rat segmental defect model

Objective To determine whether locally applied tobramycin influences the ability of recombinant human bone morphogenetic protein 2 (rhBMP-2) to heal a segmental defect in the rat femur. Methods The influence of tobramycin on the osteogenic differentiation of mesenchymal stem cells was first evaluated in vitro. For the subsequent, in vivo experiments, a 5-mm segmental defect was created in the right femur of each of 25 Sprague-Dawley rats and stabilized with an external fixator and four Kirschner wires. Rats were divided in four groups: empty control, tobramycin (11 mg)/absorbable collagen sponge, rhBMP-2 (11 μg)/absorbable collagen sponge, and rhBMP-2/absorbable collagen sponge with tobramycin. Bone healing was monitored by radiography at 3 and 8 weeks. Animals were euthanized at 8 weeks and the properties of the defect were compared with the intact contralateral femur. Bone formation in the defect region was assessed by dual-energy x-ray absorptiometry, microcomputed tomography, histology, and mechanical testing. Results Tobramycin exerted a dose-dependent inhibition of alkaline phosphatase induction and calcium deposition by mesenchymal stem cells cultured under osteogenic conditions. The inhibition was reversed in the presence of 500 ng/mL of rhBMP-2. Segmental defects in the rat femora failed to heal in the absence of rhBMP-2. Tobramycin exerted no inhibitory effects on the ability of rhBMP-2 to heal these defects and increased the bone area of the defects treated with rhBMP-2. Data obtained from all other parameters of healing, including dual-energy x-ray absorptiometry, microcomputed tomography, histology, and mechanical testing, were unaffected by tobramycin. Conclusions Although our in vitro results suggested that tobramycin inhibits the osteogenic differentiation of mesenchymal stem cells, this could be overcome by rhBMP-2. Tobramycin did not impair the ability of rhBMP-2 to heal critical-sized femoral defects in rats. Indeed, bone area was increased by nearly 20% in the rhBMP-2 group treated with tobramycin. This study shows that locally applied tobramycin can be used in conjunction with rhBMP-2 to enhance bone formation at fracture sites.

The impact of viral respiratory infection on the severity and recovery from an asthma exacerbation

Background Viral respiratory illness triggers asthma exacerbations, but the influence of respiratory illness on the acute severity and recovery of childhood asthma is unknown. Our objective was to evaluate the impact of a concurrent acute respiratory illness (based on a clinical definition and PCR detection of a panel of respiratory viruses, Mycoplasma pneumoniae and Chlamydia pneumoniae) on the severity and resolution of symptoms in children with a nonhospitalized exacerbation of asthma. Methods Subjects were children aged 2 to 15 years presenting to an emergency department for an acute asthma exacerbation and not hospitalized. Acute respiratory illness (ARI) was clinically defined. Nasopharyngeal aspirates (NPA) were examined for respiratory viruses, Chlamydia and Mycoplasma using PCR. The primary outcome was quality of life (QOL) on presentation, day 7 and day 14. Secondary outcomes were acute asthma severity score, asthma diary, and cough diary scores on days 5, 7,10, and 14. Results On multivariate regression, presence of ARI was statistically but not clinically significantly associated with QOL score on presentation (B = 0.36, P = 0.025). By day 7 and 14, there was no difference between groups. Asthma diary score was significantly higher in children with ARI (B = 0.41, P = 0.039) on day 5 but not on presentation or subsequent days. Respiratory viruses were detected in 54% of the 78 NPAs obtained. There was no difference in the any of the asthma outcomes of children grouped by positive or negative NPA. Conclusions The presence of a viral respiratory illness has a modest influence on asthma severity, and does not influence recovery from a nonhospitalized asthma exacerbation.

Age and gender differences in objectively measured physical activity in youth

Purpose The purpose of this study was to evaluate age and gender differences in objectively measured physical activity (PA) in a population-based sample of students in grades 1–12. Methods Participants (185 male, 190 female) wore a CSA 7164 accelerometer for 7 consecutive days. To examine age-related trends, students were grouped as follows: grades 1–3 (N = 90), grades 4–6 (N = 91), grades 7–9 (N = 96), and grades 10–12 (N = 92). Bouts of PA and minutes spent in moderate-to-vigorous PA (MVPA) and vigorous PA (VPA) were examined. Results Daily MVPA and VPA exhibited a significant inverse relationship with grade level, with the largest differences occurring between grades 1–3 and 4–6. Boys were more active than girls; however, for overall PA, the magnitudes of the gender differences were modest. Participation in continuous 20-min bouts of PA was low to nonexistent. Conclusion Our results support the notion that PA declines rapidly during childhood and adolescence and that accelerometers are feasible alternatives to self-report methods in moderately sized population-level surveillance studies.

