A Highly Efficient Electrosynthesis of Formaldehyde Using a TEMPO-Based Polymer Electrocatalyst.

In the chemical industry, formaldehyde is an important bulk chemical. The traditional synthesis of formaldehyde involves an energy intensive oxidation of methanol over a metal oxide catalyst. The selective electrochemical oxidation of methanol is challenging. Herein, we report a catalytic system with an immobilized TEMPO electrode that selectively oxidizes methanol to formaldehyde with high turnover numbers. Upon the addition of various organic and inorganic bases, the activity of the catalyst could be tuned. The highest Faradaic efficiency that was achieved was 97.5 %, the highest turnover number was 17100. Additionally, we found that the rate determining step changed from the step in which the carbonyl specie is created from the methanol-TEMPO adduct to the oxidative regeneration of the TEMPO+ species. Finally, we showed that the system could be applied to the oxidation of other aliphatic alcohols.

Motor Disturbance in ASD: A Pilot Study Showing Hypokinetic Behavior?

Data supporting theoretical models linking autism spectrum disorders (ASD) to motor disturbance are inconclusive. In the present study, children and adolescents with ASD (n = 44) were compared with a matched group of typically developing individuals (n = 49) on both instrumental and observational assessments of motor abnormalities. No group differences were found in the instrumental data. However, more bradykinetic motor behavior was found using an observational scale in the ASD groups. More rigid motor behavior was found in the adolescents with ASD but not in the children. Individuals with ASD show significantly more hypokinetic behavior, which may not be strictly dopaminergic in origin, but may reflect a weak central coherency in neuronal networks related to the motor system in which developmental changes are present.

Initiation, Switching, and Cessation of Psoriasis Treatments Among Patients with Moderate to Severe Psoriasis in the United States.

BACKGROUND: Psoriasis patients frequently switch among multiple therapies while managing their psoriasis. Determining treatment transitions is fundamental to understanding how patients access and use treatments. OBJECTIVE: We aimed to identify patterns of treatment transitions of US patients with moderate to severe psoriasis over 5 years. METHODS: This was a retrospective, longitudinal cohort study in which US patients aged ≥18 years who had at least one psoriasis claim (International Classification of Diseases, Ninth Revision [ICD-9] diagnosis) were continuously enrolled in a health plan between October 2007 and September 2012. Data from eligible patients were projected to reflect the total US insured population with moderate to severe psoriasis, and the proportions of patients who started, stopped, switched, and restarted treatment at any time between September 2011 and September 2012 were analyzed. Treatment categories were biologics, traditional oral systemics, topicals, phototherapy, lapsed from treatment, and treatment-naive. RESULTS: There were 8.9 million patients in the claims database, of whom 0.9 million (10.4%) had a psoriasis diagnosis and 46,369 (0.5%) met the inclusion criteria. When projected, 1.7 million insured patients had moderate to severe psoriasis. Of these, an estimated 807,000 patients had lapsed treatment, an additional 346,000 were receiving treatment, and 547,000 were defined as being treatment-naive. A total of 81,000 of 346,000 patients had switched treatment in the preceding year. In addition, many patients stopped (438,000) and restarted (384,000) treatment in the 12-month period. CONCLUSION: Based on health claims data, undertreatment of moderate to severe psoriasis appeared to be common.

Under-Treatment of Patients with Moderate to Severe Psoriasis in the United States: Analysis of Medication Usage with Health Plan Data.

