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Conjugated donor-acceptor copolymers hold great potential as materials for high-performance organic photovoltaics, organic transistors and organic thermoelectric devices. Their low optical bandgap is achieved by alternation of donor and acceptor moieties along the polymer chain, leading to a pronounced charge-transfer character of electronic excitations. However, the influence of appended side chains and of chemical defects of the backbone on their photophysical and conformational properties remains largely unexplored on the level of individual chains. Here, we employ room temperature single-molecule photoluminescence spectroscopy on four compounds based on the prototypical copolymer PCDTBT with systematically changed chemical structure. Our results show that an increasing density of statistically added hexyl chains to the TBT comonomer distorts the molecular conformation, likely through the increase of average dihedral angles along the backbone. We find that, although the conformation becomes more twisted with high hexyl density, the side chains appear to stabilize the backbone in this twisted conformation. In addition, we demonstrate that homocoupling defects along the backbone barely influence the PL spectra of single chains, and thus intra-chain electronic properties.
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INTRODUCTION: Chronic knee pain is defined as pain that persists or recurs over 3 months. The most common is degenerative osteoarthritis (OA). This review represents a comprehensive description of the pathology, diagnosis, and treatment of OA of the knee. METHODS: The literature on the diagnosis and treatment of chronic knee pain was retrieved and summarized. A modified Delphi approach was used to formulate recommendations on interventional treatments. RESULTS: Patients with knee OA commonly present with insidious, chronic knee pain that gradually worsens. Pain caused by knee OA is predominantly nociceptive pain, with occasional nociplastic and infrequent neuropathic characteristics occurring in a diseased knee. A standard musculoskeletal and neurological examination is required for the diagnosis of knee OA. Although typical clinical OA findings are sufficient for diagnosis, medical imaging may be performed to improve specificity. The differential diagnosis should exclude other causes of knee pain including bone and joint disorders such as rheumatoid arthritis, spondylo- and other arthropathies, and infections. When conservative treatment fails, intra-articular injections of corticosteroids and radiofrequency (conventional and cooled) of the genicular nerves have been shown to be effective. Hyaluronic acid infiltrations are conditionally recommended. Platelet-rich plasma infiltrations, chemical ablation of genicular nerves, and neurostimulation have, at the moment, not enough evidence and can be considered in a study setting. The decision to perform joint-preserving and joint-replacement options should be made multidisciplinary. CONCLUSIONS: When conservative measures fail to provide satisfactory pain relief, a multidisciplinary approach is recommended including psychological therapy, integrative treatments, and procedural options such as intra-articular injections, radiofrequency ablation, and surgery.
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Sterically distorted donor-acceptor psystems, termed DA springs, can be progressively planarized under mechanical load causing a bathochromic shift of the photoluminescence (PL) spectrum. By combining theory and experiment, we here use a simple linear force calibration for two different conformational mechanochromophores to determine molecular forces in polymers from the mechanochromic shift in PL wavelength during multiple uniaxial tensile tests. Two systems are used, i) a highly entangled linear glassy polyphenylene and ii) a covalent elastomeric polydimethylsiloxane network. The mean forces estimated by this method are validated using known threshold forces for the mechanochemical ring-opening reactions of two different spiropyran force probes. The agreement between both approaches underlines that these DA springs provide the unique opportunity for the online monitoring of local molecular forces present in diverse polymer matrices.
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Efficient organic electronic devices are fabricated from both small molecules and disperse polymers, but materials with characteristics in between remain largely unexplored. Here, we present a gram-scale synthesis for a series of discrete n-type oligomers comprising alternating naphthalene diimide (NDI) and bithiophene (T2). Using C-H activation, discrete oligomers of type T2-(NDI-T2)n (n ≤ 7) and persistence lengths up to â¼10 nm are made. The absence of protection/deprotection reactions and the mechanistic nature of Pd-catalyzed C-H activation allow one to produce symmetrically terminated species almost exclusively, which is key to the fast preparation, high yields, and the general success of the reaction pathway. The reaction scope includes different thiophene-based monomers, end-capping to yield NDI-(T2-NDI)n (n ≤ 8), and branching at T2 units by nonselective C-H activation under certain conditions. We show how the optical, electronic, thermal, and structural properties depend on oligomer length along with a comparison to the disperse, polymeric analogue PNDIT2. From theory and experiments, we find that the molecular energy levels are not affected by chain length resulting from the strong donor-acceptor system. Absorption maxima saturate for n = 4 in vacuum and for n = 8 in solution. Linear oligomers T2-(NDI-T2)n are highly crystalline with large melting enthalpies up to 33 J/g; NDI-terminated oligomers show reduced crystallinity, stronger supercooling, and more phase transitions. Branched oligomers and those with bulky thiophene comonomers are amorphous. Large oligomers exhibit similar packing characteristics compared to PNDIT2, making these oligomers ideal models to study length-structure-function relationships at constant energy levels.
