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Background: Carbon-fibre (CF) plates are increasingly used for fracture fixation. This systematic review evaluated complications associated with CF plate fixation. It also compared outcomes of patients treated with CF plates versus metal plates, aiming to determine if CF plates offered comparable results. The study hypothesized that CF plates display similar complication rates and clinical outcomes as metal plates for fracture fixation. Methods: The study adhered to the Preferred Reporting Items for Systematic Reviews and Meta-Analyses guidelines. The following databases were searched from database inception until June 2023: PubMed, MEDLINE, Embase, Web of Science, Cochrane Library, Emcare, Academic Search Premier and Google Scholar. Studies reporting on clinical and radiological outcomes of patients treated with CF plates for traumatic fractures and (impending) pathological fractures were included. Study quality was assessed, and complications were documented as number and percentage per anatomic region. Results: A total of 27 studies of moderate to very low quality of evidence were included. Of these, 22 studies (800 patients, median follow-up 12 months) focused on traumatic fractures, and 5 studies (102 patients, median follow-up 12 months) on (impending) pathological fractures. A total of 11 studies (497 patients, median follow-up 16 months) compared CF plates with metal plates. Regarding traumatic fractures, the following complications were mostly reported: soft tissue complications (52 out of 391; 13%) for the humerus, structural complications (6 out of 291; 2%) for the distal radius, nonunion and structural complication (1 out of 34; 3%) for the femur, and infection (4 out of 104; 4%) for the ankle. For (impending) pathological fractures, the most frequently reported complications were infections (2 out of 14; 14%) for the humerus and structural complication (6 out of 86; 7%) for the femur/tibia. Comparative studies reported mixed results, although the majority (7 out of 11; 64%) reported no significant differences in clinical or radiological outcomes between patients treated with CF or metal plates. Conclusion: This systematic review did not reveal a concerning number of complications related to CF plate fixation. Comparative studies showed no significant differences between CF plates and metal plates for traumatic fracture fixation. Therefore, CF plates appear to be a viable alternative to metal plates. However, high-quality randomized controlled trials (RCTs) with long-term follow-up are strongly recommended to provide additional evidence supporting the use of CF plates. Level of evidence: III, systematic review. [ABSTRACT FROM AUTHOR]

Simple Summary: The only cure for children with Ewing sarcoma (ES) is surgery. Unfortunately, surgeons are often not able to differentiate healthy from malignant tissue. Fluorescent imaging during the operation will facilitate recognition of malignant cells, but unfortunately there are no ES specific tracers available yet. We searched for proteins on ES cells that could be used as a target against which specific tracers could be developed. The most promising proteins, CD99, CD117, and GD2, were found in paraffin-embedded tissue samples collected from ES patients. Tracers against CD99 and CD117, consisting of monoclonal antibodies attached with a fluorescent dye, showed positive signals on cultured ES cells. In a proof-of-concept study, these tracers were topically applied on fresh ES tissue, showing a signal in the tumor. Our results indicate the applicability for fluorescence-guided surgery of ES-based tracers, but these data have to be confirmed in a larger cohort of pediatric ES patients. Fluorescence-guided surgery (FGS), based on fluorescent tracers binding to tumor-specific biomarkers, could assist surgeons to achieve complete tumor resections. This study evaluated potential biomarkers for FGS in pediatric Ewing sarcoma (ES). Immunohistochemistry (IHC) was performed to assess CD99, CXCR4, CD117, NPY-R-Y1, and IGF-1R expression in ES biopsies and resection specimens. LINGO-1 and GD2 evaluation did not work on the acquired tissue. Based on the immunoreactive scores, anti-CD99 and anti-CD117 were evaluated for binding specificity using flow cytometry and immunofluorescence microscopy. Anti-GD2, a tracer in the developmental phase, was also tested. These three tracers were topically applied to a freshly resected ES tumor and adjacent healthy tissue. IHC demonstrated moderate/strong CD99 and CD117 expression in ES tumor samples, while adjacent healthy tissue had limited expression. Flow cytometry and immunofluorescence microscopy confirmed high CD99 expression, along with low/moderate CD117 and low GD2 expression, in ES cell lines. Topical anti-CD99 and anti-GD2 application on ES tumor showed fluorescence, while anti-CD117 did not show fluorescence for this patient. In conclusion, CD99-targeting tracers hold promise for FGS of ES. CD117 and GD2 tracers could be potential alternatives. The next step towards development of ES-specific FGS tracers could be ex vivo topical application experiments on a large cohort of ES patients. [ABSTRACT FROM AUTHOR]

Carbon-fiber (CF) plates are a promising alternative to metal plates. However, reported experience in orthopaedic oncology remains limited. The aim of this study was to identify complications of patients with bone tumors treated with CF plates. Between February 2015 and May 2021, 13 centers retrospectively registered patients with bone tumors that were reconstructed using CF plates. Complications were identified, and timing and etiology of complications were noted. Similar complications were tabulated and classified based on mechanical, non-mechanical and paediatric complications. Mechanical complications included: (1) aseptic loosening or graft-host non-union, and (2) structural complications. Non-mechanical complications included: (3) soft tissue complications, (4) infection and (5) tumor progression. Specific paediatric complications included (6) growth arrest resulting in longitudinal or angular deformity. Ninety-six patients were included with a median follow-up time of 35 months. In total, 22 (23%) patients had complications. Mechanical complications included: 1 (1%) aseptic loosening, 2 (2%) non-unions, and 7 (7%) structural complications. Non-mechanical complications included 1 (1%) soft tissue complication, 4 (4%) infections and 5 (5%) tumor progressions. Paediatric complications occurred in 2 (2%) patients. This study suggests CF plates are safe to use in demanding reconstructions after bone tumor resections, presenting a seemingly low complication profile. [ABSTRACT FROM AUTHOR]

Background: Shoulder injections for conditions such as adhesive capsulitis are commonly performed and can be administered through image-based or landmark-based injection approaches. Ultrasound-guided injections are widely used and accurate because ultrasound allows real-time visualization of the needle and injected contrast. Landmark-based injections would be advantageous, if they were accurate, because they would save the time and expense associated with ultrasound. However, few prospective studies have compared well-described landmark-based shoulder injection techniques without ultrasound.Question/purpose: Using anatomic landmarks, and without using ultrasound, is the accuracy of glenohumeral injection for adhesive capsulitis greater via the posterior approach or via a new anterior approach?Methods: Between 2018 and 2020, we treated 108 patients potentially eligible for adhesive capsulitis treatment. These patients had clinical symptoms of aggravating shoulder pain with a duration of less than 4 months and passively impaired, painful glenohumeral ROM. Due to the exclusion of patients with other shoulder conditions (full-thickness rotator cuff ruptures and posttraumatic stiffness), 95 patients received an injection in this sequential, prospective, comparative study. Between 2018 and 2019, 41 patients (17 males and 24 females; mean age 52 ± 5 years; mean BMI 24 ± 3 kg/m2) were injected through the posterior approach, with the acromion as the anatomical landmark, during the first part of the study period. After that, between 2019 and 2020, 54 patients (20 males and 34 females; mean age 54 ± 4 years; mean BMI 23 ± 3 kg/m2) received an injection through a new anterior approach, with the acromioclavicular joint as the anatomic landmark, during the second part of the study period. Injections via both approaches were administered by two experienced shoulder specialists (both with more than 10 years of experience). Both specialists had experience with the posterior approach before this study, and neither had previous training with the new anterior approach. Injections contained a corticosteroid, local anaesthetic, and contrast medium. Radiographs were taken within 20 minutes after the injection, and a radiologist blinded to the technique determined accuracy. Accurate injections were defined as having contrast fluid limited to the glenohumeral joint, while inaccurate injections displayed leakage of contrast fluid into the soft tissue or subacromial space. All of the enrolled patients were analyzed.Results: In the group with the posterior approach, the accuracy was 78% (32 of 41) in contrast to 94% (51 of 54, odds ratio 0.21 [95% CI 0.05 to 0.83]; p = 0.03) in patients with the new anterior approach.Conclusion: The new anterior approach without the use of ultrasound was more accurate than the posterior approach. In fact, it was nearly as accurate as previously published ultrasound-guided approaches. We recommend using the new anterior approach for intraarticular glenohumeral injections instead of ultrasound-guided injections because it will save time and costs associated with ultrasound. Still, the clinical effects (anxiety, pain, functional outcome, and adverse events) of the new anterior approach should be compared with ultrasound-guided injections in a randomized study.Level Of Evidence: Level II, therapeutic study. [ABSTRACT FROM AUTHOR]

