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We report the infrared photodissociation spectrum of tagged protonated valine in the range 1000-1900 cm-1, prepared in a cryogenic ion trap. Comparison of experimental results with calculated infrared spectra based on density functional theory shows that the hydroxyl group of the carboxylic acid functionality and the protonated amine group adopt a trans configuration. Nitrogen and methane molecules were used as messenger tags with optimal tagging temperatures of 30 K for N2 and 60 K for CH4. While the calculated infrared spectra of the tagged ion suggest only a weak influence of the messenger tag on the frequency positions of ValH+, the measured intensities for N2-tagged ValH+ appear strongly suppressed for all but the highest frequency feature at 1773 cm-1. We trace this behavior to the binding energy of the N2 tag, which is significantly higher than that of CH4, based on density functional and coupled cluster calculations and rate estimates for photoinduced unimolecular dissociation from statistical theory.
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BACKGROUND: House dust mite (HDM) sensitisation can contribute to the development of allergic rhinoconjunctivitis (AR) or allergic asthma (AA). As treatment, allergen immunotherapy (AIT) is a promising approach, since it aims building immunotolerance against allergens, therewith establishing long-term efficacy. The evaluation of AIT has been investigated in many randomised controlled trials, whereas few real-world evidence studies are available. METHODS: We used data from the longitudinal prescription data base IQVIA™ LRx. Data on initial AIT prescriptions against HDM from January 2009 to December 2013 was analysed regarding treatment (subcutaneous AIT with either depigmented polymerised allergen extract [dSCIT] or other allergens [oSCIT], or sublingual immunotherapy [SLIT]) and treatment duration. Treatment groups were compared with a control group of AR patients not receiving AIT. Data on symptomatic medication was collected until February 2017 and progression of AR and AA was compared. RESULTS: Data of 7260 patients with AIT prescriptions and of 21,780 control patients was analysed. AIT was associated with a significant decrease of AR medication intake compared with control (dSCIT: -34.0%, p < 0.0001; oSCIT: -25.7%, p < 0.0001; SLIT: -37.7%, p = 0.0026). In asthmatics, SCIT was associated with a significant decrease of asthma medication compared with control (dSCIT: -45.2%, p < 0.0001; oSCIT: -32.9%, p < 0.0001). Further, a significantly reduced likelihood for onset of asthma medication was demonstrated in patients treated with SCIT compared with controls (dSCIT OR: 0.759, p = 0.0476; oSCIT OR: 0.815, p = 0.0339). CONCLUSION: Real-world data analyses indicate that AIT, particularly given via a subcutaneous route, reduces the need of medication against AR and AA and might delay the onset of asthma medication in patients with AR.
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The present study demonstrates successful herd sanitation and eradication of contagious mastitis caused by Staphylococcus aureus genotype B (S. aureus GTB) in an entire Swiss district (Ticino) including 3,364 dairy cows from 168 farms. Herd sanitation included testing of all cows using a highly GTB specific and sensitive qPCR assay, implementation of related on-farm measures, appropriate antibiotic therapy of GTB-positive cows and culling of therapy-resistant animals, respectively. A treatment index was used as an objective criterion to select GTB-positive cows eligible for culling and replacement payment. 62 herds (37%) were initially GTB-positive with a cow prevalence between 10% and 100% and were submitted to sanitation. Twenty mo after the start of the campaign, all these herds were free from S. aureus GTB, whereby 73% of them were sanitized during the first 7 mo. At the cow level, a total of 343 animals were infected. 50 of them were immediately culled and financially compensated based on their treatment index value. The remaining 293 cows were intramammarily treated with antibiotics either during lactation using the combination of cephalexin-kanamycin or penicillin-gentamicin or at dry-off using cloxacillin. Out of these cows, 275 (93.9%) were treated successfully meaning that their milk was twice GTB-negative by qPCR after therapy. For lactational treatment, control samples were taken ≥10 and ≥20 d after treatment, for dry off treatment ≥14 and ≥24 d after parturition. Neither lactation number nor SCC before treatment of the cow nor the type of therapy were associated with therapeutic cure. Using data of 30 GTB-positive and 71 GTB-negative herds (1855 observations), the impact of GTB sanitation on bulk tank milk SCC (BTSCC) was evaluated applying a linear mixed statistical model. In the year before sanitation, BTSCC was always higher in GTB positive than in GTB negative herds. After the start of the campaign, BTSCC declined rapidly in the herds under GTB sanitation and achieved values that no longer differed statistically from those of GTB-free herds after only 2 mo, remaining very similar for the rest of the campaign. The farmers were very satisfied with the outcome of the campaign as all GTB positive herds could be sanitized rapidly, sanitation was sustainable, and milk quality increased.