Neck movement and muscle activity characteristics in female office workers with neck pain

Study Design Cross-sectional study. Objective To explore aspects of cervical musculoskeletal function in female office workers with neck pain. Summary of Background Data Evidence of physical characteristics that differentiate computer workers with and without neck pain is sparse. Patients with chronic neck pain demonstrate reduced motion and altered patterns of muscle control in the cervical flexor and upper trapezius (UT) muscles during specific tasks. Understanding cervical musculoskeletal function in office workers will better direct intervention and prevention strategies. Methods Measures included neck range of motion; superficial neck flexor muscle activity during a clinical test, the craniocerivcal flexion test; and a motor task, a unilateral muscle coordination task, to assess the activity of both the anterior and posterior neck muscles. Office workers with and without neck pain were formed into 3 groups based on their scores on the Neck Disability Index. Nonworking women without neck pain formed the control group. Surface electromyographic activity was recorded bilaterally from the sternocleidomastoid, anterior scalene (AS), cervical extensor (CE) and UT muscles. Results Workers with neck pain had reduced rotation range and increased activity of the superficial cervical flexors during the craniocervical flexion test. During the coordination task, workers with pain demonstrated greater activity in the CE muscles bilaterally. On completion of the task, the UT and dominant CE and AS muscles demonstrated an inability to relax in workers with pain. In general, there was a linear relationship between the workers’ self-reported levels of pain and disability and the movement and muscle changes. Conclusion These results are consistent with those found in other cervical musculoskeletal disorders and may represent an altered muscle recruitment strategy to stabilize the head and neck. An exercise program including motor reeducation may assist in the management of neck pain in office workers.

Effects of short-duration and long-duration exercise on lipoprotein(a)

Purpose Most studies that use either a single exercise session, exercise training, or a cross-sectional design have failed to find a relationship between exercise and plasma lipoprotein(a) [Lp(a)] concentrations. However, a few studies investigating the effects of longer and/or more strenuous exercise have shown elevated Lp(a) concentrations, possibly as an acute-phase reactant to muscle damage. Based on the assumption that greater muscle damage would occur with exercise of longer duration, the purpose of the present study was to determine whether exercise of longer duration would increase Lp(a) concentration and creatine kinase. (CK) activity more than exercise of shorter duration. Methods Ten endurance-trained men (mean +/- SD: age, 27 +/- 6 yr; maximal oxygen consumption [(V)over dotO(2max)], 57 +/- 7 mL(.)kg(-1) min(-1)) completed two separate exercise sessions at 70% (V)over dotO(2max). One session required 900 kcal of energy expenditure (60 +/- 6 min), and the other required 1500 kcal (112 +/- 12 min). Fasted blood samples were taken immediately before (0-pre), immediately after (0-post), 1 d after (1-post), and 2 d after (2-post) each exercise session. Results CK activity increased after both exercise sessions (mean +/- SE; 800 kcal: 0-pre 55 +/- 11, 1-post 168 +/- 64 U(.)L(-1.)min(-1); 1500 kcal: 0-pre 51 +/- 5, 1-post 187 +/- 30, 2-post 123 +/- 19 U(.)L(-1.)min(-1); P < 0.05). However, median Lp(a) concentrations were not altered by either exercise session (800 kcal: 0-pre 5.0 mg(.)dL(-1), 0-post 3.2 mg(.)dL(-1), 1-post 4.0 mg(.)dL(-1), 2-post 3.4 mg(.)dL(-1); 1500 kcal: 0-pre 5.8 mg(.)dL(-1), 0-post 4.3 mg(.)dL(-1), 1-post 3.2 mg(.)dL(-1), 2-post 5.3 mg(.)dL(-1)). In addition, no relationship existed between exercise-induced changes in CK activity and Lp(a) concentration (800 kcal: r = -0.26; 1500 kcal: r = -0.02). Conclusion These results suggest that plasma Lp(a) concentration will not increase in response to minor exercise-induced muscle damage in endurance-trained runners.