Fault impact analysis is an important step in developing Fault Detection and Diagnosis (FDD) tools for Heating, Ventilation and Air-Conditioning (HVAC) systems. It provides an insight into how HVAC systems react in the presence of operational faults and helps to prioritise which faults to focus on. The research in the existing literature has mostly focused on modelling several faults occurring in various HVAC systems and components to evaluate the effect of the fault on energy performance and the predicted thermal comfort of occupants. However, the real frequency of fault occurrence, an important factor which affects the overall impact a fault has on the system's performance, has barely been addressed in the reviewed literature. This paper addresses this gap by considering real fault occurrence frequency data in addition to the effect of the faults on the energy performance of the building to assess their total energy impact. A real office building in the Netherlands was modelled using DesignBuilder and its energy performance was simulated using EnergyPlus. Air Handling Unit (AHU) faults were introduced using the native fault object and Energy Management System (EMS) features available in EnergyPlus. The fault occurrence data was extracted from AHU work orders using text mining. The fault modelling and text mining results were combined to get the total energy impact of the fault and, subsequently, the faults were prioritised using the Pareto principle. The research identified that fan failure, Heat Recovery Wheel (HRW) failure, fan stuck at 50% and Heating Coil Valve (HCV) stuck at 0% are the priority faults for winter and fan failure is the priority fault for summer. [ABSTRACT FROM AUTHOR]

The photoionization dynamics of rotationally hot CO, photodissociated from OCS, have been studied using laser photoelectron spectroscopy via the intermediate B [sup 1]Σ[sup +] Rydberg state leading to the X [sup 2]Σ[sup +] of the ion. The photodissociation of OCS near 230 nm produces rotationally hot, but vibrationally cold CO (X [sup 1]Σ[sup +],N[sup ″],v[sup ″]=0,1) fragments along with S ([sup 1]D) atoms. These high rotational levels show photoelectron spectra with a very strong ΔN=0 transition and weaker ΔN=±1, ±2, and ±3 transitions. Agreement between measured and calculated spectra is good and suggests that there is significant angular momentum coupling in the photoelectron orbital. In the ionization step not only Δv=0, but also off-diagonal, non-Franck–Condon (Δv≠0) transitions are observed. The intensities of these transitions vary strongly within the region studied and can be explained by the excitation of superexcited Rydberg states with an A [sup 2]Π core. © 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]

There are data suggesting that intravenous dexamethasone has an effect on postoperative analgesia when given during single-shot spinal anaesthesia. However, the research literature is equivocal. We performed a systematic literature search followed by conventional meta-analysis (random effects model). We used trial sequential analysis to control for type-1 and -2 statistical errors. We also performed a leave-one-out meta-analysis for our primary outcome, the consumption of intravenous morphine in the first 24 postoperative hours. We applied the Grading of Recommendations Assessment, Development and Evaluation (GRADE) system to rate the level of evidence. We obtained data from 1133 patients, reported in 17 trials. Reporting quality was high, with low risk of bias. Dexamethasone use was associated with a significant reduction in 24-h morphine consumption, the mean difference (95%CI) being -4.01 (-5.01 to -3.01) mg, 6 trials, 326 participants, I2 = 0%. Trial sequential analysis showed that there was firm evidence for the primary outcome, and leave-one-out meta-analysis showed that our result was not driven by one single trial. The GRADE evaluation showed a high level of evidence, suggesting that further studies are unlikely to alter the result. The time to first analgesic request (95%CI) was significantly prolonged by 86.62 (10.62-162.62) min, I2 = 93%, in the dexamethasone group. For other secondary outcomes including number of patients requiring rescue analgesia, or visual analogue scale pain scores, we found no evidence of a significant difference between the treatment arms. We report a high level of evidence that intravenous dexamethasone improves postoperative analgesia after spinal anaesthesia. [ABSTRACT FROM AUTHOR]

The thermal reactions of [CoX]+ (X = CN, F, Cl, Br, O, OH) with carbon dioxide have been investigated experimentally and theoretically by using electrospray ionization mass spectrometry (ESI-MS) and density functional theory. Surprisingly, in contrast to the complete inertness of [CoX]+ (X = F, Cl, Br, O, OH) toward carbon dioxide, [Co(CN)]+ activates carbon dioxide to form the elusive [NCCO2Co]+ ion in the gas phase. Mechanistic investigation into this ligand-controlled CO2 activation via C_C bond formation, mediated by a first-row late transition-metal complex, reveals that the inertness of [CoX]+ (X = F, Cl, Br, O, OH) is due to kinetic barriers located above the entrance asymptote. The exception is the [Co(CN)]+/CO2 couple, for which the thermal C-C bond formation is both thermochemically and kinetically accessible. Interestingly, a cyanoformate ligand is most likely also formed in the reaction of [Fe(CN)]+ with CO2; cyanoformate formation had been suggested earlier as a protective mechanism to prevent cyanide complexation to the iron-containing active site of the enzyme ACC oxidase (Murphy et al., in Science 344:75-78, 2014). [ABSTRACT FROM AUTHOR]

Background: F901318 is a new antifungal agent with a novel mechanism of action with activity against Aspergillus species. We investigated the in vitro activity of F901318 against a collection of Aspergillus isolates.Methods: A total of 213 Aspergillus isolates were used in this study. A total of 143 Aspergillus fumigatus sensu stricto isolates were used, of which 133 were azole resistant [25 TR34/L98H; 25 TR46/Y121F/T289A; 33 A. fumigatus with cyp51A-associated point mutations (25 G54, 1 G432 and 7 M220); and 50 azole-resistant A. fumigatus without known resistance mechanisms]. Ten azole-susceptible A. fumigatus isolates were used as WT controls. The in vitro activity was also determined against Aspergillus calidoustus (25 isolates), Aspergillus flavus (10), Aspergillus nidulans (10) and Aspergillus tubingensis (25). F901318 activity was compared with that of itraconazole, voriconazole, posaconazole, isavuconazole, amphotericin B and anidulafungin. Minimum effective concentrations and MICs were determined using the EUCAST broth microdilution method.Results: F901318 was active against all tested isolates: A. fumigatus WT, MIC90 0.125 mg/L (range 0.031-0.125); TR34/L98H,TR46/Y121F/T289A and azole resistant without known resistance mechanisms, MIC90 0.125 mg/L (range 0.031-0.25); A. fumigatus with cyp51A-associated point mutations, MIC90 0.062 mg/L (range 0.015-0.125); and other species, A. calidoustus MIC90 0.5 mg/L (range 0.125-0.5), A. flavus MIC90 0.062 mg/L (range 0.015-0.62), A. nidulans MIC90 0.125 mg/L (range 0.062-0.25) and A. tubingensis MIC90 0.062 mg/L (range 0.015-0.25).Conclusions: F901318 showed potent and consistent in vitro activity against difficult-to-treat Aspergillus spp. with intrinsic and acquired antifungal resistance due to known and unknown resistance mechanisms, suggesting no significant implications of azole resistance mechanisms for the mode of action of F901318. [ABSTRACT FROM AUTHOR]

The thermal reactions of [Ta,O,H]+ with methane and carbon dioxide have been investigated experimentally and theoretically by using electrospray ionization mass spectrometry (ESI MS) and density functional theory calculations. Although the activation of methane proceeds by liberation of H2, the activation of CO2 gives rise to the formation of [OTa(OH)]+ under the elimination of CO. Computational studies of the reactions of methane and carbon dioxide with the two isomers of [Ta,O,H]+, namely, [HTaO]+ and [Ta(OH)]+, have been performed to elucidate mechanistic aspects and to explain characteristic reaction patterns. [ABSTRACT FROM AUTHOR]