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Inverse vulcanization is a promising route to stabilize sulfur in lithium-sulfur batteries, but the resulting sulfur strand lengths in the materials are elusive. We address the strand length by characterization via sulfur near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Theoretical predictions of NEXAFS spectra for model molecules containing strands with up to three sulfur atoms are verified by experiment. The near perfect agreement between simulation and experiment on the absolute energy scale allows for the predictions for larger chain lengths also. Inspection and interpretation of NEXAFS spectra from real battery materials on this basis reveals the appearance of single connecting sulfur atoms for very low sulfur content, and of longer strands when the sulfur fraction increases.
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PURPOSE: To develop a quick and cost-effective alternative to a chandelier light for vitrectomy. METHODS: The surgical material available in an ophthalmologic operating room was used to create a sleeve for the vitrectomy light probe and tested on 30 consecutive retinal detachment cases for feasibility. RESULTS: A 64 × 5-mm cotton swab stick was cut into the length of the light probe minus the length of the trocar and subsequently pierced by a blunt needle. With this sleeve, the light probe could be safely handled similar to a chandelier light during surgery. CONCLUSION: A sleeve for the light probe can serve as a substitute for a chandelier light during scleral depression in retinal detachment surgery.
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Descolamento Retiniano , Humanos , Descolamento Retiniano/cirurgia , Acuidade Visual , Retina/cirurgia , Vitrectomia , Recurvamento da Esclera , Resultado do TratamentoRESUMO
Mechanochromophores based on conformational changes of donor-acceptor-donor (DAD) springs allow sensing of forces acting on polymer chains by monotonic changes of absorbance or photoluminescence (PL) wavelength. Here, we identify a series of thiophene (D)-flanked quinoxalines (A) as molecular torsional springs for force sensing in bulk polymers at room temperature. The mode of DAD linkage to the polymer matrix and linker rigidity are key parameters that influence the efficacy of force transduction to the DAD spring and thus mechanochromic response, as probed by in situ PL spectroscopy of bulk films during stress-strain experiments. The largest shift of the PL maximum, and thus the highest sensitivity, is obtained from an ansa-DAD spring exhibiting bridged D units and a stiff A linker. Using detailed spectroscopy and density functional theory calculations, we reveal conformer redistribution in the form of a thiophene ring flip as the major part of the overall mechanochromic response. At forces as low as 27 pN at early stages of deformation, the ring flip precedes mechanically induced planarization of the ansa-DAD spring, the latter process producing a PL shift of 21 nm nN-1. Within the stress-strain diagram, the thiophene ring flip and DAD planarization are thus two separated processes that also cause irreversible and reversible mechanochromic responses, respectively, upon sample failure. As the thiophene ring flip requires much smaller forces than planarization of the DAD spring, such micromechanical motion gives access to sensing of tiny forces and expands both sensitivity and the force range of conformational mechanochromophores.