INTRODUCTION: Psoriasis is a chronic inflammatory disorder with significant morbidity and mortality, but a persistent gap appears to exist for the adequate treatment of patients with moderate to severe disease. As the extent of under-treatment is unknown, we attempted to determine overall treatment patterns and estimate under-treatment using a large database. METHODS: Data from the US National Health and Wellness Survey was used to estimate the proportion of patients with mild, moderate or severe psoriasis. The proportion with moderate to severe disease was estimated by excluding those with mild disease, and projecting this to the total insured US population, weighted by age and gender. Using US health plan claims data, patient totals by treatment type were determined between October 1, 2007 and September 30, 2012. Patients had to be continuously enrolled in a health plan and be ≥18 years at the end of the analysis window. Psoriasis was confirmed if patients had at least one claim of any type of psoriasis except psoriatic arthropathy (ICD-9 code 696.1). A monthly treatment history, classified by biologic, traditional oral systemic, phototherapy and topical therapy, was recorded for each patient. RESULTS: There were an estimated 1.7 million insured US patients with moderate to severe psoriasis. Of these, 1 million (59%) were not treated for their condition in the preceding year. Among 695,488 patients who were treated for psoriasis in the preceding year, 346,201 were currently receiving treatment and 349,287 had lapsed treatment. Of the patients lapsed and currently treated in this period, the numbers who received each treatment type were 156,409 (biologic), 222,657 (traditional oral systemic), 22,911 (phototherapy), and 293,511 (topical). A limitation of the study was that only insurance claims were analyzed. CONCLUSION: Moderate to severe psoriasis remains persistently untreated or under-treated. We suggest that potential barriers preventing access to care be explored. FUNDING: This study was sponsored by Pfizer Inc.

Laser propagation measurements in long-scale-length underdense plasmas relevant to magnetized liner inertial fusion.

We report experimental results and simulations showing efficient laser energy coupling into plasmas at conditions relevant to the magnetized liner inertial fusion (MagLIF) concept. In MagLIF, to limit convergence and increase the hydrodynamic stability of the implosion, the fuel must be efficiently preheated. To determine the efficiency and physics of preheating by a laser, an Ar plasma with n_{e}/n_{crit}∼0.04 is irradiated by a multi-ns, multi-kJ, 0.35-µm, phase-plate-smoothed laser at spot-averaged intensities ranging from 1.0×10^{14} to 2.5×10^{14}W/cm^{2} and pulse widths from 2 to 10 ns. Time-resolved x-ray images of the laser-heated plasma are compared to two-dimensional radiation-hydrodynamic simulations that show agreement with the propagating emission front, a comparison that constrains laser energy deposition to the plasma. The experiments show that long-pulse, modest-intensity (I=1.5×10^{14}W/cm^{2}) beams can efficiently couple energy (∼82% of the incident energy) to MagLIF-relevant long-length (9.5 mm) underdense plasmas. The demonstrated heating efficiency is significantly higher than is thought to have been achieved in early integrated MagLIF experiments [A. B. Sefkow et al., Phys. Plasmas 21, 072711 (2014)10.1063/1.4890298].

Risk factors for lower extremity injuries among half marathon and marathon runners of the Lage Landen Marathon Eindhoven 2012: A prospective cohort study in the Netherlands.

To determine risk factors for running injuries during the Lage Landen Marathon Eindhoven 2012. Prospective cohort study. Population-based study. This study included 943 runners. Running injuries after the Lage Landen Marathon. Sociodemographic and training-related factors as well as lifestyle factors were considered as potential risk factors and assessed in a questionnaire 1 month before the running event. The association between potential risk factors and injuries was determined, per running distance separately, using univariate and multivariate logistic regression analysis. In total, 154 respondents sustained a running injury. Among the marathon runners, in the univariate model, body mass index ≥ 26 kg/m(2), ≤ 5 years of running experience, and often performing interval training, were significantly associated with running injuries, whereas in the multivariate model only ≤ 5 years of running experience and not performing interval training on a regular basis were significantly associated with running injuries. Among marathon runners, no multivariate model could be created because of the low number of injuries and participants. This study indicates that interval training on a regular basis may be recommended to marathon runners to reduce the risk of injury.

[Instrumental registration of psychomotor symptoms in schizophrenia: has the time come to use the technique in clinical practice?]. / Instrumenteel meten van psycho-motorische symptomen bij schizofrenie: klaar voor de praktijk?