Traveling wave ion mobility spectrometry (TWIMS) isomer separation was exploited to react the particularly well-defined ionic species [LCuO]+ (L = 1,10-phenanthroline) with the neutral fluoromethane substrates CH(4-n)Fn (n = 1-3) in the gas phase. Experimentally, the monofluoromethane substrate (n = 1) undergoes both hydrogen-atom transfer, forming the copper hydroxide complex [LCuOH]+ and concomitantly a CH2F? radical, and oxygen-atom transfer, yielding the observable ionic product [LCu]+ plus the neutral oxidized substrate [C,H3,O,F]. DFT calculations reveal that the mechanism for both product channels relies on the initial C-H bond activation of the substrate. Compared to nonfluorinated methane, the addition of fluorine to the substrate assists the reactivity through a lowering of the C-H bond energy and reaction preorganization (through noncovalent interaction in the encounter complex). A two-state reactivity scenario is mandatory for the oxidation, which competitively results in the unusual fluoromethanol product, CH2FOH, or the decomposed products, CH2O and HF, with the latter channel being kinetically disfavored. Difluoromethane (n = 2) is predicted to undergo the analogous reactions at room temperature, although the reactions are less favored than those of monofluoromethane. The reaction of trifluoromethane (n = 3, fluoroform) through C-H activation is kinetically hindered under ambient conditions but might be expected to occur in the condensed phase upon heating or with further lowering of reaction barriers through templation with counterions, such as potassium. Overall, formation of CH(3-n)Fn? and CH(3-n)FnOH occurs under relatively gentle energetic conditions, which sheds light on their potential as reactive intermediates in fluoromethylation reactions mediated by copper in the presence of oxygen. [ABSTRACT FROM AUTHOR]

The number of separations and analyses of molecular species using traveling wave ion-mobility spectrometry-mass spectrometry (TWIMS-MS) is increasing, including those extending the technique to analytes containing metal atoms. A critical aspect of such applications of TWIMS-MS is the validity of the collisional cross sections (CCSs) measured and whether they can be accurately calibrated against other ion-mobility spectrometry (IMS) techniques. Many metal containing species have potential reactivity toward molecular nitrogen, which is present in high concentration in the typical Synapt-G2 TWIMS cell. Here, we analyze the effect of nitrogen on the drift time of a series of cationic 1,10-phenanthroline complexes of the late transition metals, [(phen)M]+, (M = Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and Hg) in order to understand potential deviations from expected drift time behaviors. These metal complexes were chosen for their metal open-coordination site and lack of rotameric species. The target species were generated via electrospray ionization (ESI), analyzed using TWIMS in N2 drift gas, and the observed drift time trends compared. Theoretically derived CCSs for all species (via both the projection approximation and trajectory method) were also compared. The results show that, indeed, for metal containing species in this size regime, reaction with molecular nitrogen has a dramatic effect on measured drift times and must not be ignored when comparing and interpreting TWIMS arrival time distributions. Density-functional theory (DFT) calculations are employed to analyze the periodic differences due to the metal' s interaction with nitrogen (and background water) in detail. [ABSTRACT FROM AUTHOR]

Wereport mid-infrared spectra and potential energy surfaces offour anionic, 2′-deoxynucleotide-5′-monophosphates (dNMPs)and the ionic DNA pairs [dGMP-dCMP–H]1–,[dAMP-dTMP–H]1–with a total charge of thecomplex equal to −1. We recorded IR action spectra by resonantIR multiple-photon dissociation (IRMPD) using the FELIX free electronlaser. The potential energy surface study employed an on-the-fly moleculardynamics quenching method (MD/Q), using a semiempirical AM1 method,followed by an optimization of the most stable structures using densityfunctional theory. By employing infrared multiple-photon dissociation(IRMPD) spectroscopy in combination with high-level computationalmethods, we aim at a better understanding of the hydrogen bondingcompetition between the phosphate moieties and the nucleobases. Wefind that, unlike in multimer double stranded DNA structures, thehydrogen bonds in these isolated nucleotide pairs are predominantlyformed between the phosphate groups. This intermolecular interactionappears to exceed the stabilization energy resulting from base pairingand directs the overall cluster structure and alignment. [ABSTRACT FROM AUTHOR]

CO2 activation mediated by [LTiH]+ (L=Cp2, O) is observed in the gas phase at room temperature using electrospray-ionization mass spectrometry, and reaction details are derived from traveling wave ion-mobility mass spectrometry. Wheresas oxygen-atom transfer prevails in the reaction of the oxide complex [OTiH]+ with CO2, generating [OTi(OH)]+ under the elimination of CO, insertion of CO2 into the metal-hydrogen bond of the cyclopentadienyl complex, [Cp2TiH]+, gives rise to the formate complex [Cp2Ti(O2CH)]+. DFT-based methods were employed to understand how the ligand controls the observed variation in reactivity toward CO2. Insertion of CO2 into the TiH bond constitutes the initial step for the reaction of both [Cp2TiH]+ and [OTiH]+, thus generating formate complexes as intermediates. In contrast to [Cp2Ti(O2CH)]+ which is kinetically stable, facile decarbonylation of [OTi(O2CH)]+ results in the hydroxo complex [OTi(OH)]+. The longer lifetime of [Cp2Ti(O2CH)]+ allows for secondary reactions with background water, as a result of which, [Cp2Ti(OH)]+ is formed. Further, computational studies reveal a good linear correlation between the hydride affinity of [LTi]2+ and the barrier for CO2 insertion into various [LTiH]+ complexes. Understanding the intrinsic ligand effects may provide insight into the selective activation of CO2. [ABSTRACT FROM AUTHOR]

Objectives: To examine the association of employment status and characteristics with prevalent and incident memory complaints (MC) in 55–64-year-olds. Methods: Subjects were participants of the Longitudinal Aging Study Amsterdam (LASA). Respondents with baseline data were selected to examine the association of employment status (n = 1525) and employment characteristics (n = 1071) with prevalent MC (i.e., MC at baseline). Respondents without MC at baseline were selected to examine the association of employment (n = 526) and employment characteristics (n = 379; working hours, job prestige, job level, psychological job demands, iso-strain) with incident MC (i.e., no MC at baseline and MC at three-year follow-up). Associations were adjusted for relevant covariates (demographics, memory performance, physical health, mental health, personality traits). Logistic regression was applied. Data were weighed according to gender and age of the Dutch population. Results: At baseline 20.5% reported MC. At three-year follow-up, 15.4% had incident MC. No associations were found between employment status and MC. Adjusted analysis revealed that individuals with high occupational cognitive demands were more likely to have prevalent MC. Conclusions: Middle-aged workers are equally as likely to experience MC as non-working age-peers. Among workers, those with cognitively demanding work were more likely to experience MC, independent of memory performance. Memory decline due to ageing may be noticed sooner in 55–64-year-olds performing cognitively demanding work. [ABSTRACT FROM AUTHOR]

Decarboxylationchemistry has a rich history, and in more recent times, it has beenrecruited in the quest to develop cheaper, cleaner, and more efficientbond-coupling reactions. Thus, over the past two decades, there hasbeen intense investigation into new metal-catalyzed reactions of carboxylicsubstrates. Understanding the elementary steps of metal-mediated transformationsis at the heart of inventing new reactions and improving the performanceof existing ones. Fortunately, during the same time period, therehas been a convergence in mass spectrometry (MS) techniques, whichallows these catalytic processes to be examined efficiently in thegas phase. Thus, electrospray ionization (ESI) sources have been combinedwith ion-trap mass spectrometers, which in turn have been modified to either accept radiation from tunable OPO lasers for spectroscopy based structural assignment of ions or to allow the study of ion–molecule reactions (IMR). The resultant “complete” gas-phasechemical laboratories provide a platform to study the elementary stepsof metal-catalyzed decarboxylation reactions in exquisite detail. [ABSTRACT FROM AUTHOR]