Effect of a single session of exercise on lipoprotein(a)

Lipoprotein(a) (Lp(a)) is bound to apolipoprotein B-100 by disulfide linkage and is associated in the upper density range of low density lipoprotein cholesterol. Persons with elevated concentrations of Lp(a) are regarded as having an increased risk for premature coronary artery disease. Although many studies exist evaluating the effects of a single session of exercise on lipids and lipoproteins, little information is available concerning the effects of exercise on Lp(a). Therefore, the purpose of this study was to determine the effects of a single exercise session on plasma Lp(a). Twelve physically active men completed two 30-min submaximal treadmill exercise sessions: low intensity (LI, 50% VO2max) and high intensity (HI, 80% VO2max). Blood samples were obtained immediately before and after exercise. Total cholesterol (LI: before 4.22 +/- 0.26, after 4.24 +/- 0.28; HI: before 4.24 +/- 0.31, after 4.11 +/- 0.28 mmol . l(-1), mean +/- SE) and triglyceride (LI: before 1.14 +/- 0.16, after 1.06 +/- 0.16; HI: before 1.12 +/- 0.19, after 1.21 +/- 0.19 mmol . l(-1)) concentrations did not differ immediately after either exercise session, nor did Lp(a) concentrations differ immediately after either exercise session (LI: before 4.1 +/- 2.2, after 4.0 +/- 2.1; HI: before 3.9 +/- 2.2, after 3.7 +/- 2.0 mg . dl(-1)). These results suggest that neither a low nor a high intensity exercise session lasting 30 min in duration has an immediate effect on plasma Lp(a).

Tracking of physical activity in young children

The purpose of this study was to determine whether physical activity behavior tracks during early childhood. Forty-seven children (22 males, 25 females) aged 3-4 yr at the beginning of the study were followed over a 3-yr period. Heart rates were measured at least 2 and up to 4 d . yr(-1) with a Quantum XL Telemetry heart rate monitor. Physical activity was quantified as the percentage of observed minutes between 3:00 and 6:00 p.m. during which heart rate was 50% or more above individual resting heart rate (PAHR-50 Index). Tracking of physical activity was analyzed using Pearson and Spearman correlations. Yearly PAHR-50 index tertiles were created and examined for percent agreement and Cohen's kappa. Repeated measures ANOVA was used to calculate the intraclass correlation coefficient across the 3 yr of the study. Spearman rank order correlations ranged from 0.57 to 0.66 (P < 0.0001). Percent agreement ranged from 49% to 62%. The intraclass R for the 3 yr was 0.81. It was concluded that physical activity behavior tends to track during early childhood.

Using objective physical activity measures with youth : How many days of monitoring are needed?

Purpose The purpose of this study was to establish the minimal number of days of monitoring required for accelerometers to assess usual physical activity in children. Methods A total of 381 students (189 M, 192 F) wore a CSA 7164 uniaxial accelerometer for seven consecutive days. To examine age-related trends students were grouped as follows: Group I: grades 1-3 (N = 92); Group II: grades 4-6 (N = 98); Group III: grades 7-9 (N = 97); Group IV: grades 10-12 (N = 94). Average daily time spent in moderate-to-vigorous physical activity (MVPA) was calculated from minute-by-minute activity counts using the regression equation developed by Freedson et al. (1997). Results Compared with adolescents in grades 7 to 12, children in grades 1 to 6 exhibited less day-to-day variability in MVPA behavior. Spearman-Brown analysts indicated that between 4 and 5 d of monitoring would be necessary to a achieve a reliability of 0.80 in children, and between 8 and 9 d of monitoring would be necessary to achieve a reliability of 0.80 in adolescents. Within all grade levels, the 7-d monitoring protocol produced acceptable estimates of daily participation in MVPA (R = 0.76 (0.71-0.81) to 0.87 (0.84-0.90)). Compared with weekdays, children exhibited significantly higher levels of MVPA on weekends, whereas adolescents exhibited significantly lower levels of MVPA on weekends. Principal components analysis revealed two distinct time components for MVPA during the day for children (early morning, rest of the day), and three distinct time components for MVPA during the day for adolescents (morning, afternoon, early evening). Conclusions These results indicate that a 7-d monitoring protocol provides reliable estimates of usual physical activity behavior in children and adolescents and accounts for potentially important differences in weekend versus weekday activity behavior as well as differences in activity patterns within a given day.