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In this work, we report the infrared spectrum of the pyrene anion, measured using messenger tagging with up to three Ar atoms. We assign the spectrum using density functional theory and vibrational perturbation theory. We discuss our results in the context of computed and experimental spectra from the literature as well as recent observations from astronomical sources, addressing the question of whether polycyclic aromatic hydrocarbon anions could contribute to the strong infrared emission bands at 3.29 µm from carbon-rich regions of space.
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We present infrared spectra and density functional theory calculations of hydrated pyrene anion clusters with up to four water molecules. The experimental spectra were acquired by using infrared Ar messenger photodissociation spectroscopy. Water molecules form clusters on the surface of the pyrene, forming hydrogen bonds with the π-system. The structures of the water clusters and their interaction with the π-system are encoded in OH stretching vibrational modes. We find that the interactions between water molecules are stronger than the interactions between water molecules and the π-system. While all clusters show multiple conformers, three- and four-membered rings are the lowest energy structures in the larger hydrates.
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Ion receptors are molecular hosts that bind ionic guests, often with great selectivity. The interplay of solvation and ion binding in anion host-guest complexes in solution governs the binding efficiency and selectivity of such ion receptors. To gain molecular-level insight into the intrinsic binding properties of octamethyl calix[4]pyrrole (omC4P) host molecules with halide guest ions, we performed cryogenic ion vibrational spectroscopy (CIVS) of omC4P in complexes with fluoride, chloride, and bromide ions. We interpret the spectra using density functional theory, describing the infrared spectra of these complexes with both harmonic and anharmonic second-order vibrational perturbation theory (VPT2) calculations. The NH stretching modes of the pyrrole moieties serve as sensitive probes of the ion binding properties, as their frequencies encode the ion-receptor interactions. While scaled harmonic spectra reproduce the experimental NH stretching modes of the chloride and bromide complexes in broad strokes, the high proton affinity of fluoride introduces strong anharmonic effects. As a result, the spectrum of F-·omC4P is not even qualitatively captured by harmonic calculations, but it is recovered very well by VPT2 calculations. In addition, the VPT2 calculations recover the intricate coupling of the NH stretching modes with overtones and combination bands of CH stretching and NH bending modes and with low-frequency vibrations of the omC4P macrocycle, which are apparent for all of the halide ion complexes investigated here. A comparison of the CIVS spectra with infrared spectra of solutions of the same ion-receptor complexes in d3-acetonitrile and d6-acetone shows how ion solvation changes the ion-receptor interactions for the different halide ions.
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Interactions between water and polycyclic aromatic hydrocarbons are essential in many aspects of chemistry, from interstellar and atmospheric processes to interfacial hydrophobicity and wetting phenomena. Despite their growing importance, the intermolecular potentials of the water-hydrocarbon interactions are underdeveloped compared to the water-water potentials, and there are similarly few experimental probes that are sensitive to the details of the water-hydrocarbon potential. We present a combined experimental and computational study of anionic pyrene monohydrate, one of the simplest water/hydrocarbon clusters. The action spectrum in the OH region of the mass-selected cluster ion provides a rigorous benchmark for intermolecular potentials and computational methodologies. We identify missing intermolecular interactions and shortcomings in conventional dynamics calculations by comparing experimental data to density functional theory and classical molecular dynamics calculations. Kinetic trapping is prevalent, even for one water molecule and one pyrene molecule, leading to slow equilibration in conventional molecular dynamics calculations, even on nanosecond time scales and at low temperatures (50 K). At constant energy, temperature fluctuations for the pair of molecules are substantial. Immersing the system in a bath of soft spheres and employing parallel tempering alleviates kinetic trapping and dampens temperature fluctuations, bringing the system closer to the thermodynamic limit. With such augmented sampling, a simple, flexible water model reproduces the line width and the asymmetric broadening of the symmetric OH stretching mode, which we assign to spectral diffusion. In the OH stretching region, dynamics calculations predict a more intense antisymmetric peak than experiments observe but do not predict the bimodal split symmetric peak that the experiments show. Our work suggests that electronic polarization, missing in the empirical force field, is responsible for the first discrepancy and that quantum nuclear effects, captured neither in density functional theory nor in classical dynamics, may be responsible for the second.