The long suspected presence of two isomeric copper complexes (A and B), proportionally dependent on ESI cone voltage, was confirmed by their isolation, separation and characterization in a travelling wave ion mobility spectrometry-mass spectrometer (TWIMS-MS) with modifications to allow for ion/molecule reactions to be performed. Despite their small difference in cross-sectional area (~1%) the isomers were well resolved, in part due to a strong interaction of isomer B with the N2 buffer gas. The reactivity of each TWIMS-separated isomer was probed: propane reacted with isomer A via CH bond activation and O-atom transfer, while no such reactions were observed for isomer B; the aryl halides PhX (X=F, Cl, Br, I) also reacted solely with A, via either concerted oxidation and halide transfer, or O-atom transfer. DFT calculations reveal that the aryl CX bond activation of PhX by isomer A involves several mechanistic pathways. [ABSTRACT FROM AUTHOR]

Objectives: A general population job-exposure matrix (GPJEM) including physical and psychosocial demands as well as psychosocial resources applicable to older and retired workers was developed. Its validity was evaluated by examining associations of physical demands and iso-strain (combination of high psychosocial demands and low resources) with health. Methods: Physical and psychosocial work exposures reported by 55–64 year olds were derived from the Netherlands Working Conditions Survey and linked to the Netherlands Standard Classification of Occupations 1992. A GPJEM with low, moderate, and high probability of exposure to demands and resources was developed. To examine associations with health, two groups of the Longitudinal Aging Study Amsterdam were selected: current (i.e. at the time of the interview, 55–64 years) and former workers (55–84 years). Linear and logistic regression models were applied. Results: Use of force and work in uncomfortable positions were significantly associated with functional limitations and self-perceived health (SPH), but not hip or knee osteoarthritis (OA), in current and former workers. A moderate probability of repetitive movements was associated with functional limitations in former workers. A high probability of repetitive movements was associated with functional limitations in current and former workers as well as with SPH and hip and knee OA in former workers. Respondents formerly exposed to iso-strain had significantly higher diastolic blood pressure and more often hypertension. No such associations were found in current workers. No association was found with cardiovascular disease. Conclusions: The results suggest that our GPJEM accurately classifies jobs according to physical demands and, although less clearly, iso-strain. [ABSTRACT FROM AUTHOR]

The near thermal conditions of an ion-trap mass spectrometer were used to examine the intrinsic gas-phase reactivity and selectivity of nucleophilic substitution reactions. The well-defined organocuprate anions [CH3CuR]- (R = CH3CH2, CH3CH2CH2, (CH3)2CH, PhCH2CH2, PhCH2, Ph, C3H5, and H) were reacted with CH3I. The rates (reaction efficiencies, φ) and selectivities (the product ion branching ratios) were compared with those of [CH3CuCH3]- reacting with CH3I. Alkyl R groups yielded similar efficiencies, with selectivity for C-C bond formation at the coordinated R group. Inclusion of unsaturated R groups curbed the overall reactivity (φ = 1 to 2 orders of magnitude lower). With the exception of R = PhCH2CH2, these switched their selectivity to C-C bond formation at the CH3 group. Replacing an organyl ligand with R = H significantly enhanced the reactivity (8-fold), resulting in the selective formation of methane. Unique decomposition and side-reactions observed include: (1) spontaneous β-hydride elimination from [RCuI]- byproducts; and (2) homocoupling of the pre-existing organocuprate ligands in [CH3CuC3H5]-, as shown by deuterium labeling. DFT (B3LYP-D/Def2-QZVP//B3LYP/SDD:6-31+G(d)) predicts that the alkylation mechanism for all species is via oxidative addition/reductive elimination (OA/RE). OA is the rate-limiting step, while RE determines selectivity: the effects of R on each were examined. [ABSTRACT FROM AUTHOR]

Background: Whether middle-aged individuals are capable of employment continuation may be limited by poor memory. Subjective memory complaints may be used to identify those at risk of poor memory. Research questions, therefore, were (i) are prevalent memory complaints associated with relevantly poor memory performance and decline in 55 to 64-year-olds; (ii) are incident memory complaints associated with relevant memory decline; and (iii) do these associations differ between employed and not employed individuals? Methods: Participants of the Longitudinal Aging Study Amsterdam (LASA) were examined. Data were weighted by sex, age and region. To examine the association of prevalent memory complaints with relevantly poor learning ability (n = 903) and delayed recall (n = 897; both assessed with the Auditory Verbal Learning Test), subnormal (≤ mean − 1 SD) and impaired (≤ mean − 1.5 SD) memory performance were defined. To examine the association of prevalent and incident memory complaints with relevant decline after 3 years in learning ability (n = 774 and 611, respectively) and delayed recall (n = 768 and 603, respectively), above normal (≤ mean − 1 SD) and clinically relevant (≤ mean − 1.5 SD) memory decline were investigated. Logistic regression analyses were applied. Results: Adjusted for gender, education and age, individuals with memory complaints more often had impaired delayed recall and clinically relevant decline in learning ability. Incident memory complaints were borderline significantly associated with clinically relevant decline in learning in continuously employed individuals (paid job ≥1 h weekly), but not in continuously not employed individuals. Conclusion: Memory complaints may identify 55 to 64-year-olds at risk of memory impairment and decline. Our results provide hypotheses about the association between memory complaints and decline in employed 55 to 64-year-olds. [ABSTRACT FROM AUTHOR]

Campylobacter jejuni is the most common bacterial cause of human gastroenteritis and often precedes development of Guillain-Barré syndrome (GBS), a life-threatening paralytic disease. The incorporation of the carbohydrate sialic acid into C. jejuni lipooligosaccharides (LOS) is associated with increased severity of gastroenteritis and with induction of GBS; however, the underlying mechanisms remain completely unknown. In this study, we demonstrate that sialic acids in C. jejuni endotoxin enhance the rapid production of IFN-β and TNF-α by human dendritic cells (DCs). Using neutralizing Abs and receptors it was shown that these DC-derived cytokines promote the proliferation of human mucosal B cells in a T cell-independent manner. The production of both IFN-β and TNF-α by DCs in response to LOS requires CD14, and the amplified response of DCs to sialylated C. jejuni LOS is CD14 dependent. Together, these results indicate that sialylation of C. jejuni LOS increases DC activation and promotes subsequent B cell responses through CD14-driven production of IFN-β and TNF-α. This enhanced DC/B cell response may explain the increased pathogenicity of sialylated C. jejuni and may be key to the initiation of B cell-mediated autoimmunity in GBS. [ABSTRACT FROM AUTHOR]

Allylic alkylation of organocuprates represents an importantclass of C–C bond forming reactions. A drawback of these reactionsis their stoichiometric nature. Although metal-catalyzed decarboxylativecoupling reactions offer new opportunities for formation of C–Cbonds, catalytic allylic alkylation reactions of organocuprates havenot been previously reported. Here, multistage mass spectrometry experimentsperformed on ion trap mass spectrometers in conjunction with electronicstructure calculations are used to demonstrate that the dimethylcuprateanion, [CH3CuCH3]−, can catalyzedecarboxylative coupling of allyl acetate in the gas phase via a simpletwo-step catalytic cycle. In step 1, [CH3CuCH3]−undergoes a cross-coupling reaction with allylacetate to yield [CH3CuO2CCH3]−as the major product ion. Step 2 involves subjectingthe product ion to collision-induced decarboxylation to re-form [CH3CuCH3]−, thereby closing thecatalytic cycle. Since the details of step 2 have been previouslydescribed (Rijs, N.; Khairallah, G. N.; Waters, T.; O’Hair, R. A. J.J. Am. Chem. Soc.2008, 130, 1069−1079), here the focus is on step 1. Comparisonof the reactivity of dimethylcuprate toward allylic susbtrates revealsthat while allyl acetate reacts around 70 times more slowly than allyliodide, it is more selective for cross-coupling. This is rationalizedby DFT calculations, which reveal that an increase in kinetic barrieris responsible for both reactivity trends. The lowest energy pathwas found to involve a stepwise π-oxidative addition proceedingvia an η2-C3H5O2CCH3intermediate and extrusion of a leaving group (LG)anion, followed by a reductive elimination where this LG is recomplexedto the copper center. Finally, DFT calculations were used to shedlight on the role of leaving groups LG = CH3CO2–, I–, Br–,Cl–in the allylic alkylation. While selectivityis indeed achieved at the cost of reactivity, the LG effects weremore complex than can be accounted for by a simple consideration ofthe anion proton affinity (APA) of the LG. [ABSTRACT FROM AUTHOR]