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TiofenosRESUMO
Peatlands ecosystem is one of the largest global terrestrial carbon pools. However, there is a shortness of its characterisation and information through new proximal sensing approaches. The visible and near-infrared spectroscopy is an inexpensive, quick, non-evasive, proximal sensing and low-cost analysis employed in field and/or laboratory. Despite that, there is another current issue in using this tool for creating global models, which is how it can retrieve local characteristics such as soil organic carbon (SOC) and total nitrogen (TN) in peatlands ecosystems. The aims in this study were to: (i) create a local model for quantifying SOC and TN finding the best pre-processing and machine learning methods in peatlands ecosystem, and (ii) evaluate the contribution of SOC and TN data collected in that ecosystem to global models in European Union. The hypothesis was that the SOC and TN data sampled in peatlands ecosystem can improve analytical quantification of those soil properties. The soil and spectral datasets were retrieved from the Land Use/Cover Area frame Statistical Survey with 21,771 observations at 0-20 cm depth and 63 soil cores in a degraded peatland in Germany with 262 observations up to 2 m depth. We evaluated three spectral pre-processing techniques with the Partial Least Square Regression (PLSR), Random Forest (RF), and Cubist machine learning algorithms. The best pre-processing technique was achieved applying Savitzky-Golay smoothing with a window size of 71 points, 2nd order polynomial, and zero derivative with Cubist algorithm for both SOC and TN predictions. Furthermore, merging the local with global data for global modelling demonstrated to improve SOC and TN predictions because of the local data representativeness and quality. Therefore, the SOC and TN data sampled in peatlands ecosystem can improve quantification of those soil properties in field and laboratory, which are crucial proxies for GHG emissions and climate change.
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Carbono , Solo , Carbono/química , Ecossistema , Nitrogênio/análise , Solo/química , Espectroscopia de Luz Próxima ao Infravermelho/métodosRESUMO
Spiropyran (SP) derivatives can be converted into the colored merocyanine (MC) form using a variety of triggers. Optical switching by light for memories and dynamic systems is long known. Recently, mechanical force has been reported as an additional stimulus that converts SP into MC. SP-based mechanochromic systems are especially interesting for polymer scientists, as the covalent attachment of polymer chains is ideal to transduce force to the SP level. Whether such materials are investigated to better understand fundamental processes or long standing questions in polymer science, to design force sensors or to self-report damage, or simply pose fascinating materials which turn colored upon deformation, they have intrigued polymer scientists for more than a decade. With the chemistry of SPs being feasible and SP functionalization important to modulate SP/MC equilibria, a significant amount of work on SP structure- mechanochromic function relations has accumulated. SPs can be used as bifunctional initiators, cross-linkers, monomers, or be synthesized during polymerization. This feature article provides an overview of how the chemistry used sets the boundaries within which the mechanochromic response of SP containing polymers can be modulated.
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Benzopiranos , Indóis , Humanos , NitrocompostosRESUMO
The backbone conformation of conjugated polymers affects, to a large extent, their optical and electronic properties. The usually flexible substituents provide solubility and influence the packing behavior of conjugated polymers in films or in bad solvents. However, the role of the side chains in determining and potentially controlling the backbone conformation, and thus the optical and electronic properties on the single polymer level, is currently under debate. Here, we investigate directly the impact of the side chains by studying the bulky-substituted poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT) and the common poly(3-hexylthiophene) (P3HT), both with a defined molecular weight and high regioregularity, using low-temperature single-chain photoluminescence (PL) spectroscopy and quantum-classical simulations. Surprisingly, the optical transition energy of PDOPT is significantly (â¼2,000 cm-1 or 0.25 eV) red-shifted relative to P3HT despite a higher static and dynamic disorder in the former. We ascribe this red shift to a side-chain induced backbone planarization in PDOPT, supported by temperature-dependent ensemble PL spectroscopy. Our atomistic simulations reveal that the bulkier 2,5-dioctylphenyl side chains of PDOPT adopt a clear secondary helical structural motif and thus protect conjugation, i.e., enforce backbone planarity, whereas, for P3HT, this is not the case. These different degrees of planarity in both thiophenes do not result in different conjugation lengths, which we found to be similar. It is rather the stronger electronic coupling between the repeating units in the more planar PDOPT which gives rise to the observed spectral red shift as well as to a reduced calculated electron-hole polarization.
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We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C-N isomerization reactions. The isomerized compounds are excellent ligands for CoII â centers. Strong agostic interactions with the "C-H"-groups of the cyclohexyl substituents result in an unusual low-spin square planar CoII â complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral CoII â center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these CoII complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands.
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Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor:acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant. Here, we establish that common p-dopants can in fact accept two electrons per molecule from conjugated polymers with a low ionization energy. Each dopant molecule participates in two charge-transfer events, leading to the formation of dopant dianions and an ionization efficiency of up to 200%. Furthermore, we show that the resulting integer charge-transfer complex can dissociate with an efficiency of up to 170%. The concept of double doping introduced here may allow the dopant fraction required to optimize charge conduction to be halved.