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BACKGROUND: Interprofessional training wards (ITW) are increasingly being integrated into teaching and training concepts in visceral surgery clinics. OBJECTIVE: How safe is patient care on an ITW in visceral surgery? MATERIAL AND METHODS: Data collection took place from November 2021 to December 2022. In this nonrandomized prospective evaluation study the frequency and severity of adverse events (AE) in 3 groups of 100 patients each in a tertiary referral center hospital for visceral surgery were investigated. The groups consisted of patients on the ITW and on the conventional ward before and after implementation of the ITW. The Global Trigger Tool (GTT) was used to search for AE. Simultaneously, a survey of the treatment was conducted according to the Picker method to measure patient reported outcome. RESULTS: Baseline characteristics and clinical outcome parameters of the patients in the three groups were comparable. The GTT analysis found 74 nonpreventable and 5 preventable AE in 63 (21%) of the patients and 12â¯AE occurred before the hospital stay. During the hospital stay 50â¯AE occurred in the operating theater and 17 on the conventional ward. None of the five preventable AE (in 1.7% of the patients) was caused by the treatment on the ITW. Patients rated the safety on the ITW better than in 90% of the hospitals included in the Picker benchmark cohort and as good as on the normal ward. CONCLUSION: The GTT-based data as well as from the patients' point of view show that patient care on a carefully implemented ITW in visceral surgery is safe.
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Procedimentos Cirúrgicos do Sistema Digestório , Equipe de Assistência ao Paciente , Humanos , Centros de Atenção Terciária , Inquéritos e Questionários , Tempo de Internação , Procedimentos Cirúrgicos do Sistema Digestório/efeitos adversosRESUMO
Schistosoma reflexum (SR) is a lethal congenital syndrome characterized by U-shaped dorsal retroflexion of the spine and exposure of abdominal viscera. SR is usually associated with severe dystocia. The syndrome is thought to be inherited as a Mendelian trait. We collected a series of 23 SR-affected calves from four breeds (20 Holstein, one Red Danish, one Limousin, one Romagnola) and performed whole-genome sequencing (WGS). WGS was performed on 51 cattle, including 14 cases with parents (trio-based; Group 1) and nine single cases (solo-based; Group 2). Sequencing-based genome-wide association studies with 20 Holstein cases and 154 controls showed no association (above Bonferroni threshold; P-value<3 ×10-09). Assuming a monogenic recessive inheritance, no region of shared homozygosity was observed, suggesting heterogeneity. Alternatively, the presence of possible dominant acting de novo mutations were assessed. In Group 1, heterozygous private variants, absent in both parents, were found in seven cases. These involved the ACTL6A, FLNA, GLG1, IQSEC2, MAST3, MBTPS2, and MLLT1 genes. In addition, heterozygous private variants affecting the genes DYNC1LI1, PPP2R2B, SCAF8, SUGP1, and UBP1 were identified in five cases from Group 2. The detected frameshift and missense variants are predicted to cause haploinsufficiency. Each of these 12 affected genes belong to the class of haploinsufficient loss-of-function genes or are involved in embryonic and pre-weaning lethality or are known to be associated with severe malformation syndromes in humans and/or mice. This study presents for the first time a detailed genomic evaluation of bovine SR, suggesting that independent de novo mutations may explain the sporadic occurrence of SR in cattle.
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Doenças dos Bovinos , Doenças dos Roedores , Humanos , Bovinos , Animais , Camundongos , Estudo de Associação Genômica Ampla/veterinária , Linhagem , Síndrome , Fenótipo , Mutação , Actinas/genética , Proteínas Cromossômicas não Histona/genética , Proteínas de Ligação a DNA/genética , Fatores de Troca do Nucleotídeo Guanina/genética , Dineínas do Citoplasma/genética , Proteínas do Tecido Nervoso/genética , Doenças dos Bovinos/genéticaRESUMO
Silicon photonic ring resonator thermometers have been shown to provide temperature measurements with a 10 mK accuracy. In this work we identify and quantify the intrinsic on-chip impairments that may limit further improvement in temperature measurement accuracy. The impairments arise from optically induced changes in the waveguide effective index, and from back-reflections and scattering at defects and interfaces inside the ring cavity and along the path between light source and detector. These impairments are characterized for 220 × 500â nm Si waveguide rings by experimental measurement in a calibrated temperature bath and by phenomenological models of ring response. At different optical power levels both positive and negative light induced resonance shifts are observed. For a ring with L = 100â µm cavity length, the self-heating induced resonance red shift can alter the temperature reading by 200 mK at 1â mW incident power, while a small blue shift is observed below 100 µW. The effect of self-heating is shown to be effectively suppressed by choosing longer ring cavities. Scattering and back-reflections often produce split and distorted resonance line shapes. Although these distortions can vary with resonance order, they are almost completely invariant with temperature for a given resonance and do not lead to measurement errors in themselves. The effect of line shape distortions can largely be mitigated by tracking only selected resonance orders with negligible shape distortion, and by measuring the resonance minimum wavelength directly, rather than attempting to fit the entire resonance line shape. The results demonstrate the temperature error due to these impairments can be limited to below the 3 mK level through appropriate design choices and measurement procedures.