Copper-mediated allylic substitution reactions are widely used in organic synthesis, whereas the analogous reactions for silver and gold are essentially unknown. To unravel why this is the case, the gas-phase reactions of allyl iodide with the coinage metal dimethylmetallates, [CH3MCH3]- (M = Cu, Ag and Au), were examined under the near thermal conditions of an ion trap mass spectrometer and via electronic structure calculations. [CH3CuCH3]- reacted with allyl iodide with a reaction efficiency of 6.6% of the collision rate to yield: I- (75%); the cross-coupling product, [CH3CuI]- (24%); and the homo-coupling product, [C3H5CuI]- (1%). [CH3AgCH3]- and [CH3AuCH3]- reacted substantially slower (reaction efficiencies of 0.028% and 0.072%). [CH3AgCH3]- forms I- (19%) and [CH3AgI]- (81%), while only I- is formed from [CH3AuCH3]-. Because the experiments do not detect the neutral product(s) formed, which might otherwise help identify the mechanisms of reaction, and to rationalize the observed ionic products and reactivity order, calculations at the B3LYP/def2-QZVP//B3LYP/SDD6-31+G(d) level were conducted on four different mechanisms: (i) SN2; (ii) SN2'; (iii) oxidative-addition/reductive elimination (OA/RE) via an M(III) η³-allyl intermediate; and (iv) OA/RE via an M(III) η¹-allyl intermediate. For copper, mechanisms (iii) and (iv) are predicted to be competitive. Only the Cu(III) η³-allyl intermediate undergoes reductive elimination via two different transition states to yield either the cross-coupling or the homo-coupling products. Their relative barriers are consistent with homo-coupling being a minor pathway. For silver, the kinetically most probable pathway is the SN2 reaction, consistent with no homo-coupling product, [C3H5AgI]-, being observed. For gold, no C-C coupling reaction is kinetically viable. Instead, I- is predicted to be formed along with a stable Au(III) η³-allyl complex. These results clearly highlight the superiority of organocuprates in allylic substitution reactions. [ABSTRACT FROM AUTHOR]

Health consequences of retirement have not been included in the current public debate about increasing the age at retirement, which might be due to the fact that studies aimed at health consequences of retirement show ambiguous results. The literature indicates that various contextual characteristics might explain conflicting results. The current study examines the effect of retirement and age at retirement (55-64 years) on self-perceived health. Characteristics tested for confounding and effect modification were: demographic, health, psychological, job, and retirement characteristics. Subjects were 506 participants in the Longitudinal Aging Study Amsterdam (LASA). After three years, 216 retired and 290 remained employed. Multinomial logistic regression analyses show no main effect for retirement compared to continued employment. Modal (59-60) retirees were more likely to attain excellent or good self-perceived health (less than good self-perceived health as the reference category). Early (55-58) and late (61-64) retirees were unaffected by retirement if they did not receive a disability pension. Early and late retirees who received a disability pension were less likely to attain excellent self-perceived health after retirement. Higher educated were less likely to attain excellent self-perceived health after retirement, especially at late retirement age, although health selection might explain this result. Finally, mastery possibly acts as an adjustment resource. The paper concludes with a discussion on explanations for the effect of retirement and age at retirement. [ABSTRACT FROM AUTHOR]

Health consequences of retirement have not been included in the current public debate about increasing the age at retirement, which might be due to the fact that studies aimed at health consequences of retirement show ambiguous results. The literature indicates that various contextual characteristics might explain conflicting results. The current study examines the effect of retirement and age at retirement (55–64 years) on self-perceived health. Characteristics tested for confounding and effect modification were: demographic, health, psychological, job, and retirement characteristics. Subjects were 506 participants in the Longitudinal Aging Study Amsterdam (LASA). After three years, 216 retired and 290 remained employed. Multinomial logistic regression analyses show no main effect for retirement compared to continued employment. Modal (59–60) retirees were more likely to attain excellent or good self-perceived health (less than good self-perceived health as the reference category). Early (55–58) and late (61–64) retirees were unaffected by retirement if they did not receive a disability pension. Early and late retirees who received a disability pension were less likely to attain excellent self-perceived health after retirement. Higher educated were less likely to attain excellent self-perceived health after retirement, especially at late retirement age, although health selection might explain this result. Finally, mastery possibly acts as an adjustment resource. The paper concludes with a discussion on explanations for the effect of retirement and age at retirement. [ABSTRACT FROM PUBLISHER]

High-resolution IR spectroscopy has been employed to study isolated, switchable [2]rotaxanes. IR absorption spectra of two-station rotaxanes, their separate thread, and macrocycle components, as well as those of the individual stations incorporated into the thread, have been measured in the 1800-1000 cm-1 region. These spectra have been fully analyzed, aided by quantum chemical predictions of the IR spectra. From these analyses, a comprehensive picture emerges of the contormational structure and binding interactions between the mechanically interlocked components of the rotaxane. [ABSTRACT FROM AUTHOR]

A combination of multistage mass spectrometry experiments and DFT calculations were used to examine the synthesis and reactivity of dimethylaurate. Collision induced dissociation (CID) of [(CH3CO2)4Au]−proceeded viareductive elimination of acetylperoxide to yield the diacetate [CH3CO2AuO2CCH3]−, which in turn underwent sequential CID decarboxylation reactions to yield the organoaurates [CH3CO2AuCH3]−and [CH3AuCH3]−. The unimolecular chemistry of the dimethylaurate proceeds viaa combination of bond homolysis to yield the methyl aurate radical anion [CH3Au]−as well as formation of the gold dihydride [HAuH]−. DFT calculations reveal that the latter anion is formed viaa 1,2-dyotropic rearrangement to yield the isomer [CH3CH2AuH]−, followed by a β-hydride elimination reaction. Ion-molecule reactions of [CH3AuCH3]−with methyl iodide did not yield any products even at relatively high concentrations of the neutral substrate and longer reaction times, indicating a reaction efficiency of less than 1 in 20 000 collisions. DFT calculations were carried out on two different potential energy surfaces (PES) for the reaction of [CH3AuCH3]−with CH3I: (i) an SN2 mechanism proceeding viaa side-on transition state; and (ii) a stepwise mechanism proceeding viaoxidative addition followed by reductive elimination. Both pathways have significant endothermic barriers, consistent with the lack of C–C bond coupling products being formed in the experiments. Finally, the reactivity of [CH3AuCH3]−is compared to the previously studied [CH3AgCH3]−and [CH3CuCH3]−, as well as condensed phase studies on dimethylaurate salts. [ABSTRACT FROM AUTHOR]

A benchmark of tunable and switchable devices at microwave frequencies is presented on the basis of physical limitations to show their potential for reconfigurable cellular applications. Performance limitations are outlined for each given technology focusing on the quality factor (Q) and tuning ratio (η) as figures of merit. The state of the art in terms of these figures of merit of several tunable and switchable technologies is visualized and discussed. If the performance of these criteria is not met, the application will not be feasible. The quality factor can typically be traded off for tuning ratio. The benchmark of tunable capacitor technologies shows that transistor-switched capacitors, varactor diodes, and ferroelectric varactors perform well at 2 GHz for tuning ratios below 3, with an advantage for GaAs varactor diodes. Planar microelectromechanical capacitive switches have the potential to outperform all other technologies at tuning ratios higher than 8. Capacitors based on tunable dielectrics have the highest miniaturization potential, whereas semiconductor devices benefit from the existing manufacturing infrastructure. [ABSTRACT FROM AUTHOR]

