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1.
Proc Natl Acad Sci U S A ; 120(39): e2307049120, 2023 Sep 26.
Article in English | MEDLINE | ID: mdl-37725646

ABSTRACT

The dynamics of lattice vibrations govern many material processes, such as acoustic wave propagation, displacive phase transitions, and ballistic thermal transport. The maximum velocity of these processes and their effects is determined by the speed of sound, which therefore defines the temporal resolution (picoseconds) needed to resolve these phenomena on their characteristic length scales (nanometers). Here, we present an X-ray microscope capable of imaging acoustic waves with subpicosecond resolution within mm-sized crystals. We directly visualize the generation, propagation, branching, and energy dissipation of longitudinal and transverse acoustic waves in diamond, demonstrating how mechanical energy thermalizes from picosecond to microsecond timescales. Bulk characterization techniques capable of resolving this level of structural detail have previously been available on millisecond time scales-orders of magnitude too slow to capture these fundamental phenomena in solid-state physics and geoscience. As such, the reported results provide broad insights into the interaction of acoustic waves with the structure of materials, and the availability of ultrafast time-resolved dark-field X-ray microscopy opens a vista of new opportunities for 3D imaging of materials dynamics on their intrinsic submicrosecond time scales.

2.
PLoS Biol ; 20(8): e3001707, 2022 08.
Article in English | MEDLINE | ID: mdl-36040953

ABSTRACT

Hunting and its impacts on wildlife are typically studied regionally, with a particular focus on the Global South. Hunting can, however, also undermine rewilding efforts or threaten wildlife in the Global North. Little is known about how hunting manifests under varying socioeconomic and ecological contexts across the Global South and North. Herein, we examined differences and commonalities in hunting characteristics across an exemplary Global South-North gradient approximated by the Human Development Index (HDI) using face-to-face interviews with 114 protected area (PA) managers in 25 African and European countries. Generally, we observed that hunting ranges from the illegal, economically motivated, and unsustainable hunting of herbivores in the South to the legal, socially and ecologically motivated hunting of ungulates within parks and the illegal hunting of mainly predators outside parks in the North. Commonalities across this Africa-Europe South-North gradient included increased conflict-related killings in human-dominated landscapes and decreased illegal hunting with beneficial community conditions, such as mutual trust resulting from community involvement in PA management. Nevertheless, local conditions cannot outweigh the strong effect of the HDI on unsustainable hunting. Our findings highlight regional challenges that require collaborative, integrative efforts in wildlife conservation across actors, while identified commonalities may outline universal mechanisms for achieving this goal.


Subject(s)
Animals, Wild , Conservation of Natural Resources , Africa , Animals , Europe , Humans , Hunting , Mammals
3.
J Am Chem Soc ; 146(20): 13962-13973, 2024 May 22.
Article in English | MEDLINE | ID: mdl-38727611

ABSTRACT

Dimeric complexes composed of d8 square planar metal centers and rigid bridging ligands provide model systems to understand the interplay between attractive dispersion forces and steric strain in order to assist the development of reliable methods to model metal dimer complexes more broadly. [Ir2 (dimen)4]2+ (dimen = para-diisocyanomenthane) presents a unique case study for such phenomena, as distortions of the optimal structure of a ligand with limited conformational flexibility counteract the attractive dispersive forces from the metal and ligand to yield a complex with two ground state deformational isomers. Here, we use ultrafast X-ray solution scattering (XSS) and optical transient absorption spectroscopy (OTAS) to reveal the nature of the equilibrium distribution and the exchange rate between the deformational isomers. The two ground state isomers have spectrally distinct electronic excitations that enable the selective excitation of one isomer or the other using a femtosecond duration pulse of visible light. We then track the dynamics of the nonequilibrium depletion of the electronic ground state population─often termed the ground state hole─with ultrafast XSS and OTAS, revealing a restoration of the ground state equilibrium in 2.3 ps. This combined experimental and theoretical study provides a critical test of various density functional approximations in the description of bridged d8-d8 metal complexes. The results show that density functional theory calculations can reproduce the primary experimental observations if dispersion interactions are added, and a hybrid functional, which includes exact exchange, is used.