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The symmetric (νs) and antisymmetric (νas) O-C-O stretching modes of CO2-containing compounds encode structural information that can be difficult to decipher, due to the sensitivity of these spectral features to small shifts in charge distribution and structure, as well as the anharmonicities of these two vibrational modes. In this work, we discuss the relation between the frequency of these modes and the geometry of the O-C-O group, showing that the splitting between νs and νas (Δνas-s = νas - νs) can be predicted based only on the O-C-O bond angle obtained from quantum chemical calculations with reasonable accuracy (±46 cm-1, R2 = 0.994). The relationship is shown to hold for the infrared spectra of a variety of CO2-containing molecules measured in vacuo. The origins of this model are discussed in the framework of elementary mode analysis.
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Laser-heated melts based on the 43CaO-57Fe2O3-x eutectic, close to the calcium ferrite (CF) composition, were measured with high-energy X-ray diffraction using aerodynamic levitation over a range of redox states controlled by CO/CO2 gas atmospheres. The iron-oxygen coordination number was found to rise from 4.4 ± 0.3 at 15% Fe3+ to 5.3 ± 0.3 at 87% Fe3+. Empirical potential structure refinement modelling was used to obtain the ferric and ferrous partial pair distribution functions. It was found that the Fe2+ iron-oxygen coordination number is consistently approximately 10% higher in CF than in pure iron oxide, while Fe3+ is essentially identical in all but the most oxygen-rich environments (where it is higher in CF compared with FeOx). The model also shows calcium octahedra to be the dominant species across all redox environments, although the population of CaO7 increases with the availability of oxygen at the expense of CaO4 and CaO5. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.
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A non-traditional approach for the synthesis of pyrrole carboxamides from pyrrole carboxaldehyde and formamides or amines with catalytic amounts of nBu4NI and TBHP as oxidants is reported herein. The method is operationally simple providing straightforward access to primary, secondary, and tertiary pyrrole carboxamides in good to excellent yields utilizing inexpensive reagents under mild conditions. Unlike traditional amidations that involve ionic reactions, a mechanistic study of our current method unveils the involvement of 2- or 3-pyrrole acyl radicals that are otherwise rarely postulated. The applicability of the current method is further demonstrated in the synthesis of a drug-like compound, i.e., an optically pure carboetomidate amide.
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We present the vibrational spectra of a series of dicationic, organometallic complexes consisting of a transition metal center (Co, Ni, or Cu) coordinated by 4,4'-di(tert-butyl)-2,2'-bipyridine (DTBbpy) ligands and a formate adduct. Spectral features are analyzed and assigned through comparison with density functional theory calculations, and structures are reported. Natural population analysis shows that the DTBbpy ligands serve as flexible charge reservoirs in each complex. Shifts in the vibrational signatures of the formate moiety reveal that the nature of the metal center plays a crucial role in the charge distribution and formate-metal binding motif in each complex, illustrating the impact of the metal center on the structural and electronic properties of these complexes.
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High-energy x-ray diffraction from molten and glassy BaB2O4 and BaB4O7 has been performed using aerodynamic levitation and laser heating over a wide range of temperatures. Remarkably, even in the presence of a heavy metal modifier dominating x-ray scattering, it was possible to extract accurate values for the tetrahedral, sp3, boron fraction, N4, which declines with increasing temperature, using bond valence-based mapping from the measured mean B-O bond lengths while accounting for vibrational thermal expansion. These are used within a boron-coordination-change model to extract enthalpies, ΔH, and entropies, ΔS, of isomerization between sp2 and sp3 boron. The results for BaB4O7, ΔH = 22(3) kJ mol-1 boron, ΔS = 19(2) J mol-1 boron K-1, agree quantitatively with those found previously for Na2B4O7. Analytical expressions for N4(J, T) and associated configurational heat capacity, CPconf(J, T), and entropy, Sconf(J, T), contributions are extended to cover a wide composition range 0 ≤ J = BaO/B2O3 ≤ 3 using a model for ΔH(J) and ΔS(J) derived empirically for lithium borates. Maxima in the CPconf(J, Tg) and fragility index contributions are thereby predicted for J â² 1, higher than the maximum observed and predicted in N4(J, Tg) at J ≃ 0.6. We discuss the utility of the boron-coordination-change isomerization model in the context of borate liquids containing other modifiers and the prospect of neutron diffraction to aid in empirical determinations of modifier-dependent effects, illustrated by new neutron diffraction data on Ba11B4O7 glass, its well-known α-polymorph, and lesser-known δ-phase.