The gas-phase double decarboxylation of the silver carboxylate centers [RCO2AgO2CR]−and [MeCO2AgO2CR]−was investigated as a means of synthesizing homo- [RAgR]−(R = Me and Et) and heteroargenates [MeAgR]−(R = Et, Pr, iPr, tBu, Allyl, PhCH2, Ph). The formation of these organoargenates was examined by multistage mass spectrometry experiments employing collision-induced dissociation (CID) and by density functional theory. A key side reaction in competition with the second stage of decarboxylation involves the loss of the anionic carboxylate ligand. Interpretation of the decarboxylation pathway of the heterocarboxylates [MeCO2AgO2CR]−was more complex due to the possibility of decarboxylation occurring at either of the two different carboxylate ligands, giving rise to the possible isomers [MeAgO2CR]−and [MeCO2AgR]−. This difficulty was overcome through the use of 13C labeling experiments in which [Me13CO2AgO2CR]−was subjected to CID, thereby providing direct evidence for the relative population of the isomers through the losses of 13CO2and CO2. For example, [Me13CO2AgO2CtBu]−underwent exclusive loss of 13CO2, indicating decarboxylation from the MeCO2−ligand, while [Me13CO2AgO2CAllyl]−underwent exclusive loss of CO2, indicating decarboxylation from the AllylCO2−ligand. MeCO2−was preferentially decarboxylated when R = Et, Pr, iPr, and tBu, while RCO2−was preferred for R = Allyl, PhCH2, and Ph. Subsequent fragmentation was in agreement with the assigned structures, including in cases where sufficient yields of both the isomeric products [Me13CO2AgR]−and [MeAgO2CR]−were formed (R = PhCH2and Ph), each being independently isolated and subjected to CID. Detailed DFT calculations were carried out on the potential energy surfaces for the first and second decarboxylation reactions of all homo- and heteroargenates, as well as possible competing reactions. These reveal that in all cases the first decarboxylation reaction is favored over loss of the carboxylate ligand. In contrast, carboxylate ligand loss can become favored over the second decarboxylation reaction. Organoargenate species formed included [MeAgMe]−and [MeAgR]−(where R = Et, Pr, Allyl, PhCH2, and Ph). The organoargenate [MeAgR]−is the principle product for R = Allyl, PhCH2, and Ph but is only a minor product when R = Et and Pr. Finally, comparisons are made with previous results on the gas-phase formation of organocuprates via double decarboxylation of the related copper carboxylate centers [RCO2CuO2CR]−and [MeCO2CuO2CR]−. [ABSTRACT FROM AUTHOR]

The homocuprates [MeCuMe]- and [EtCuEt]- were generated in the gas phase by double decarboxylation of the copper carboxylate centers [MeCO2CuO2CMe]- and [EtCO2CuO2CEt]-, respectively. The same strategy was explored for generating the heterocuprates [MeCuR]- from [MeCO2CuO2CR]- (R = Et, Pr, iPr, tBu, allyl, benzyl, Ph). The formation of these organocuprates was examined by multistage mass spectrometry experiments, including collision-induced dissociation and ion-molecule reactions, and theoretically by density functional theory. A number of side reactions were observed to be in competition with the second stage of decarboxylation, including loss of the anionic carboxylate ligand and loss of neutral alkene via β-hydride transfer elimination. Interpretation of decarboxylation of the heterocarboxylates [MeCO2CuO2CR]- was more complex because of the possibility of decarboxylation occurring at either of the two different carboxylate ligands and giving rise to the possible isomers [MeCuO2CR]- or [MeCO2CuR]-. Ion-molecule reactions of the products of initial decarboxylation with allyl iodide resulted in C-C coupling to producethe ionic products [ICuO2CR] or [MeCO2CuI]-, which provided insights into the relative population of the isomers, and indicated that the site of decarboxylation was dependent on R. For example, [MeCO2CuO2CtBu]- underwent decarboxylation at MeCO2- to give [MeCuO2CtBu]-, while [MeCO2CuO2CCH2Ph]- underwentdecarboxylation at PhCH2CO2- to give [MeCO2CuCH2Ph]-. Each of the heterocuprates [MeCuR]- (R = Et, Pr, iPr, allyl, benzyl, Ph) could be generated by the double decarboxylation strategy. However, when R = tBu, intermediate [MeCuO2CtBu]- only underwent loss of tBuCO2-, a consequence of the steric bulk of tBu disfavoring decarboxylation and stabilizing the competing channel of carboxylate anion loss. Detailed DFT calculations were carried out on the potential energy surfaces for the first and second decarboxylation reactions of all homo- and heterocuprates, as well as possible competing reactions. These reveal that in all cases the first decarboxylation reaction is favored over loss of the carboxylate ligand. In contrast, other reactions such as carboxylate ligand loss and β-hydride transfer become more competitive with the second decarboxylation reaction. [ABSTRACT FROM AUTHOR]

Ultrafast molecular elimination reactions are studied using the velocity map ion imaging technique in combination with femtosecond pump-probe laser excitation. A pump laser is used to initiate the dissociative reaction, and after a predetermined time delay a probe laser "interrogates" the molecular system. Ionic fragments are detected with a two-dimensional velocity map imaging detector providing detailed information about the energetic and vectorial properties of mass selected photofragments. In this paper we discuss the ultrafast elimination of molecular iodine, I2, from IF2C-CF2I, where the iodine atoms originate from neighboring carbon atoms. By varying the femtosecond delay between pump and probe pulse, it is found that elimination of molecular iodine is a concerted process, although the two carbon-iodine bonds are not broken synchronously. Energetic considerations suggest that the crucial step in this fragmentation process is an electron transfer between the two iodine atoms in the parent molecule, which leads to Coulombic attraction and the creation of an ion-pair state in the molecular iodine fragment. [ABSTRACT FROM AUTHOR]

The photoionization dynamics of CS have been studied using high-resolution laser photoelectron spectroscopy. The photodissociation of CS2 at ~308 nm results in highly rotationally excited CS in its X1Σ+ singlet ground state, as well as in rotationally cold CS in the excited a3Π triplet state. The ground-state CS fragments are formed together with sulfur in its 3P, 1D, and 1S electronic states; triplet CS is produced in coincidence with ground-state sulfur (3P). In both channels the photoelectron spectra are dominated by Δv = 0 propensity, but transitions involving Δv = 1 and 2 are also observed. [ABSTRACT FROM AUTHOR]

Pharmaceutical products for humans or animals, as well as their related metabolites (degradation products) end up in the aquatic environment after use. Recent investigations from abroad show that low concentrations of pharmaceuticals are detectable in municipal waste water, surface water, groundwater and even drinking water. Little is known about the effects, and with that the risk, of long term exposure to low concentrations of pharmaceuticals for aquatic organisms. On the basis of the current knowledge, further attention to map the presence and effects of pharmaceutical residues on aquatic organisms is justified. To map the Dutch situation, recently a monitoring program has started. [ABSTRACT FROM AUTHOR]

Evaluates the wastewater treatment performance of constructed wetlands planted with local plant species in Uganda. Operation mode of constructed wetlands; Mean influent and effluent concentrations.

1. Partly purified mucus collected from the skin of three species of fish contains a protein that, on sodium dodecyl sulphate/polyacrylamide gel electrophoresis, comigrates with bovine brain calmodulin and shows the same calciumdependent shift in electrophoretic mobility as calmodulin. 2. Fish mucus contains a heat-stable activator of cyclic nucleotide phosphodiesterase; activation is concentration dependent and sensitive to the specific calmodulin inhibitor calmidazolium (R 24571). 3. The presence of calmodulin in fish mucus is further indicated by means of a specific radioimmunoassay. 4. A drop in the calcium concentration oF the water induces an increase in the immunoassayable calmodulin concentration of mucus, which indicates that the function of calmodulin in mucus is related to control oF permeability of the skin epithelium to water and ions. [ABSTRACT FROM AUTHOR]

This article focuses on trends in Danish religion. Any discussion of religious trends in Denmark must necessarily begin with the status of Lutheran Church or National Church. Since the Lutheran Reformation of 1536, the evangelical Lutheran Church has held a near-monopoly as the religious institution of Denmark. In practice local congregations have a wide span of self-determination. Episcopal powers have been reduced in the 20th century. However, the Parliament remains the final administrative power center for the National Church. The National Church is inclusive in its character and covers a wide spectrum. The broadness of this church may explain why other Protestant churches have had so little success in Denmark. Only Jehovah's witnesses and the Baptists have membership rate above 1 per 1,000 inhabitants. The remaining large denominations in Denmark are non-Protestant, and in large part there memberships are made up of immigrants. There are about 28,000 Roman Catholics, 7,000 members of the Mosaic congregation and 30,000 people with Muslim backgrounds. There are very few people who leave the fold of the National Church. However, the core group of regular church attendants is quite small.