BACKGROUND: In clinical practice, psychomotor deficits are currently assessed by means of observation scales. However, instrumental (including mechanical and electronic) measurement techniques might also be valuable in clinical practice. AIM: To discuss the added value of using instrumental registration of psychomotor functioning into clinical practice. METHOD: We investigated the main pros and cons of instrumental registration by searching the literature systematically and we discuss our findings using concrete examples. RESULTS: Compared to observation scales, instrumental registration yields more reliable and sensitive information about the psychomotor functioning of patients. Another advantage of instrumental registration is that it gives us an opportunity to study affected sub-processes and underlying mechanisms. However, the validity of these measurements depends on whether instrumental registration can adequately reflect aspects of a movement that can be observed clinically. CONCLUSION: Clinical practice could benefit substantially from using instrumental registration of psychomotor disturbances in schizophrenia. However, more time and money needs to be invested in research before the new technique is fully validated and ready for use in clinical practice.

Isotope effects on the photodesorption processes of X2O (X = H,D) and HOD ice.

To investigate the isotope effects on the photodesorption processes of X2O (X = H,D) ice, molecular dynamics calculations have been performed on the ultraviolet photodissociation of an H2O or a D2O molecule in an H2O or a D2O amorphous ice surface, and on HOD photodissociation in an H2O amorphous ice surface, where the photodissociated molecules were located in the top four or five monolayers at ice temperatures of 10, 20, 30, 60, and 90 K. Three photodesorption processes can occur upon X2O photodissociation: X atom photodesorption, OX radical photodesorption, and X2O (or HOD) molecule photodesorption. X2O (or HOD) photodesorption can occur after recombination of X and OX, or after an energetic X atom photofragment kicks a surrounding X2O molecule from the ice surface. Isotope effects are observed for the X atom and the OX radical photodesorption as well as for the kick-out photodesorption. However, no isotope effects were noticeable for the photodesorption of recombined X2O molecules. The average D atom photodesorption probabilities are about a factor 0.9 smaller than those for the H atom, regardless of the isotope of the surrounding ice system. Also, the kick-out mechanism is more likely to occur if a D photofragment is created upon dissociation than if an H atom is created. These observations can be explained by more efficient energy transfer from the D atom to water molecules than from the H atom. Reasoning based on the X2O phonon frequencies associated with the librational modes and energy transfer efficiencies explain why the OX radical photodesorption probabilities are noticeably larger if the OX radical desorbs from a D2O ice system than from an H2O ice system. Also, the OX radical photodesorption is more probable upon dissociation of DOX (X = H,D) than upon dissociation of HOX (X = H,D), because the initial kinetic energy of the OX radical is larger if the dissociation products are D + OX than H + OX. The branching ratio of OD/OH desorption following photodissociation of an HOD molecule in ice (about 1.0) is much lower than the OD/OH branching ratio in gas-phase HOD photodissociation. This may lead to differences in isotope fractionation in OH(g) formation in dense and diffuse clouds in the interstellar medium.

Effects of wind application on thermal perception and self-paced performance.

Physiological and perceptual effects of wind cooling are often intertwined and have scarcely been studied in self-paced exercise. Therefore, we aimed to investigate (1) the independent perceptual effect of wind cooling and its impact on performance and (2) the responses to temporary wind cooling during self-paced exercise. Ten male subjects completed four trials involving 15 min standardized incremental intensity cycling, followed by a 15-km self-paced cycling time trial. Three trials were performed in different climates inducing equivalent thermal strain: hot humid with wind (WIND) and warm humid (HUMID) and hot dry (DRY) without wind. The fourth trial (W3-12) was equal to HUMID, except that wind cooling was unexpectedly provided during kilometers 3-12. Physiological, perceptual and performance parameters were measured. Subjects felt generally cooler during the WIND than the HUMID and DRY trials, despite similar heart rate, rectal and skin temperatures and a WBGT of ~4 °C higher. The cooler thermal sensation was not reflected in differences in thermal comfort or performance. Comparing W3-12 to HUMID, skin temperature was 1.47 ± 0.43 °C lower during the wind interval, leading to more favorable ratings of perceived exertion, thermal sensation and thermal comfort. Overall, power output was higher in the W3-12 than the HUMID-trial (256 ± 29 vs. 246 ± 22 W), leading to a 67 ± 48 s faster finish time. In conclusion, during self-paced exercise in the heat, wind provides immediate and constant benefits in physiological strain, thermal perception and performance. Independent of physiological changes, wind still provides a greater sensation of coolness, but does not impact thermal comfort or performance.

