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The use of an angular ligand drives the formation of an irregular Hofmann framework whereby 6-coordinate and rare 5-coordinate FeII species co-exist – the 6-coordinate species show a spin-crossover transition.

The resonance-stabilized 2-methylallyl radical, 2-MA, is considered as a possible intermediate in the formation of polycyclic aromatic hydrocarbons (PAHs) in combustion processes. In this work, we report on its contribution to molecular growth in a high-temperature microreactor and provide mass-selective IR/UV ion dip spectra of the radical, as well as the various jet-cooled reaction products, employing free electron laser radiation in the mid-infrared region. Small (aromatic) hydrocarbons such as fulvene, benzene, styrene, or

Journal of molecular spectroscopy 386, 111629 (2022). doi:10.1016/j.jms.2022.111629, The formation and dissociation mechanisms of polycyclic aromatic hydrocarbons (PAHs) as well as their reactivity with other interstellar molecules are elusive. In this work, we have investigated the electrical discharge chemistry of the PAH naphthalene and acetonitrile, a molecule known to be present in interstellar environments, using a combination of mass-selective IR-UV ion dip spectroscopy with the free electron laser FELIX in the mid-IR frequency region (550 – 1800 cm$^{-1}$), and quantum chemical calculations. In addition to the species known to be produced in the electrical discharge of pure naphthalene, –CH$_3$ and –CN substituted unsaturated hydrocarbons have been identified. Most of them, in particular those containing a nitrogen atom in the molecular framework, such as benzo[7]annulene‐6‐carbonitrile, have a substantial dipole moment and, therefore, can be considered as potential candidates for astronomical searches. Among the species observed, the two isomers 1- and 2-cyanonaphthalene, which have been recently detected in the TMC-1, have been unambiguously identified in our experiment, thus highlighting the use of electrical discharge sources as a valuable tool to produce astronomically relevant species., Published by Academic Press, Orlando, Fla.

Frontiers in physics 10, 880793 (2022). doi:10.3389/fphy.2022.880793 special issue: "Electronic and Nuclear Quantum Dynamics of Molecules in Intense Laser Fields", We report on the use of extreme ultraviolet (XUV, 30.3 nm) radiation from the Free-electron LASer in Hamburg (FLASH) and visible (Vis, 405 nm) photons from an optical laser to investigate the relaxation and fragmentation dynamics of fluorene ions. The ultrashort laser pulses allow to resolve the molecular processes occurring on the femtosecond timescales. Fluorene is a prototypical small polycyclic aromatic hydrocarbon (PAH). Through their infrared emission signature, PAHs have been shown to be ubiquitous in the universe, and they are assumed to play an important role in the chemistry of the interstellar medium. Our experiments track the ionization and dissociative ionization products of fluorene through time-of-flight mass spectrometry and velocity-map imaging. Multiple processes involved in the formation of each of the fragment ions are disentangled through analysis of the ion images. The relaxation lifetimes of the excited fluorene monocation and dication obtained through the fragment formation channels are reported to be in the range of a few tens of femtoseconds to a few picoseconds., Published by Frontiers Media, Lausanne

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Isolated 2-phenylallyl radicals (2-PA), C 9 H 9 , generated by pyrolysis from a nitrite precursor, have been investigated by IR/UV ion dip spectroscopy using free electron laser radiation. 2-PA is a resonance-stabilized radical that is considered to be involved in the formation of polycyclic aromatic hydrocarbons (PAH) in combustion, but also in interstellar space. The radical is identified based on its gas-phase IR spectrum. Furthermore, a number of bimolecular reaction products are identified, showing that the self-reaction as well as reactions with unimolecular decomposition products of 2-PA form several PAH efficiently. Possible mechanisms are discussed and the chemistry of 2-PA is compared with the one of the related 2-methylallyl and phenylpropargyl radicals.