Simple Summary: Near-infrared imaging of tumors during surgery facilitates the oncologic surgeon to distinguish malignant from healthy tissue. The technique is based on fluorescent tracers binding to tumor biomarkers on malignant cells. Currently, there are no clinically available fluorescent tracers that specifically target soft tissue sarcomas. This review searched the literature to find candidate biomarkers for soft tissue sarcomas, based on clinically used therapeutic antibodies. The search revealed 7 biomarkers: TEM1, VEGFR-1, EGFR, VEGFR-2, IGF-1R, PDGFRα, and CD40. These biomarkers are abundantly present on soft tissue sarcoma tumor cells and are already being targeted with humanized monoclonal antibodies. The conjugation of these antibodies with a fluorescent dye will yield in specific tracers for image-guided surgery of soft tissue sarcomas to improve the success rates of tumor resections. Surgery is the mainstay of treatment for localized soft tissue sarcomas (STS). The curative treatment highly depends on complete tumor resection, as positive margins are associated with local recurrence (LR) and prognosis. However, determining the tumor margin during surgery is challenging. Real-time tumor-specific imaging can facilitate complete resection by visualizing tumor tissue during surgery. Unfortunately, STS specific tracers are presently not clinically available. In this review, STS-associated cell surface-expressed biomarkers, which are currently already clinically targeted with monoclonal antibodies for therapeutic purposes, are evaluated for their use in near-infrared fluorescence (NIRF) imaging of STS. Clinically targeted biomarkers in STS were extracted from clinical trial registers and a PubMed search was performed. Data on biomarker characteristics, sample size, percentage of biomarker-positive STS samples, pattern of biomarker expression, biomarker internalization features, and previous applications of the biomarker in imaging were extracted. The biomarkers were ranked utilizing a previously described scoring system. Eleven cell surface-expressed biomarkers were identified from which 7 were selected as potential biomarkers for NIRF imaging: TEM1, VEGFR-1, EGFR, VEGFR-2, IGF-1R, PDGFRα, and CD40. Promising biomarkers in common and aggressive STS subtypes are TEM1 for myxofibrosarcoma, TEM1, and PDGFRα for undifferentiated soft tissue sarcoma and EGFR for synovial sarcoma. [ABSTRACT FROM AUTHOR]

Sixty-eight commercial bottled mineral waters (64 brands, 68 different ‘best-before dates’) were tested for the presence of bacteria and fungi. Six samples were Legionella antigen positive and six were Legionella pneumophila PCR positive. Two samples were both Legionella antigen and L. pneumophila PCR positive. Legionella cultures were negative. Although the PCR might have detected only dead Legionella cells, the PCR has been described to detect specifically viable but not culturable (VBNC) L. pneumophila cells as well. Whether VBNC bacteria may be present in bottled mineral waters and the risk for infection this may pose for severely immunocompromised patients should be investigated. [ABSTRACT FROM AUTHOR]

Here the monocation complexes of seven anti-cryptophanes are examined with high-resolution ion-mobility mass spectrometry. The relative size of the [cation + cryptophane]+ complexes were compared based on their measured mobilities and derived collisional cross sections. A paradoxical trend of structural contraction was observed for complexes of increasing cation size. Density functional theory confirmed encapsulation occurs for cation = Na+, K+, Rb+, Cs+ and NH4+. However, cation = Li+ preferred oxygen coordination at a linker over encapsulation within the cavity, leading to a slightly larger gas phase structure overall. Protonated cryptophanes yielded much larger collision cross sections via imploded cryptophane structures. Thus, competing physical effects led to the observed non-periodic size trend of the complexes. Trends in complexation from isothermal titration calorimetry and other condensed phase techniques were borne out by the gas phase studies. Further, predicted cavity sizes compared with the gas phase experimental findings reveal more about the encapsulation mechanisms themselves. [ABSTRACT FROM AUTHOR]

The photoionization dynamics of rotationally hot molecular nitrogen are studied employing resonance enhanced multiphoton ionization in combination with photoelectron spectroscopy. Photodissociation of N[sub 2]O at ∼203 nm results in highly rotationally excited N[sub 2] fragments in X [sup 1]∑[sub g][sup +](N[sup ″],v[sup ″]=0,1) states and O atoms in the excited [sup 1]D[sub 2] state. Photoelectron detection of the rotationally hot N[sub 2] states is performed by a two-photon excitation to the lowest a[sup ″] [sup 1]∑[sub g][sup +] Rydberg state followed by one-photon ionization. The large number of observed rotational levels, from N[sup ′]=49 up to N[sup ′]=94, results in improved rotational parameters for a[sup ″] [sup 1]∑[sub g][sup +] (v[sup ′]=0). In addition, experimental and theoretical rotationally resolved photoelectron spectra of the a[sup ″] [sup 1]∑[sub g][sup +](v[sup ′]=0,1;N[sup ′]) state are presented. In these spectra only ΔN=N[sup +]-N[sup ′]=even transitions are observed, with a dominant ΔN=0 peak and rather weak ΔN=±2 peaks. The one-photon ionization is dominated by ejection of electrons in p and f partial waves. The agreement between experimental and calculated spectra is excellent. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Peptide segments with phenylalanine residues are commonly found in proteins that are related to neurodegenerative diseases. However, the self-assembly of phenylalanine-based peptides can be also functional. Peptides containing phenylalanine residues with different side caps, composition, and chemical alteration can form different types of nanostructures that find many applications in technology and medicine. Various studies have been performed in order to explain the remarkable stability of the resulting nanostructures. Here, we study the early stages of self-assembly of two phenylalanine derived peptides in the gas phase using IR action spectroscopy. Our focus lies on the identification of the key intra- and intermolecular interactions that govern the formation of the dimers. The far-IR region allowed us to distinguish between structural families and to assign the 2-(2-amino-2-phenylacetamido)-2-phenylacetic acid (PhgPhg) dimer to a very symmetric structure with two intermolecular hydrogen bonds and its aromatic rings folded away from the backbone. By comparison with the phenylalanine-based peptide cyclic L-phenylalanyl-L-phenylalanine (cyclo-FF), we found that the linear FF dimer likely adopts a less ordered structure. However, when one more phenylalanine residue is added (FFF), a more structurally organized dimer is formed with several intermolecular hydrogen bonds. [ABSTRACT FROM AUTHOR]

Intramedullary spinal cord tumors (IMSCT) comprise the least common types of spinal neoplasms; surgery is mostly conducted with intraoperative neuromonitoring (IONM). However, although IONM is widely used to prevent neurologic damage and many single-center studies have been reported, the added value, in terms of overall sensitivity and specificity, of different monitoring techniques used in IMSCT surgery remains to be clearly defined. To summarize and review the reported evidence on the use of IONM in IMSCT surgery, including our own case series (n = 75 patients). We systematically searched the literature published from January 2000 to February 2018. Articles included patients with IMSCT who underwent surgery with neuromonitoring. We estimated the sensitivity, specificity, 95% confidence interval (CI), positive likelihood ratio, and negative likelihood ratio. Of 1385 eligible articles, 31 were included in the systematic review. Fifteen of these articles were used for a meta-analysis, complemented with our own case series. All neuromonitoring modalities showed acceptable but not optimal test characteristics. For the indications used in the different studies, the motor evoked potentials approach showed the highest sensitivity (0.838; 95% CI, 0.703–0.919) and the best specificity (0.829; 95% CI, 0.668–0.921) for detecting neuronal injury. In our own case series, the extent of resection was significantly smaller in the false-positive group than in the true-negative group (P = 0.045). IONM showed high but not perfect sensitivity and specificity. IONM prevents neurologic damage but can also limit the extent of tumor resection. Prospective studies will have to define the definitive value of IONM. [ABSTRACT FROM AUTHOR]