4.
Parasitology ; : 1-8, 2024 Apr 17.
Article in English | MEDLINE | ID: mdl-38629125

ABSTRACT

Equine strongylid parasites are ubiquitous around the world and are main targets of parasite control programmes. In recent years, automated fecal egg counting systems based on image analysis have become available allowing for collection and analysis of large-scale egg count data. This study aimed to evaluate equine strongylid fecal egg count (FEC) data generated with an automated system over three years in the US with specific attention to seasonal and regional trends in egg count magnitude and sampling activity. Five US regions were defined; North East, South East, North Central, South Central and West. The data set included state, region and zip code for each FEC. The number of FECs falling in each of the following categories were recorded: (1) 0 eggs per gram (EPG), (2) 1 ⩽ 200 EPG, (3) 201 ⩽ 500 EPG and (4) >500 EPG. The data included 58 329 FECs. A fixed effects model was constructed fitting the number of samples analysed per month, year and region, and a mixed effects model was constructed to fit the number of FECs falling in each of the 4 egg count categories defined above. The overall proportion of horses responsible for 80% of the total FEC output was 18.1%, and this was consistent across years, months and all regions except West, where the proportion was closer to 12%. Statistical analyses showed significant seasonal trends and regional differences of sampling frequency and FEC category. The data demonstrated that veterinarians tended to follow a biphasic pattern when monitoring strongylid FECs in horses, regardless of location.

5.
Acta Anaesthesiol Scand ; 68(2): 254-262, 2024 Feb.
Article in English | MEDLINE | ID: mdl-37800379

ABSTRACT

BACKGROUND: Optimizing pain management following cesarean section is crucial for the well-being of both mother and infant. Various types of quadratus lumborum blocks have exhibited reduced opioid consumption and pain scores after cesarean section. However, duration of block effect is relatively short. The aim of this study was to investigate the analgesic efficacy of the anterior quadratus lumborum catheters for cesarean section. METHODS: All 32 enrolled participants were allocated to postoperative bilateral ultrasound-guided anterior quadratus lumborum catheter placement with injection of 60 mL ropivacaine 0.375% after cesarean section. Randomization at 2 h resulted in either 60 mL ropivacaine 0.2% or 60 mL isotonic saline injected through the catheters, with subsequent 22-h infusion of either ropivacaine 0.2% or isotonic saline with an infusion rate of 4 mL h-1 per catheter. Participants in the active group received a total of 697 mg ropivacaine during the first 24 h. All participants received the standard postoperative multimodal pain regimen, and a final bilateral injection at 24-h post-catheter placement of 60 mL ropivacaine 0.375% in total. The primary outcome was time to first opioid administration. Secondary outcomes were pain scores, time to first ambulation, nausea and vomiting, accumulated opioid consumption, and catheter displacement rates. RESULTS: No significant intergroup differences were observed following the randomized intervention. Median time to first opioid (IQR) was (active vs. placebo) 414 (283, 597) vs. 428 (245, 552) minutes, with a median difference (CI) of -14 (-184 to 262) min, p = .32. CONCLUSION: Bilateral anterior quadratus lumborum catheters with continuous infusion did not prolong time to first opioid after elective cesarean section.