The large numbers of 3,4-methylenedioxy-N-methylamphetamine (MDMA) formulations encountered by the police and border security necessitates the need for safe, rapid and reliable tests to be performed on-site. Near-infrared (NIR) spectroscopy is a promising technique for on-scene illicit-drug detection because of its rapid analysis, non-invasive nature, broad scope to detect various substances, and small-sized sensors suitable for portable operation. The NIR spectrum of MDMA shows an intriguing, intense peak at ∼2000 nm that was found characteristic for MDMA within a large set of drugs and drug-related substances. Herein, we show that this peak can be attributed to water molecules of crystallization in the MDMA lattice. Drying experiments showed that both an anhydrous and hydrated form of MDMA·HCl exists with significantly different NIR spectra. At ambient conditions, the anhydrous form converted back to the hydrated form within 2 months. Our data analysis model was able to identify MDMA·HCl in mixtures of both forms. Assessment of seized casework materials showed that the majority of MDMA·HCl in The Netherlands is of the hydrated type. This is explained by the use of water-containing concentrated hydrochloric acid in the final conversion step of MDMA-base to the hydrochloride salt in clandestine laboratories. These findings provide insight in the challenges associated with NIR-based identification of drugs that may appear in various crystalline forms. Awareness on the existence of these forms and the consequences of library and data-model design to cope with this phenomenon will increase the robustness of on-site NIR-based drug detection.

The intensity ratio of the 11.2/3.3 µm emission bands is considered to be a reliable tracer of the size distribution of polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM)....

We investigate the gas-phase structure of the neutral pentaalanine peptide. The IR spectrum in the 340-1820 cm-1 frequency range is obtained by employing supersonic jet cooling, infrared multiphoton dissociation, and vacuum-ultraviolet action spectroscopy. Comparison with quantum chemical spectral calculations suggests that the molecule assumes multiple stable conformations, mainly of two structure types. In the most stable conformation theoretically found, the N-terminus forms a C5 ring and the backbone resembles that of an 310-helix with two beta-turns. Additionally, the conformational preferences of pentaalanine have been evaluated using Born-Oppenheimer molecular dynamics, showing that a nonzero simulation time step causes a systematic frequency shift. Funding Agencies|Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO); Swedish Research Council [2019-04439]

Uronic acids are carbohydrates carrying a terminal carboxylic acid and have a unique reactivity in stereoselective glycosylation reactions. Herein, the competing intramolecular stabilization of uronic acid cations by the C-5 carboxylic acid or the C-4 acetyl group was studied with infrared ion spectroscopy (IRIS). IRIS reveals that a mixture of bridged ions is formed, in which the mixture is driven towards the C-1,C-5 dioxolanium ion when the C-5,C-2-relationship is cis, and towards the formation of the C-1,C-4 dioxepanium ion when this relation is trans. Isomer-population analysis and interconversion barrier computations show that the two bridged structures are not in dynamic equilibrium and that their ratio parallels the density functional theory computed stability of the structures. These studies reveal how the intrinsic interplay of the different functional groups influences the formation of the different regioisomeric products.

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.

By preventing hypoxia and hypercapnia, advanced airway management can save lives among patients with traumatic brain injury. During endotracheal intubation (ETI), tracheal stimulation causes an increase in intracranial pressure (ICP), which may impair brain perfusion. It has been suggested that intravenous lidocaine might attenuate this ICP response. We hypothesized that adding lidocaine to the standard induction medication for general anesthesia might reduce the ICP response to ETI. Here, we measured the optical nerve sheath diameter (ONSD) as a correlate of ICP and evaluated the effect of intravenous lidocaine on ONSD during and after ETI in patients undergoing anesthesia.This double-blinded, randomized placebo-controlled trial included 60 patients with American Society of Anesthesiologists I or II physical status that were scheduled for elective surgery under general anesthesia. In addition to the standard anesthesia medication, 30 subjects received 1.5 mg/kg 1% lidocaine (0.15 ml/kg, ONSDlidocaine) and 30 received 0.15 ml/kg 0.9% NaCl (ONSDplacebo). ONSDs were measured with ultrasound on the left eye, before (T0), during (T1), and 4 times after ETI (T2-5 at 5-min intervals).Compared to placebo, lidocaine did not significantly affect the baseline ONSD after anesthesia induction measured at T0. During ETI, the ONSDlidocaine was significantly smaller (β=-0.24 mm P=0.022) than the ONSDplacebo. At T4 and T5, the ONSDplacebo increased steadily, up to 20 min after ETI, but the ONSDlidocaine tended to return to baseline levels.We found that the ONSD was distended during and after ETI in anesthetized patients, and intravenous lidocaine attenuated this effect.