The vapor compression heat pumps are very popular solutions regarding heat supply systems of modern, low energy buildings. It is partly due to the fact that they are treated as a sustainable heat supply. The question arises: Can a vapor compression heat pump be treated as a sustainable heat supply? To answer this question; the exergy model of a heat pump system operation has been proposed. The proposed model has been employed for evaluation of exergy efficiency of an existing heat supply system equipped with two heat pumps installed in an educational building located on the campus of Poznan University of Technology, Poznan, Poland. The analysis shows that the system exergy efficiency decreases with an increase in outdoor temperature and its values are in the range of 10.9% to 42.0%. The primary exergy efficiency, which considers the conversion of fossil fuel into electricity, is on average 3.2 times lower than the system exergy efficiency for the outdoor temperature range of −9 °C to 11 °C. The performed analysis allowed for the identification of a set of solutions that may increase the exergy and primary exergy efficiency of the system. The first solution is to cover a part of the electricity demand by a renewable energy source. The second proposition is to apply a low-temperature emission system for heating. The third idea is to apply a district heating network as the heat supply instead of the heat pump. The conclusion is that the exergy performance of systems with heat pumps is rather poor because they generate low-quality heat from high-quality electricity. The best way to improve the primary exergy efficiency of a heat pump system is to power the system by electricity generated from a renewable energy source. [ABSTRACT FROM AUTHOR]

Intradural extramedullary spinal cord tumors (ID-EMSCT) make up 40% of all spinal neoplasms. Resection of these tumors is mostly conducted using intraoperative neuromonitoring (IONM). However, the literature shows heterogenous data on its added value for ID-EMSCT. The aim of this study is to define sensitivity and specificity of IONM in ID-EMSCT resection and to study possible correlations between preoperative, intraoperative, and postoperative variables and neurologic outcomes after ID-EMSCT resection. Data of patients undergoing ID-EMSCT surgeries with IONM from January 2012 until July 2019 were examined. Using neurologic status 6 weeks and 1 year postoperatively, sensitivity and specificity for IONM were calculated. IONM test results and neurologic outcomes were paired to preoperative, intraoperative, and postoperative parameters. Data of 78 patients were analyzed. 6 weeks postoperatively, 14.10% of patients had worse neurologic status, decreasing to 9.84% 1 year postoperatively. Multimodal IONM showed a sensitivity of 0.73 (95% confidence interval [CI], 0.39–0.94) and a specificity of 0.78 (95% CI, 0.66–0.87) after 6 weeks, and a sensitivity of 1.00 (95% CI, 0.54–1.00) and a specificity of 0.71 (95% CI, 0.57–0.82) after 1 year. IONM yielded high to perfect sensitivity and high specificity. However, IONM signals did not always determine the extent of resection, and false-positive results did not always result in incomplete tumor resections, because of surgeons overruling IONM. Therefore, IONM cannot fully replace clinical judgment and other perioperative information. [ABSTRACT FROM AUTHOR]

Summary: Postoperative pain might be different after intravenous vs. oral paracetamol. We systematically reviewed randomised controlled trials in patients >15 years that compared intravenous with oral paracetamol for postoperative pain. We identified 14 trials with 1695 participants. There was inconclusive evidence for an effect of route of paracetamol administration on postoperative pain at 0–2 h (734 participants), 2–6 h (766 participants), 6–24 h (1115 participants) and >24 h (248 participants), with differences in standardised mean (95%CI) pain scores for intravenous vs. oral of −0.17 (−0.45 to 0.10), −0.09 (−0.24 to 0.06), 0.06 (−0.12 to 0.23) and 0.03 (−0.22 to 0.28), respectively. Trial sequential analyses suggested that a total of 3948 participants would be needed to demonstrate a meaningful difference in pain or its absence at 0–2 h. There were no differences in secondary outcomes. Intravenous paracetamol is more expensive than oral paracetamol. Substitution of oral paracetamol in half the patients given intravenous paracetamol in our hospital would save around £ 38,711 (€ 43,960 or US$ 47,498) per annum. [ABSTRACT FROM AUTHOR]

Background: Intrathecal hydrophilic opioids decrease systemic opioid consumption after abdominal surgery and potentially facilitate enhanced recovery. A meta-analysis is needed to quantify associated risks and benefits.Methods: A systematic search was performed to find RCTs investigating intrathecal hydrophilic opioids in abdominal surgery. Caesarean section and continuous regional or neuraxial techniques were excluded. Several subgroup analyses were prespecified. A conventional meta-analysis, meta-regression, trial sequential analysis, and provision of GRADE scores were planned.Results: The search yielded 40 trials consisting of 2500 patients. A difference was detected in 'i.v. morphine consumption' at Day 1 {mean difference [MD] -18.4 mg, (95% confidence interval [CI]: -22.3 to -14.4)} and Day 2 (MD -25.5 mg [95% CI: -30.2 to -20.8]), pain scores at Day 1 in rest (MD -0.9 [95% CI: -1.1 to -0.7]) and during movement (MD -1.2 [95% CI: -1.6 to -0.8]), length of stay (MD -0.2 days [95% CI: -0.4 to -0.1]) and pruritus (relative risk 4.3 [95% CI: 2.5-7.5]) but not in nausea or sedation. A difference was detected for respiratory depression (odds ratio 5.5 [95% CI: 2.1-14.2]) but not when two small outlying studies were excluded (odds ratio 1.4 [95% CI: 0.4-5.2]). The level of evidence was graded as high for morphine consumption, in part because the required information size was reached.Conclusions: This study showed important opioid-sparing effects of intrathecal hydrophilic opioids. Our data suggest a dose-dependent relationship between the risk of respiratory depression and the dose of intrathecal opioids. Excluding two high-dose studies, intrathecal opioids have a comparable incidence of respiratory depression as the control group.Clinical Trial Registration: PROSPERO-registry: CRD42018090682. [ABSTRACT FROM AUTHOR]

Phenylephrine is recommended for the management of hypotension after spinal anaesthesia in women undergoing caesarean section. Noradrenaline, an adrenergic agonist with weak β-adrenergic activity, has been reported to have a more favourable haemodynamic profile than phenylephrine. However, there are concerns that noradrenaline may be associated with a higher risk of fetal acidosis, defined as an umbilical artery pH < 7.20. We performed a systematic review of trials comparing noradrenaline with phenylephrine, concentrating on primary outcomes of fetal acidosis and maternal hypotension. We identified 13 randomised controlled trials including 2002 patients. Heterogeneity among the studies was high, and there were too few data to calculate a pooled effect estimate. Fetal acidosis was assessed in four studies that had a low risk of bias and a low risk of confounding, that is, studies which used a prophylactic vasopressor and where women received the allocated vasopressor only. There were no significant differences between these studies. No significant differences were observed for hypotension. Two trials found a significantly lower incidence of bradycardia when using noradrenaline. Cardiac output was significantly higher after noradrenaline in two of three studies. For other secondary outcomes including nausea, vomiting and Apgar scores at 1 and 5 min, no studies found significant differences. The evidence so far is too limited to support an advantage of noradrenaline over phenylephrine. Concerns of a deleterious effect of noradrenaline on fetal blood gas status cannot currently be assuaged by the available data from randomised controlled studies. [ABSTRACT FROM AUTHOR]

The spontaneous aggregation of proteins and peptides is widely studied owing to its relation to neurodegenerative diseases. To understand the underlying principles of peptide aggregation, elucidation of structure and structural changes upon their formation is key. This level of detail can be obtained by studying the peptide self‐assembly in the gas phase. Structural characterization of aggregates is mainly done on charged species, as adding charges is an intrinsic part of the technique to bring molecules into the gas phase. Studying neutral peptide aggregates will complement the existing picture. These studies are restricted to dimers due to experimental limitations. Herein, we present advances in laser desorption molecular beam spectroscopy to form neutral peptide aggregates consisting of up to 14 monomeric peptides in the gas phase. The combination of this technique with IR–UV spectroscopy allowed us to select each aggregate by size and subsequently characterize its structure. [ABSTRACT FROM AUTHOR]