Validity of the computer science and applications (CSA) activity monitor in children

Purpose The purpose of this study was to evaluate the validity of the CSA activity monitor as a measure of children's physical activity using energy expenditure (EE) as a criterion measure. Methods Thirty subjects aged 10 to 14 performed three 5-min treadmill bouts at 3, 4, and 6 mph, respectively. While on the treadmill, subjects wore CSA (WAM 7164) activity monitors on the right and left hips. (V) over dot O-2 was monitored continuously by an automated system. EE was determined by multiplying the average (V) over dot O-2 by the caloric equivalent of the mean respiratory exchange ratio. Results Repeated measures ANOVA indicated that both CSA monitors were sensitive to changes in treadmill speed. Mean activity counts from each CSA unit were not significantly different and the intraclass reliability coefficient for the two CSA units across all speeds was 0.87. Activity counts from both CSA units were strongly correlated with EE (r = 0.86 and 0.87, P < 0.001). An EE prediction equation was developed from 20 randomly selected subjects and cross-validated on the remaining 10. The equation predicted mean EE within 0.01 kcal.min(-1). The correlation between actual and predicted values was 0.93 (P < 0.01) and the SEE was 0.93 kcal.min(-1). Conclusion These data indicate that the CSA monitor is a valid and reliable tool for quantifying treadmill walking and running in children.

Long-term stability of adipose tissue generated from a vascularized pedicled fat flap inside a chamber

Background Numerous studies demonstrate the generation and short-term survival of adipose tissue; however, long-term persistence remains elusive. This study evaluates long-term survival and transferability of de novo adipose constructs based on a ligated vascular pedicle and tissue engineering chamber combination. Methods Defined adipose tissue flaps were implanted into rats in either intact or perforated domed chambers. In half of the groups, the chambers were removed after 10 weeks and the constructs transferred on their vascular pedicle to a new site, where they were observed for a further 10 weeks. In the remaining groups, the tissue construct was observed for 20 weeks inside the chamber. Tissue volume was assessed using magnetic resonance imaging and histologic measures, and constructs were assessed for stability and necrosis. Sections were assessed histologically and for proliferation using Ki-67. Results At 20 weeks, volume analysis revealed an increase in adipose volume from 0.04 ± 0.001 ml at the time of insertion into the chambers to 0.27 ± 0.004 ml in the closed and 0.44 ± 0.014 ml in the perforated chambers. There was an additional increase of approximately 10 to 15 percent in tissue volume in flaps that remained in chambers for 20 weeks, whereas the volume of the transferred tissue not in chambers remained unaltered. Histomorphometric assessment of the tissues documented no signs of hypertrophy, fat necrosis, or atypical changes of the newly generated tissue. Conclusion This study presents a promising new method of generating significant amounts of mature, vascularized, stable, and transferable adipose tissue for permanent autologous soft-tissue replacement.

Long-term persistence of tissue-engineered adipose flaps in a murine model to 1 year : an update

BACKGROUND Tissue engineering of patient-specific adipose tissue has the potential to revolutionize reconstructive surgery. Numerous models have been described for the production of adipose tissue with success in the short term, but little has been reported on the stability of this tissue-engineered fat beyond 4 months. METHODS A murine model of de novo adipogenesis producing a potentially transplantable adipose tissue flap within 4 to 6 weeks was developed in the authors' laboratory. In this study, the authors assess the ability of three-chamber (44-μl volume) configurations shown to be adipogenic in previous short-term studies (autograft, n = 8; open, n = 6; fat flap, n = 11) to maintain their tissue volume for up to 12 months in vivo, to determine the most adipogenic configuration in the long term. RESULTS Those chambers having the most contact with existing vascularized adipose tissue (open and fat flap groups) showed increased mean adipose tissue percentage (77 ± 5.6 percent and 81 ± 6.9 percent, respectively; p < 0.0007) and volume (12 ± 6.8 μl and 30 ± 14 μl, respectively; p < 0.025) when compared with short-term controls and greater adipose tissue volume than the autograft (sealed) chamber group (4.9 ± 5.8 μl; p = 0.0001) at 1 year. Inclusion of a vascularized fat flap within the chamber produced the best results, with new fat completely filling the chamber by 1 year. CONCLUSIONS These findings demonstrate that fat produced by tissue engineering is capable of maintaining its volume when the appropriate microenvironment is provided. This has important implications for the application of tissue-engineering techniques in humans.