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Balanced charge transport is particularly important for transistors. Hence, ambipolar organic semiconductors with comparable transport capabilities for both positive and negative charges are highly sought-after. Here, we report detailed insights into the electronic structure of PNDITBT, which is an alternating copolymer of naphthalene diimide (NDI), thiophene, benzothiodiazole (B), and thiophene (T) units, as gained by time-resolved electron paramagnetic resonance (TREPR) spectroscopy combined with quantum-chemical calculations. The results are compared to those obtained for PNDIT2 and PCDTBT, which are derivatives without B and NDI acceptor units, respectively. These two polymers show dominant n- and p-channel behavior in organic field-effect transistors. The TBT moiety clearly dominates the electronic structure of PNDITBT, although less so than in PCDTBT. Furthermore, the triplet exciton most probably delocalizes along the backbone, exhibits a highly homogeneous environment, and planarizes the polymer backbone. Obtaining the zero-field splitting tensors of these triplet states by means of quantum-chemical calculations reveals the triplet energy sublevel associated with the molecular axis parallel to the backbone to be preferentially populated, while the one perpendicular to the aromatic plane is not populated at all, consistent with the spin-density distribution. PNDITBT consisting of two acceptors (NDI and B) has a complex electronic structure, as evident from the two charge-transfer bands in its absorption spectrum. TREPR spectroscopy provides a detailed insight on a molecular level not available by and complementing other methods.
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The high-mobility n-type donor/acceptor polymer PNDIT2 is well-known to form aggregates in solution depending on the solvent used. To gain additional insight into this process, we probed the local environment of triplet excitons in two different solvents and with two different polymer chain lengths using time-resolved electron paramagnetic resonance (TREPR) spectroscopy. Results clearly show aggregation to introduce a high degree of local order in the polymer and to dramatically enhance the delocalisation of the exciton. Furthermore, triplet exciton delocalisation is only affected by the solvent used and hence by aggregate formation, not by chain length. Finally, aggregation changes the mode of delocalisation from intrachain to interchain when forming aggregates, the latter mode dominating as well in thin films. Taken together, TREPR proves to be a valuable tool for investigating aggregation and order in polymers on a molecular length-scale, ideally complementing preceding optical data.
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A simple and high-yielding route to tough polyarylenes of the type poly(meta,meta,para-phenylene) (PmmpP) is developed. PmmpP is tough even in its as-synthesized state which has an intermediate molar mass of Mw ≈60â kg mol-1 and exhibits outstanding mechanical properties at further optimized molecular weight of Mw =96â kg mol-1 , E=0.9â GPa, ϵ=300 %. Statistical copolymers with para,para-spiropyran (SP) are mechanochromic, and the toughness allows mechanochromism to be investigated. Strained samples instantaneously lose color upon force release. DFT calculations show this phenomenon to be caused by the PmmpP matrix that allows build-up of sufficiently large forces to be transduced to SP, and the relatively unstable corresponding merocyanine (MC) form arising from the aromatic co-monomer. MC units covalently incorporated into PmmpP show a drastically reduced half life time of 3.1â s compared to 4.5â h obtained for SP derivatives with common 6-nitro substitution.
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We present herein the synthesis of three new bis(corrolato-ruthenium(III)) complexes containing unsupported Ru-Ru bonds and their characterization in different redox states. The 1 Hâ NMR spectra of the bis(corrolato-ruthenium(III)) complexes displayed "normal" chemical shifts and the compounds proved to be EPR-silent. Crystallographic characterization of the dimers indicated Ru-Ru distances of 2.175â Å, consistent with a triple bond between the two ruthenium centers. All of the synthesized complexes undergo two successive reversible oxidations and a single reversible reduction. A combination of UV/Vis/NIR/EPR spectroelectrochemical studies and DFT calculations established the redox state distributions in these ruthenium-ruthenium-bonded dimers. Whereas reduction of the dimers is metal-based and leads to metal-metal-bonded mixed-valent RuII -RuIII species, one-electron oxidation largely retains the RuIII -RuIII situation with the generation of metal-bound corrolato radicals. The present study thus concerns the first UV/Vis/NIR/EPR spectroelectrochemical characterization and DFT calculations of ruthenium-ruthenium-bonded rotationally ordered corrole dimers. The mean plane separation between the two corrole units in these dimers is around 3.543â Å, which is in close agreement to that in the "special pair" in chlorophyll. Oxidation of these ruthenium-ruthenium-bonded dimers gives rise to two new electronic absorption bands in the NIR region (similar to those of the special pair), which have apparently not been mentioned/observed in earlier reports on ruthenium-ruthenium-bonded corrole dimers. These bands mainly originate from inter-corrole transitions.