Factors affecting gross efficiency in cycling.

There is little standardization of how to measure cycling gross efficiency (GE). Therefore, the purposes of these studies were to evaluate the effect of: i) stage duration, ii) relative exercise intensity, iii) work capacity and iv) a prior maximal incremental test on GE. Trained subjects (n=28) performed incremental tests with stage durations of 1-, 3-, and 6-min to establish the effect of stage duration and relative exercise intensity on GE. The effect of work capacity was evaluated by correlating GE with peak power output (PPO). In different subjects (n=9), GE was measured at 50% PPO with and without a prior maximal incremental test. GE was similar in 3- and 6-min stages (19.7 ± 2.8% and 19.3 ± 2.0%), but significantly higher during 1-min stages (21.1 ± 2.7%), GE increased with relative exercise intensity, up to 50% PPO or the power output corresponding to the ventilatory threshold and then remained stable. No relationship between work capacity and GE was found. Prior maximal exercise had a small effect on GE measures; GE was lower after maximal exercise. In conclusion, GE can be determined robustly so long as steady state exercise is performed and RER ≤ 1.0.

Low complication rates in the use of port-a-caths in oncology patients.

BACKGROUND: Port-a-caths (PACs) represent an important component of the care of cancer patients, in particular for administration of chemotherapy. We sought to analyse the longevity and complications of PACs in cancer patients in a large community hospital. METHODS: We retrospectively analysed the indications, duration of use, complications and reasons for removal of PACs in cancer patients treated in our centre from January 2005 to December 2010, and compared these with findings in patients who received a PAC in the same period for reasons not related to cancer. RESULTS: During the study period 152 cancer patients received a total of 170 PACs; in the same period, 21 patients received a total of 35 PACs for reasons unrelated to cancer. The total analysis comprised 70,919 days of PAC use. Most cancer patients had a solid tumour (97%). PACs were removed because of a complication in 25 cases in cancer patients (14.7%) vs 15 cases in non-cancer patients (42.9%, p.

Telemetry pill versus rectal and esophageal temperature during extreme rates of exercise-induced core temperature change.

Core temperature measurement with an ingestible telemetry pill has been scarcely investigated during extreme rates of temperature change, induced by short high-intensity exercise in the heat. Therefore, nine participants performed a protocol of rest, (sub)maximal cycling and recovery at 30 °C. The pill temperature (T(pill)) was compared with the rectal temperature (T(re)) and esophageal temperature (T(es)). T(pill) corresponded well to T(re) during the entire trial, but deviated considerably from T(es) during the exercise and recovery periods. During maximal exercise, the average ΔT(pill)-T(re) and ΔT(pill)-T(es) were 0.13 ± 0.26 and -0.57 ± 0.53 °C, respectively. The response time from the start of exercise, the rate of change during exercise and the peak temperature were similar for T(pill) and T(re.) T(es) responded 5 min earlier, increased more than twice as fast and its peak value was 0.42 ± 0.46 °C higher than T(pill). In conclusion, also during considerable temperature changes at a very high rate, T(pill) is still a representative of T(re). The extent of the deviation in the pattern and peak values between T(pill) and T(es) (up to >1 °C) strengthens the assumption that T(pill) is unsuited to evaluate central blood temperature when body temperatures change rapidly.

Relative importance of pacing strategy and mean power output in 1500-m self-paced cycling.