Subject(s)
Analgesics, Opioid , Anesthetics, Local , Humans , Female , Pregnancy , Ropivacaine , Cesarean Section/methods , Pain, Postoperative/prevention & control , Pain, Postoperative/drug therapy , Catheters , Double-Blind Method
6.
BMC Pediatr ; 24(1): 24, 2024 01 08.
Article in English | MEDLINE | ID: mdl-38191332

ABSTRACT

BACKGROUND: A low incidence of eosinophilic esophagitis (EoE) in children in the North Denmark Region (NDR) were measured in 2007-2017. Few of the children diagnosed before 2017 were treated to remission suggesting a lack of awareness. While there currently are no guidelines for treating EoE in Denmark, a new English guideline was published in 2022 renewing focus on the disease. OBJECTIVE: The aim of this study was to measure the difference of current Danish clinical practice for treatment and follow-up of EoE children in the NDR with the new English guideline from the British Society of Gastroenterology (BSG) and the British Society of Pediatric Gastroenterology, Hepatology and Nutrition (BSPGHAN). METHODS: This retrospective, register-based DanEoE cohort study included 31 children diagnosed with EoE between 2007 and 2021 in NDR. Medical records were reviewed and information about treatment and follow-up were collected. RESULTS: In 32% of the children with EoE in the NDR, first-line treatment corresponded with the new English guideline. One in 6 children were never started on any treatment even though treatment always is recommended. Histologic evaluation within 12 weeks as recommended was performed in 13% of the children. CONCLUSIONS: In Denmark focus on improving EoE treatment and follow-up for children is needed, as there is a significant difference between current clinical practice and the recommendations in the new English guideline.


Subject(s)
Eosinophilic Esophagitis , Child , Humans , Eosinophilic Esophagitis/diagnosis , Eosinophilic Esophagitis/therapy , Cohort Studies , Retrospective Studies , Child Nutritional Physiological Phenomena , Denmark
7.
J Am Chem Soc ; 145(10): 5655-5663, 2023 Mar 15.
Article in English | MEDLINE | ID: mdl-36867088

ABSTRACT

High catalytic activities of Ru-PNP [Ru = ruthenium; PNP = bis alkyl- or aryl ethylphosphinoamine complexes in ionic liquids (ILs) were obtained for the reversible hydrogenation of CO2 and dehydrogenation of formic acid (FA) under exceedingly mild conditions and without sacrificial additives. The novel catalytic system relies on the synergic combination of Ru-PNP and IL and proceeds with CO2 hydrogenation already at 25 °C under a continuous flow of 1 bar of CO2/H2 (1:5), leading to 14 mol % FA with respect to the IL. A pressure of 40 bar of CO2/H2 (1:1) provides 126 mol % of FA/IL corresponding to a space-time yield (STY) of FA of 0.15 mol L-1 h-1. The conversion of CO2 contained in imitated biogas was also achieved at 25 °C. Furthermore, the Ru-PNP/IL system catalyzes FA dehydrogenation with average turnover frequencies up to 11,000 h-1 under heat-integrated conditions for proton-exchange membrane fuel cell applications (<100 °C). Thus, 4 mL of a 0.005 M Ru-PNP/IL system converted 14.5 L FA over 4 months with a turnover number exceeding 18,000,000 and a STY of CO2 and H2 of 35.7 mol L-1 h-1. Finally, 13 hydrogenation/dehydrogenation cycles were achieved with no sign of deactivation. These results demonstrate the potential of the Ru-PNP/IL system to serve as a FA/CO2 battery, a H2 releaser, and a hydrogenative CO2 converter.

8.
J Am Chem Soc ; 145(29): 15754-15765, 2023 Jul 26.
Article in English | MEDLINE | ID: mdl-37163700

ABSTRACT

Resolving the structural dynamics of bond breaking, bond formation, and solvation is required for a deeper understanding of solution-phase chemical reactions. In this work, we investigate the photodissociation of triiodide in four solvents using femtosecond time-resolved X-ray solution scattering following 400 nm photoexcitation. Structural analysis of the scattering data resolves the solvent-dependent structural evolution during the bond cleavage, internal rearrangements, solvent-cage escape, and bond reformation in real time. The nature and structure of the reaction intermediates during the recombination are determined, elucidating the full mechanism of photodissociation and recombination on ultrafast time scales. We resolve the structure of the precursor state for recombination as a geminate pair. Further, we determine the size of the solvent cages from the refined structures of the radical pair. The observed structural dynamics present a comprehensive picture of the solvent influence on structure and dynamics of dissociation reactions.