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Boratos , Boro , Entropia , Boratos/química , Bário , Temperatura AltaRESUMO
PVP is a hydrophilic polymer commonly used as an excipient in pharmaceutical formulations. Here we have performed time-resolved high-energy X-ray scattering experiments on pellets of PVP at different humidity conditions for 1-2 days. A two-phase exponential decay in water sorption is found with a peak in the differential pair distribution function at 2.85 Å, which is attributed to the average (hydrogen bonded) carbonyl oxygen-water oxygen distance. Additional scattering measurements on powders with fixed compositions ranging from 2 to 12.3 wt % H2O were modeled with Empirical Potential Structure Refinement (EPSR). The models reveal approximately linear relations between the carbonyl oxygen-water oxygen coordination number (nOC-OW) and the water oxygen-water oxygen coordination number (nOW-OW) versus water content in PVP. A stronger preference for water-water hydrogen bonding over carbonyl-water bonding is found. At all the concentrations studied the majority of water molecules were found to be randomly isolated, but a wide distribution of coordination environments of water molecules is found within the PVP polymer strands at the highest concentrations. Overall, the EPSR models indicate a continuous evolution in structure versus water content with nOW-OW=1 occurring at â¼12 wt % H2O, i.e., the composition where, on average, each water molecule is surrounded by one other water molecule.
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Povidona , Água , Povidona/química , Água/química , Difração de Raios X , Polímeros/química , OxigênioRESUMO
We investigate the microhydration structures of complexes of alkaline earth dications and ethylenediaminetetraacetic acid (EDTA) for up to two water molecules, using cryogenic ion vibrational spectroscopy in concert with density functional theory (DFT). The interaction with water shows a clear dependence on the chemical identity of the bound ion. For Mg2+, microhydration mostly involves the carboxylate groups of EDTA and does not entail direct contact with the dication. In contrast, the larger ions (Ca2+, Sr2+, and Ba2+) interact electrostatically with the microhydration environment, and this interaction increases in importance with the size of the ion. This trend reflects the ion position in the EDTA binding pocket, which comes closer to the rim of the pocket with increasing ion size.
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The vibrational spectra of cold complexes of ethylenediaminetetraacetic acid (EDTA) with transition metal dications in vacuo show how the electronic structure of the metal provides a geometric template for interaction with the functional groups of the binding pocket. The OCO stretching modes of the carboxylate groups of EDTA serve as structural probes, informing on the spin state of the ion as well as the coordination number in the complex. The results highlight the flexibility of EDTA in accepting a large range of metal cations in its binding site.
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BACKGROUND: Colonization of near-patient surfaces in hospitals plays an important role as a source of healthcare-associated infections. Routine disinfection methods only result in short-term elimination of pathogens. AIM: To investigate the efficiency of a newly developed antimicrobial coating containing nanosilver in long-term reduction of bacterial burden in hospital surfaces to close the gap between routine disinfection cycles. METHODS: In this prospective, double-blinded trial, frequently touched surfaces of a routinely used treatment room in an emergency unit of a level-I hospital were treated with a surface coating (nanosilver/DCOIT-coated surface, NCS) containing nanosilver particles and another organic biocidal agent (4,5-dichloro-2-octyl-4-isothiazolin-3-one, DCOIT), whereas surfaces of another room were treated with a coating missing both the nanosilver- and DCOIT-containing ingredient and served as control. Bacterial contamination of the surfaces was examined using contact plates and liquid-based swabs daily for a total trial duration of 90 days. After incubation, total microbial counts and species were assessed. FINDINGS: In a total of 2880 antimicrobial samples, a significant reduction of the overall bacterial load was observed in the NCS room (median: 0.31 cfu/cm2; interquartile range: 0.00-1.13) compared with the control coated surfaces (0.69 cfu/cm2; 0.06-2.00; P < 0.001). The nanosilver- and DCOIT-containing surface coating reduced the relative risk of a critical bacterial load (defined as >5 cfu/cm2) by 60% (odds ratio 0.38, P < 0.001). No significant difference in species distribution was detected between NCS and control group. CONCLUSION: Nanosilver-/DCOIT-containing surface coating has shown efficiency for sustainable reduction of bacterial load of frequently touched surfaces in a clinical setting.