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The azide anion is widely used as a ligand in coordination chemistry. Despite its ubiquitous presence, controlled synthesis of azido complexes remains a challenging task. Making use of click-derived tripodal ligands, we present here various coordination motifs of the azido ligands, the formation of which appears to be controlled by the peripheral substituents on the tripodal ligands with otherwise identical structure of the coordination moieties. Thus, the flexible benzyl substituents on the tripodal ligand TBTA led to the formation of the first example of an unsupported and solely µ1,1-azido-bridged dicobalt(II) complex. The more rigid phenyl substituents on the TPTA ligand deliver an unsupported and solely µ1,3-azido-bridged dicobalt(II) complex. Bulky diisopropylphenyl substituents on the TDTA ligand deliver a doubly µ1,1-azido-bridged dicobalt(II) complex. Intriguingly, the mononuclear copper(II) complex [Cu(TBTA)N3]+ is an excellent synthon for generating mixed dinuclear complexes of the form [(TBTA)Co(µ1,1-N3)Cu(TBTA)]3+ or [(TBTA)Cu(µ1,1-N3)Cu(TPTA)]3+, both of which contain a single unsupported µ1,1-N3 as a bridge. To the best of our knowledge, these are also the first examples of mixed dinuclear complexes with a µ1,1-N3 monoazido bridge. All complexes were crystallographically characterized, and selected examples were probed via magnetometry and high-field EPR spectroscopy to elucidate the electronic structures of these complexes and the nature of magnetic coupling in the various azido-bridged complexes. These results thus prove the power of click-tripodal ligands in generating hitherto unknown chemical structures and properties.
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The modification of molecular properties by the use of substituents is a versatile route for molecular design. Here we show for the example of multiresponsive spiropyrans that substituent effects and their correlations can be accurately described by Hammett constants, which in turn can be obtained directly from density functional theory calculations. The internal energetic difference ΔU between the noncolored and the colored form is determined for 63 spiropyran derivatives with substituents at the spiropyran N- and C6-positions, and can be described by only five parameters with an accuracy better than 0.1 eV (9.75 kJ/mol) using Hammett constants. This enables the prediction of ΔU values for other substituents without the need for further calculations nor experiments.
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Drainage has turned peatlands from a carbon sink into one of the world's largest greenhouse gas (GHG) sources from cultivated soils. We analyzed a unique data set (12 peatlands, 48 sites and 122 annual budgets) of mainly unpublished GHG emissions from grasslands on bog and fen peat as well as other soils rich in soil organic carbon (SOC) in Germany. Emissions and environmental variables were measured with identical methods. Site-averaged GHG budgets were surprisingly variable (29.2 ± 17.4 t CO2 -eq. ha-1 yr-1 ) and partially higher than all published data and the IPCC default emission factors for GHG inventories. Generally, CO2 (27.7 ± 17.3 t CO2 ha-1 yr-1 ) dominated the GHG budget. Nitrous oxide (2.3 ± 2.4 kg N2 O-N ha-1 yr-1 ) and methane emissions (30.8 ± 69.8 kg CH4 -C ha-1 yr-1 ) were lower than expected except for CH4 emissions from nutrient-poor acidic sites. At single peatlands, CO2 emissions clearly increased with deeper mean water table depth (WTD), but there was no general dependency of CO2 on WTD for the complete data set. Thus, regionalization of CO2 emissions by WTD only will remain uncertain. WTD dynamics explained some of the differences between peatlands as sites which became very dry during summer showed lower emissions. We introduced the aerated nitrogen stock (Nair ) as a variable combining soil nitrogen stocks with WTD. CO2 increased with Nair across peatlands. Soils with comparatively low SOC concentrations showed as high CO2 emissions as true peat soils because Nair was similar. N2 O emissions were controlled by the WTD dynamics and the nitrogen content of the topsoil. CH4 emissions can be well described by WTD and ponding duration during summer. Our results can help both to improve GHG emission reporting and to prioritize and plan emission reduction measures for peat and similar soils at different scales.