9.
Acta Oncol ; 62(11): 1418-1425, 2023 Nov.
Article in English | MEDLINE | ID: mdl-37703300

ABSTRACT

BACKGROUND: In the Danish Head and Neck Cancer Group (DAHANCA) 35 trial, patients are selected for proton treatment based on simulated reductions of Normal Tissue Complication Probability (NTCP) for proton compared to photon treatment at the referring departments. After inclusion in the trial, immobilization, scanning, contouring and planning are repeated at the national proton centre. The new contours could result in reduced expected NTCP gain of the proton plan, resulting in a loss of validity in the selection process. The present study evaluates if contour consistency can be improved by having access to AI (Artificial Intelligence) based contours. MATERIALS AND METHODS: The 63 patients in the DAHANCA 35 pilot trial had a CT from the local DAHANCA centre and one from the proton centre. A nationally validated convolutional neural network, based on nnU-Net, was used to contour OARs on both scans for each patient. Using deformable image registration, local AI and oncologist contours were transferred to the proton centre scans for comparison. Consistency was calculated with the Dice Similarity Coefficient (DSC) and Mean Surface Distance (MSD), comparing contours from AI to AI and oncologist to oncologist, respectively. Two NTCP models were applied to calculate NTCP for xerostomia and dysphagia. RESULTS: The AI contours showed significantly better consistency than the contours by oncologists. The median and interquartile range of DSC was 0.85 [0.78 - 0.90] and 0.68 [0.51 - 0.80] for AI and oncologist contours, respectively. The median and interquartile range of MSD was 0.9 mm [0.7 - 1.1] mm and 1.9 mm [1.5 - 2.6] mm for AI and oncologist contours, respectively. There was no significant difference in ΔNTCP. CONCLUSIONS: The study showed that OAR contours made by the AI algorithm were more consistent than those made by oncologists. No significant impact on the ΔNTCP calculations could be discerned.


Subject(s)
Artificial Intelligence , Head and Neck Neoplasms , Humans , Organs at Risk , Protons , Radiotherapy Planning, Computer-Assisted/methods
10.
Acta Oncol ; 62(10): 1161-1168, 2023 Oct.
Article in English | MEDLINE | ID: mdl-37850659

ABSTRACT

BACKGROUND: Previously, many radiotherapy (RT) trials were based on a few selected dose measures. Many research questions, however, rely on access to the complete dose information. To support such access, a national RT plan database was created. The system focuses on data security, ease of use, and re-use of data. This article reports on the development and structure, and the functionality and experience of this national database. METHODS AND MATERIALS: A system based on the DICOM-RT standard, DcmCollab, was implemented with direct connections to all Danish RT centres. Data is segregated into any number of collaboration projects. User access to the system is provided through a web interface. The database has a finely defined access permission model to support legal requirements. RESULTS: Currently, data for more than 14,000 patients have been submitted to the system, and more than 50 research projects are registered. The system is used for data collection, trial quality assurance, and audit data set generation.Users reported that the process of submitting data, waiting for it to be processed, and then manually attaching it to a project was resource intensive. This was accommodated with the introduction of triggering features, eliminating much of the need for users to manage data manually. Many other features, including structure name mapping, RT plan viewer, and the Audit Tool were developed based on user input. CONCLUSION: The DcmCollab system has provided an efficient means to collect and access complete datasets for multi-centre RT research. This stands in contrast with previous methods of collecting RT data in multi-centre settings, where only singular data points were manually reported. To accommodate the evolving legal environment, DcmCollab has been defined as a 'data processor', meaning that it is a tool for other research projects to use rather than a research project in and of itself.