INTRODUCTION: Both mean power output (MPO) and the distribution of the available energy over the race, that is, pacing strategy, are critical factors in performance. The purpose of this study was to determine the relative importance of both pacing strategy and MPO to performance. METHODS: Six well-trained, regionally competitive cyclists performed four 1500-m ergometer time trials (∼2 min). For each subject, the fastest (Fast) and slowest (Slow) time trials were compared and the relative importance of differences in power output and pacing strategy were determined with an energy flow model. RESULTS: The difference in final time between Fast and Slow was 4.0 (2.5) s. Fast was performed with a higher MPO (437.8 (32.3) W vs 411.3 (39.0) W), a higher aerobic peak power (295.3 (36.8) vs 287.5 (34.7) W) and a higher anaerobic peak power (828.8 (145.4) W vs 649.5 (112.2) W) combined with a relatively higher, but not statistically different anaerobic rate constant (0.051 (0.016) vs 0.041 (0.009) W). The changes in MPO (63% anaerobic, 37% aerobic) largely explained the differences in final times. Athletes chose a different pacing strategy that was close to optimal for their physiological condition in both Fast and Slow. CONCLUSION: Differences in intraindividual performance were mainly caused by differences in MPO. Athletes seemed to be able to effectively adjust their pacing profile based on their "status of the day". Keywords modelling performance, energy expenditure, aerobic, anaerobic, sports.

Limitations of temperature measurement in the aural canal with an ear mould integrated sensor.

Aural canal temperature measurement using an ear mould integrated sensor (T(ac)) might be a method suited for continuous non-invasive core temperature estimation in operational settings. We studied the effect of ambient temperature, wind and high intensity exercise on T(ac) and its ability to predict esophageal (T(es)) and rectal temperatures (T(re)). Seven subjects performed a protocol of rest at 21, 10 and 30 °C, followed by exercise and recovery at 30 °C. The subjects performed the protocol twice: with and without face-wind from halfway through the 30 °C rest period. Extra auricle insulation was applied at one side. Ambient temperature changes affected T(ac) significantly, while T(es) and T(re) remained stable. Insulating the auricle reduced but did not abolish this effect. Wind had an immediate cooling effect on T(ac) independent of auricle insulation. During exercise and recovery in 30 °C, T(ac) provided acceptable group predictions of T(re) in trials without wind (bias: -0.66 ± 0.21 °C covered, -1.20 ± 0.15 °C uncovered). Bias was considerably higher with wind, but variability was similar (-1.73 ± 0.11 °C covered, -2.49 ± 0.04 °C uncovered). Individual predictions of T(es) and T(re) showed more variation, especially with wind. We conclude that T(ac) may be used for core temperature assessment of groups in warm and stable conditions.

Anaerobic capacity: effect of computational method.

Anaerobic capacity (AnC) can be estimated by subtracting VO (2) consumed from VO (2) demand, which can be estimated from multiple submaximal exercise bouts or by gross efficiency (GE), requiring one submaximal bout. This study compares AnC using the MAOD and GE method. The precision of estimated VO (2) demand and AnC, determined by MAOD using 3 power output - VO (2) regressions, based on VO (2) from min 8-10 (10 - Y), during min 4 without (4 - Y) and with forced y-intercept (4+Y), and from GE was evaluated by the 95% confidence interval (CI). Well-trained males (n=15) performed submaximal exercise tests to establish VO (2) demand with the MAOD and GE method. To determine AnC subjects completed a constant power output trial. The 3 MAOD procedures and GE method had no significant difference for VO (2) demand and AnC. The 4+Y MAOD procedure and GE method resulted in a smaller 95% CI of VO (2) demand and AnC than the 10 - Y ( P<0.05; P<0.01) and 4 - Y ( P<0.001; P<0.01) MAOD procedures. Therefore, the 4+Y MAOD procedure and GE method are preferred for estimating AnC, but as individual differences exist, they cannot be used interchangeably.

Purification of a candidate gonadotrophin surge-inhibiting/attenuating factor (GnSIF/AF) showing MAPK as a possible target.