Deze juridische analyse gaat over de positie van zeevarende die woonachtig of afkomstig zijn uit Oekraïne die in dienst van Nederlandse reders of werkzaam zijn aan boord van Nederlandse zeeschepen (Oekraïense zeevarenden).

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.

Shape-changing mechanical metamaterials have drawn the attention of researchers toward the development of continuous-range tunable frequency selective surfaces (FSSs). In this paper, a novel tunable FSS utilizing an origami-inspired “eggbox” structure is presented featuring four-degrees of freedom that can change the frequency response of two orthogonal linear polarizations. The centrosymmetric “eggbox” structure can be folded or rotated along two axes that lead to unprecedented reconfigurability compared to traditional Miura-Ori-based structures which have fewer degrees of control. The utilized cross-shaped dipole FSS element shows enhanced bandwidth, support for orthogonal linear polarization, and ease of fabrication. The prototype is fabricated using a low-cost fully additive inkjet printing process with silver nanoparticle conductive ink. The outcome of this study shows a 25% frequency tunable range over two polarization directions. The design can be an ideal spatial filtering candidate for advanced ultra-wideband terrestrial and space applications.

Simple SummaryNear-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, PDGFR alpha, 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, PDGFR alpha, and CD40. Promising biomarkers in common and aggressive STS subtypes are TEM1 for myxofibrosarcoma, TEM1, and PDGFR alpha for undifferentiated soft tissue sarcoma and EGFR for synovial sarcoma.

Physical chemistry, chemical physics 23(16), 9721 - 9732 (2021). doi:10.1039/D1CP00898F, We report on the noncovalent intermolecular interactions established between the polycyclic aromatic hydrocarbons phenanthrene and phenanthridine with water. Such noncovalent interactions involving extended aromatic systems and water molecules are ubiquitous in a variety of chemical and biological systems. Our study provides spectroscopic results on simple model systems to understand the impact that an extended aromatic surface and the presence of a heteroatom have on the nature of the noncovalent interactions established with the solvent. Microhydrated phenanthrene and phenanthridine clusters with up to three water molecules have been observed and unambiguously characterised by means of broadband rotational spectroscopy and quantum chemical calculations. The presence of a nitrogen atom in the backbone of phenanthridine remarkably affects the geometries of the water clusters and the interaction networks at play, with O–H⋯N and C–H⋯O interactions becoming preferred in the phenanthridine–water clusters over the O–H⋯π interactions seen in the phenanthrene–water clusters. The presence of this heteroatom induces nuclear quadrupole coupling, which was used to understand the cooperativity effects found with increasing cluster size. Our results provide important insight to draw a more complete picture of the noncovalent interactions involving solvent molecules and aromatic systems larger than benzene, and they can be significant to enhance our understanding of the aromatic–polar interactions at play in a myriad of chemical and biological contexts., Published by RSC Publ., Cambridge