Subject(s)
Radiation Oncology , Radiotherapy , Humans , Clinical Trials as Topic
11.
Phys Chem Chem Phys ; 25(35): 23417-23434, 2023 Sep 13.
Article in English | MEDLINE | ID: mdl-37486006

ABSTRACT

We apply ultrashort X-ray laser pulses to track optically excited structural dynamics of [Ir2(dimen)4]2+ molecules in solution. In our exploratory study we determine angular correlations in the scattered X-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles. We unambiguously identify that in our experiment the photoinduced transition dipole moments in [Ir2(dimen)4]2+ molecules are oriented perpendicular to the Ir-Ir bond. The analysis also shows that the ground state conformer of [Ir2(dimen)4]2+ with a larger Ir-Ir distance is mostly responsible for the formation of the excited state. We also reveal that the ensemble of solute molecules can be characterized with a substantial structural heterogeneity due to solvent influence. The proposed X-ray correlation approach offers an alternative path for studies of ultrafast structural dynamics of molecular ensembles in the liquid and gas phases.

12.
Biol Conserv ; 282: 110037, 2023 Jun.
Article in English | MEDLINE | ID: mdl-37056580

ABSTRACT

In many low-income countries, the conservation of natural resources in protected areas relies on tourism revenue. However, tourist numbers in Africa were severely reduced by the COVID-19 pandemic, thus, putting the conservation of these important protected areas at risk. We use records from gate passings at national parks across Tanzania to demonstrate the immediate and severe impact on tourist numbers and revenues resulting from the COVID-19 pandemic and associated restrictions, and whether international and local (East African) tourists were affected equally. We discuss mechanisms that may reduce future negative impacts of sudden loss of revenue from international tourism, such as increasing the revenue portfolio and thereby decrease the dependency on revenues from international tourists. More important, we encourage local governments, national park authorities, and the world community to further develop and initiate external funding options to reduce the dependency on income from international nature-based tourism to preserve national parks and biodiversity. An additional long-term goal for ensuring sustained conservation would be to increase benefits to local communities adjacent to national parks, encouraging local involvement and thereby reducing the dependence on external funding in the future.

13.
Acta Anaesthesiol Scand ; 67(7): 987-992, 2023 08.
Article in English | MEDLINE | ID: mdl-37118985

ABSTRACT

BACKGROUND AND AIMS: Intertransverse process (ITP) blocks are applied on the posterior side of the thoracic paravertebral space. The modality is described as being a paravertebral block by proxy, possibly providing a similar analgesic effect as the thoracic paravertebral block. However, systematic evidence on anaesthetised dermatomes and the extent of cutaneous sensory loss following ITP blocks is sparse. This study aims to test the single- versus the multiple-injection ITP block. The primary outcome is the number of anaesthetised thoracic dermatomes for each block type. METHODS: Twelve healthy male volunteers will participate in this randomised, procedure-related, double-blinded, non-inferiority crossover trial after informed consent. Blinded participants will receive either a unilateral single-injection ITP block with 21 mL ropivacaine 7.5 mg/mL including two sham blocks or a unilateral multiple-injection ITP block with 3 × 7 mL ropivacaine 7.5 mg/mL on study Day 1, and the other modality on study Day 2. Block applicants will be blinded from outcome assessment and vice versa. Following block application sensory test by mechanical pinprick and temperature discrimination will be performed. Anterior truncal thermography will be measured three times after block application to compare skin temperature in the mid-clavicular line between the blocked and the contralateral non-blocked hemithorax. In addition, blood pressure changes are measured three times non-invasively. DISCUSSION: The current study will provide substantial knowledge regarding the cutaneous sensory loss of the ITP block. Furthermore, the study might provide insight regarding the possible clinical usage of thermography as a reliable instrument for measuring nerve block efficacy.