Gonadotrophin surge-inhibiting/attenuating factor (GnSIF/AF) has been known for over two decades, but its molecular structure has not been completely characterized yet. In the last 20 years, five different putative GnSIF/AF sequences have been published. In this article, we describe a procedure to isolate and characterize GnSIF/AF from bovine follicular fluid, a GnSIF/AF-derived synthetic peptide (SP-GnSIF/AF) was produced, and the intracellular bioactivity of GnSIF/AF was tested for intracellular action with a MAPK-assay. Two different bioactive molecular weight forms of GnSIF/AF were isolated, a 160 kDa heteromeric and a monomeric 40 kDa protein. The 40 kDa form appeared to be a subunit of the 160 kDa protein. The synthetic peptide mimicked the actions of GnSIF/AF, such as inhibition of GnRH-induced LH secretion and attenuation of the MAPK phosphorylation. The two GnSIF/AF candidates do not show similarities with previously published GnSIF/AF sequences. These are the first data showing the influence of GnSIF/AF on intracellular processes involved in GnRH self-priming and that the biological action of GnSIF/AF was preserved in the produced synthetic peptide. The results provide strong evidence that the identified candidate proteins are the true GnSIF/AF.

Movement disorders are associated with schizotypy in unaffected siblings of patients with non-affective psychosis.

BACKGROUND: Movement disorders and schizotypy are both prevalent in unaffected siblings of patients with schizophrenia and both are associated with the risk of developing psychosis or schizophrenia. However, to date there has been no research into the association between these two vulnerability factors in persons with an increased genetic risk profile. We hypothesized that unaffected siblings of patients with non-affective psychosis have more movement disorders and schizotypy than healthy controls and that these co-occur. METHOD: In a cross-sectional design we assessed the prevalence and inter-relationship of movement disorders and schizotypy in 115 unaffected siblings (mean age 27 years, 44% males) and 100 healthy controls (mean age 26 years, 51% males). Movement disorders were measured with the Abnormal Involuntary Movement Scale (AIMS), the Unified Parkinson Disease Rating Scale (UPDRS), the Barnes Akathisia Rating Scale (BARS), and one separate item for dystonia. Schizotypy was assessed with the Structured Interview for Schizotypy--Revised (SIS-R). RESULTS: There were significant differences in the prevalence of movement disorders in unaffected siblings versus healthy controls (10% v. 1%, p<0.01) but not in the prevalence of schizotypy. Unaffected siblings with a movement disorder displayed significantly more positive and total schizotypy (p=0.02 and 0.03 respectively) than those without. In addition, dyskinesia correlated with positive schizotypy (r=0.51, p=0.02). CONCLUSIONS: The association between movement disorders (dyskinesia in particular) with positive and total schizotypy in unaffected siblings suggests that certain vulnerability factors for psychosis or schizophrenia cluster in a subgroup of subjects with an increased genetic risk of developing the disease.

Non-invasive continuous core temperature measurement by zero heat flux.

Reliable continuous core temperature measurement is of major importance for monitoring patients. The zero heat flux method (ZHF) can potentially fulfil the requirements of non-invasiveness, reliability and short delay time that current measurement methods lack. The purpose of this study was to determine the performance of a new ZHF device on the forehead regarding these issues. Seven healthy subjects performed a protocol of 10 min rest, 30 min submaximal exercise (average temperature increase about 1.5 °C) and 10 min passive recovery in ambient conditions of 35 °C and 50% relative humidity. ZHF temperature (T(zhf)) was compared to oesophageal (T(es)) and rectal (T(re)) temperature. ΔT(zhf)-T(es) had an average bias ± standard deviation of 0.17 ± 0.19 °C in rest, -0.05 ± 0.18 °C during exercise and -0.01 ± 0.20 °C during recovery, the latter two being not significant. The 95% limits of agreement ranged from -0.40 to 0.40 °C and T(zhf) had hardly any delay compared to T(es). T(re) showed a substantial delay and deviation from T(es) when core temperature changed rapidly. Results indicate that the studied ZHF sensor tracks T(es) very well in hot and stable ambient conditions and may be a promising alternative for reliable non-invasive continuous core temperature measurement in hospital.