Infrared signatures of polycyclic aromatic hydrocarbons (PAHs) are detected towards many phases of stellar evolution. PAHs are major players in the carbon chemistry of the interstellar medium, forming the connection between small hydrocarbons and large fullerenes. However, as details on the formation of PAHs in these environments are still unclear, modeling their abundance and chemistry has remained far from trivial. By combining molecular beam mass-selective IR spectroscopy and calculated IR spectra, we analyze the discharge of benzene and identify resulting products including larger PAHs, radicals and intermediates that serve as promising candidates for radio astronomical searches. The identification of various reaction products indicates that different gas-phase reaction mechanisms leading to PAH growth must occur under the same conditions to account for all observed PAH-related species, thereby revealing the complex and interconnected network of PAH formation pathways. The results of this study highlight key (exothermic) reactions that need to be included in astrochemical models describing the carbon chemistry in our universe.

A high-power fully-digital Doherty transmitter (DDTX) is proposed. It features two segmented LDMOS output switch banks implemented in a custom V T -down-shifted LDMOS technology. A 40 nm CMOS controller digitally activates the individual LDMOS gate segments of the output stage at RF speed. An inverted Doherty power combiner is proposed that features non-short circuited 2 nd harmonic conditions for the main and peak switch banks to boost the RF bandwidth. To guarantee smooth output power and efficiency vs. frequency, a 2 nd harmonic trap is introduced in the power combiner, yielding an RF bandwidth of > 400 MHz. The realized demonstrator can achieve over 39 W peak output power. Its highest drain and system efficiencies, respectively 60 % and 57 %, were found at 34.2 W of output power, while in power back-off its peak drain and system efficiencies are 52 % and 48 % respectively. Over a 25 dB output range, the system efficiency is within 4 percent points of the drain efficiency.

Klimaat en klimaatverandering hebben invloed op onze gezondheid, zowel positief als negatief. Mensen kunnen bijvoorbeeld overlijden tijdens een hittegolf of huidkanker krijgen door blootstelling aan UVstraling. Maar over de invloed van klimaatverandering op onze fysieke en mentale gezondheid is ook nog veel onduidelijk. We ervaren nu al de gevolgen van klimaatverandering en daarom is het belangrijk om meer kennis te krijgen over de gezondheidsrisico’s van klimaatverandering. Het ministerie van VWS heeft daarom het RIVM gevraagd de gezondheidseffecten van klimaatverandering en de samenhang daartussen te onderzoeken. Als eerste stap daarin heeft het RIVM een Plan van Aanpak opgesteld, met een overzicht van de onderzoeksvragen die hierover bestaan. Het gaat om vragen over allergie, mentale gezondheid, infectieziekten, UV-straling en huidkanker, temperatuur en luchtkwaliteit. Deze vragen vormen de basis voor het onderzoeksprogramma van de komende jaren. Het overzicht maakt duidelijk op welke gebieden kennis ontbreekt over klimaatverandering en de gezondheidseffecten. Om een goed zicht te krijgen op gezondheidseffecten van klimaatverandering, is het belangrijk de effecten in samenhang te onderzoeken. Samenhang is belangrijk om effectieve maatregelen te kunnen nemen en te weten welke maatregelen op korte termijn nodig zijn. Zo is het belangrijk te weten of mensen sterven aan hitte, aan te veel ozon, of aan de combinatie van beide tijdens perioden van hitte. Samenhang voorkomt ook dat onderzoeken overlappen of elkaar tegenwerken. Verder is nog veel onbekend over de omvang van gezondheidseffecten die door klimaatverandering kunnen ontstaan of erger worden. Zo is niet bekend hoeveel mensen allergisch zijn voor pollen en hoeveel last ze daarvan hebben, laat staan wat het effect van klimaatverandering daarop is. Het onderzoek gaat vooral over de lichamelijke effecten van klimaatverandering, maar heeft voor het eerst ook aandacht voor mentale effecten. Bijvoorbeeld voor stress door overstromingen, zowel direct na de gebeurtenis als op de lange termijn. Bijvoorbeeld door angst voor herhaling of door financiële zorgen.