Subject(s)
Nerve Block , Humans , Male , Ropivacaine , Nerve Block/methods , Thorax , Outcome Assessment, Health Care , Anesthetics, Local , Randomized Controlled Trials as Topic
14.
Int Arch Occup Environ Health ; 96(3): 451-462, 2023 Apr.
Article in English | MEDLINE | ID: mdl-36416975

ABSTRACT

PURPOSE: It has been hypothesized that employment in a fixed-term instead of permanent contract position is associated with an increased risk of development of mental health problems. The present study aimed at estimating rate ratios between fixed-term and permanent employees in the Danish labor force, for use of psychotropic drugs and psychiatric hospital treatment due to mood, anxiety or stress-related disorders, respectively. METHODS: Employment data were drawn from the Danish Labor Force Survey of 2001-2013, which is a part of the European Labor Force Survey. Full-time employed survey participants without mental illness at the baseline interview (N = 106,501) were followed in national health registers for up to 5 years. Poisson regressions were used to estimate rate ratios for redeemed prescriptions of psychotropic drugs and psychiatric hospital treatments due to mood, anxiety or stress-related disease. The analyses were controlled for age, gender, industrial sector, nighttime work, level of education, calendar year, disposable family income and social transfer payments within 1 year prior to the baseline interview. RESULTS: The rate ratio for hospital diagnosed mood, anxiety or stress-related disorders among employees with fixed-term vs. permanent employment contracts was estimated at 1.39 (99.5% CI 1.04-1.86), while the corresponding rate ratio for redeemed prescriptions of psychotropic drugs was estimated at 1.12 (99.5% CI 1.01-1.24). CONCLUSION: The present study supports the hypothesis that employment in a fixed-term rather than permanent contract position is associated with an increased risk of developing mental health problems. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): DERR2-10.2196/24392.


Subject(s)
Employment , Mental Disorders , Humans , Cohort Studies , Employment/psychology , Psychotropic Drugs , Denmark
15.
Parasitol Res ; 123(1): 56, 2023 Dec 18.
Article in English | MEDLINE | ID: mdl-38105374

ABSTRACT

The microbiome plays an important role in health, where changes in microbiota composition can have significant downstream effects within the host, and host-microbiota relationships can be exploited to affect health outcomes. Parasitic helminths affect animals globally, but an exploration of their microbiota has been limited, despite the development of anti-Wolbachia drugs to help control infections with some filarial nematodes. The equine ascarids, Parascaris spp., are considered the most pathogenic nematodes affecting juvenile horses and are also the only ascarid parasite to have developed widespread anthelmintic resistance. The aim of this study was to characterize the microbiota of this helminth, focusing on the female gonad, determine a core microbiota for this organ, identify bacterial species, and show bacterial localization to the female gonad via in situ hybridization (ISH). A total of 22 gonads were isolated from female Parascaris spp. collected from three foals, and 9 female parasites were formalin-fixed and paraffin-embedded for ISH. Next-generation sequencing was performed using V3-V4 primers as well as the Swift Amplicon™ 16S+ ITS Panel. Overall, ten genera were identified as members of the Parascaris spp. female gonad and twelve bacterial species were identified. The most prevalent genus was Mycoplasma, followed by Reyranella, and there were no differences in alpha diversity between parasites from different horses. Specific eubacteria staining was identified in both the intestine and within the gonad using ISH. Overall, this study provided in-depth information regarding the female Parascaris spp. microbiota and was the first to identify the core microbiota within a specific parasite organ.


Subject(s)
Ascaridida Infections , Ascaridoidea , Helminths , Horse Diseases , Parasites , Animals , Horses , Female , Ascaridoidea/genetics , Horse Diseases/parasitology , Ascaridida Infections/veterinary , Ascaridida Infections/parasitology , Drug Resistance , Feces/parasitology , Gonads
16.
Z Rheumatol ; 82(2): 143-150, 2023 Mar.
Article in German | MEDLINE | ID: mdl-34825949

ABSTRACT

Mycobacterium haemophilum is a rare pathogen belonging to the group of slowly growing nontuberculous mycobacteria (NTM) that can cause infections, especially in immunocompromised patients. Detection by culturing is difficult because M. haemophilum only grows under special cultivation conditions. Therefore, it is believed that the pathogen is too rarely identified as a cause of disease overall. In addition to patients with severe immunodeficiency, e.g. due to acquired immunodeficiency syndrome (AIDS), chemotherapy or immunosuppression after transplantation, patients with underlying rheumatic diseases are increasingly described in the literature, who are at risk due to the immunosuppressive treatment regimen. Clinically, ulcerative skin alterations, lymphadenopathy and arthropathy are in the foreground. In immunosuppressed patients with unclear skin lesions, infections due to M. haemophilum should be considered and specific microbiological diagnostics should be initiated.


Subject(s)
Mycobacterium Infections, Nontuberculous , Mycobacterium haemophilum , Skin Ulcer , Humans , Mycobacterium Infections, Nontuberculous/diagnosis , Mycobacterium Infections, Nontuberculous/drug therapy , Nontuberculous Mycobacteria , Immunocompromised Host
17.
J Am Chem Soc ; 144(28): 12861-12873, 2022 07 20.
Article in English | MEDLINE | ID: mdl-35776920

ABSTRACT

The ultrafast dynamical response of solute-solvent interactions plays a key role in transition metal complexes, where charge transfer states are ubiquitous. Nonetheless, there exist very few excited-state simulations of transition metal complexes in solution. Here, we carry out a nonadiabatic dynamics study of the iron complex [Fe(CN)4(bpy)]2- (bpy = 2,2'-bipyridine) in explicit aqueous solution. Implicit solvation models were found inadequate for reproducing the strong solvatochromism in the absorption spectra. Instead, direct solute-solvent interactions, in the form of hydrogen bonds, are responsible for the large observed solvatochromic shift and the general dynamical behavior of the complex in water. The simulations reveal an overall intersystem crossing time scale of 0.21 ± 0.01 ps and a strong reliance of this process on nuclear motion. A charge transfer character analysis shows a branched decay mechanism from the initially excited singlet metal-to-ligand charge transfer (1MLCT) states to triplet states of 3MLCT and metal-centered (3MC) character. We also find that solvent reorganization after excitation is ultrafast, on the order of 50 fs around the cyanides and slower around the bpy ligand. In contrast, the nuclear vibrational dynamics, in the form of Fe-ligand bond changes, takes place on slightly longer time scales. We demonstrate that the surprisingly fast solvent reorganizing should be observable in time-resolved X-ray solution scattering experiments, as simulated signals show strong contributions from the solute-solvent scattering cross term. Altogether, the simulations paint a comprehensive picture of the coupled and concurrent electronic, nuclear, and solvent dynamics and interactions in the first hundreds of femtoseconds after excitation.


Subject(s)
Coordination Complexes , Organometallic Compounds , Iron , Ligands , Organometallic Compounds/chemistry , Quantum Theory , Solvents , Water/chemistry
18.
Parasite Immunol ; 44(10): e12941, 2022 10.
Article in English | MEDLINE | ID: mdl-35842816

ABSTRACT

This study aimed to collect information on local and systemic inflammatory responses, and goblet cell-associated components, following anthelmintic treatment with moxidectin and ivermectin in horses naturally infected with cyathostomin parasites. Thirty-six horses aged 2-5 years of age were randomly allocated to three groups. Group 1 received ivermectin/praziquantel (0.2 mg/kg), Group 2 received moxidectin/praziquantel (0.4 mg/kg) and Group 3 were untreated controls. Tissue samples from the Cecum, Dorsal and Ventral Colons were used for histopathological evaluation and preserved for RNA isolation and gene expression analysis. Whole blood was collected weekly for gene expression analysis as well. The control group had significantly higher inflammation associated with higher larval scores. The treatment groups displayed no differences in larval counts and inflammatory cell populations (p > .05). Mucosal larval counts were positively correlated with goblet cell hyperplasia scores (p = .047). The moxidectin-treated group had a significantly lower expression of IFN-γ (p < .05). The data suggest that removal of cyathostomins reduced the pro-inflammatory response associated with cyathostomin infections. Pro-inflammatory reactions associated with anthelmintic treatment were minimal, but lowest for moxidectin-treated horses. Results suggested that cecum, ventral and dorsal colons responded differently to cyathostomin larvae, which may have implications in the disease process.


Subject(s)
Anthelmintics , Horse Diseases , Animals , Anthelmintics/therapeutic use , Feces/parasitology , Horse Diseases/drug therapy , Horse Diseases/parasitology , Horses , Inflammation/drug therapy , Ivermectin/pharmacology , Ivermectin/therapeutic use , Larva , Macrolides , Parasite Egg Count , Praziquantel/therapeutic use
19.
J Org Chem ; 87(8): 5419-5423, 2022 04 15.
Article in English | MEDLINE | ID: mdl-35213167

ABSTRACT

The chemoselective reduction of enamides to α-amino acids with iPrOH and EtOH as H-donors and solvents catalyzed by Ru pincer complexes is demonstrated. A range of α-amino acids is synthesized in good to excellent yields. Applications, large scale, and a one-pot experiment are also reported. Finally, deuterium-labeling experiments show high regioselectivity between the α- and ß-positions of the alkene unit.


Subject(s)
Alkenes , Amino Acids , Alkenes/chemistry , Amino Acids/chemistry , Catalysis , Hydrogenation
20.
Acta Oncol ; 61(2): 120-126, 2022 Feb.
Article in English | MEDLINE | ID: mdl-34979878

ABSTRACT

PURPOSE: The study aimed to investigate the pattern of failure and describe compromises in the definition and coverage of the target for patients treated with curatively intended radiotherapy (RT) for sinonasal cancer (SNC). METHODS AND MATERIAL: Patients treated with curatively intended RT in 2008-2015 in Denmark for SNC were eligible for the retrospective cohort study. Information regarding diagnosis and treatment was retrieved from the national database of the Danish Head and Neck Cancer Group (DAHANCA). Imaging from the diagnosis of recurrences was collected, and the point of origin (PO) of the recurrent tumour was estimated. All treatment plans were collected and reviewed with the focus on target coverage, manual modifications of target volumes, and dose to organs at risk (OARs) above defined constraints. RESULTS: A total of 184 patients were included in the analysis, and 76 (41%) relapsed. The majority of recurrences involved T-site (76%). Recurrence imaging of 39 patients was evaluated, and PO was established. Twenty-nine POs (74%) were located within the CTV, and the minimum dose to the PO was median 64.1 Gy (3.1-70.7). The criteria for target coverage (V95%) was not met in 89/184 (48%) of the CTV and 131/184 (71%) of the PTV. A total of 24% of CTVs had been manually modified to spare OARs of high-dose irradiation. No difference in target volume modifications was observed between patients who suffered recurrence and patients with lasting remission. CONCLUSION: The majority of relapses after radical treatment of SNC were located in the T-site (the primary tumour site). Multiple compromises with regards to target coverage and tolerance levels for OARs in the sinonasal region, as defined from RT guidelines, were taken. No common practice in this respect could be derived from the study.


Subject(s)
Paranasal Sinus Neoplasms , Radiotherapy, Conformal , Radiotherapy, Intensity-Modulated , Denmark/epidemiology , Humans , Neoplasm Recurrence, Local/epidemiology , Neoplasm Recurrence, Local/radiotherapy , Paranasal Sinus Neoplasms/radiotherapy , Radiotherapy Dosage , Radiotherapy Planning, Computer-Assisted , Retrospective Studies
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