Jeppesenbenjamin4302
With 12 crystal forms, 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecabonitrile (a.k.a. ROY) holds the current record for the largest number of fully characterized organic crystal polymorphs. Ac-FLTD-CMK Four of these polymorph structures have been reported since 2019, raising the question of how many more ROY polymorphs await future discovery. Employing crystal structure prediction and accurate energy rankings derived from conformational energy-corrected density functional theory, this study presents the first crystal energy landscape for ROY that agrees well with experiment. The lattice energies suggest that the seven most stable ROY polymorphs (and nine of the twelve lowest-energy forms) on the Z' = 1 landscape have already been discovered experimentally. Discovering any new polymorphs at ambient pressure will likely require specialized crystallization techniques capable of trapping metastable forms. At pressures above 10 GPa, however, a new crystal form is predicted to become enthalpically more stable than all known polymorphs, suggesting that further high-pressure experiments on ROY may be warranted. This work highlights the value of high-accuracy crystal structure prediction for solid-form screening and demonstrates how pragmatic conformational energy corrections can overcome the limitations of conventional density functionals for conformational polymorphs.Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π-π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π-π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units. In CHCl3, both compounds are molecularly dissolved and accordingly poorly emissive due to a torsion-induced non-radiative decay. In methylcyclohexane-rich conditions, these barbiturates self-assemble to form crystalline nanofibers and exhibit strongly enhanced emission through supramolecular polymerization driven by hydrogen-bonding. Our structural analysis suggests that the barbiturates form a tape-like hydrogen-bonding motif, which is rationalized by considering that the twisted geometries of 2,3-diphenylthiophene cores prevend the competing rosettes from stacking into columnar supramolecular polymers. We also found that a small difference in the molecular polarity originating from the substitutional position of the thiophene core influences interchain association of the supramolecular polymers, affording different luminescent soft materials, gel and nanosheet.Organic nanocrystals (NCs) with high brightness are highly desirable for biological imaging. However, the preparation of NCs by a facile and fast method is still challenging. Herein, an aggregation-induced emission (AIE) luminogen of 4,4'-(5,6-difluorobenzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (DTPA-BT-F) in the deep-red region is designed with intensive crystalline features to obtain NCs by kinetically controlled nanoprecipitation. The prepared AIE NCs with high brightness and good photo-stability are then applied in super-resolution imaging via stimulated emission depletion (STED) nanoscopy. As observed, the nanostructures in lysosomes of both fixed and live cells are well visualized with superior lateral resolutions under STED nanoscopy (full width at half maximum values, 107 and 108 nm) in contrast to that in confocal imaging (548 and 740 nm). More importantly, dynamic monitoring and long-term tracking of lysosomal movements in live HeLa cells, such as lysosomal contact, can also be carried out by using DTPA-BT-F NCs at a superior resolution. To the best of our knowledge, this is the first case of AIE NCs prepared by nanoprecipitation for STED nanoscopy, thus providing a new strategy to develop high performance imaging agents for super-resolution imaging.We introduce a practically generic approach for the generation of epitope-imprinted polymer-based microarrays for protein recognition on surface plasmon resonance imaging (SPRi) chips. The SPRi platform allows the subsequent rapid screening of target binding kinetics in a multiplexed and label-free manner. The versatility of such microarrays, both as synthetic and screening platform, is demonstrated through developing highly affine molecularly imprinted polymers (MIPs) for the recognition of the receptor binding domain (RBD) of SARS-CoV-2 spike protein. A characteristic nonapeptide GFNCYFPLQ from the RBD and other control peptides were microspotted onto gold SPRi chips followed by the electrosynthesis of a polyscopoletin nanofilm to generate in one step MIP arrays. A single chip screening of essential synthesis parameters, including the surface density of the template peptide and its sequence led to MIPs with dissociation constants (K D) in the lower nanomolar range for RBD, which exceeds the affinity of RBD for its natural target, angiotensin-convertase 2 enzyme. Remarkably, the same MIPs bound SARS-CoV-2 virus like particles with even higher affinity along with excellent discrimination of influenza A (H3N2) virus. While MIPs prepared with a truncated heptapeptide template GFNCYFP showed only a slightly decreased affinity for RBD, a single mismatch in the amino acid sequence of the template, i.e. the substitution of the central cysteine with a serine, fully suppressed the RBD binding.The use of renewable energy is essential for the future of the Earth, and solar photons are the ultimate source of energy to satisfy the ever-increasing global energy demands. Photoconversion using dye-sensitized solar cells (DSCs) is becoming an established technology to contribute to the sustainable energy market, and among state-of-the art DSCs are those which rely on ruthenium(ii) sensitizers and the triiodide/iodide (I3 -/I-) redox mediator. Ruthenium is a critical raw material, and in this review, we focus on the use of coordination complexes of the more abundant first row d-block metals, in particular copper, iron and zinc, as dyes in DSCs. A major challenge in these DSCs is an enhancement of their photoconversion efficiencies (PCEs) which currently lag significantly behind those containing ruthenium-based dyes. The redox mediator in a DSC is responsible for regenerating the ground state of the dye. Although the I3 -/I- couple has become an established redox shuttle, it has disadvantages its redox potential limits the values of the open-circuit voltage (V OC) in the DSC and its use creates a corrosive chemical environment within the DSC which impacts upon the long-term stability of the cells. First row d-block metal coordination compounds, especially those containing cobalt, and copper, have come to the fore in the development of alternative redox mediators and we detail the progress in this field over the last decade, with particular attention to Cu2+/Cu+ redox mediators which, when coupled with appropriate dyes, have achieved V OC values in excess of 1000 mV. We also draw attention to aspects of the recyclability of DSCs.Semiconductor-based surface enhanced Raman spectroscopy (SERS) platforms take advantage of the multifaceted tunability of semiconductor materials to realize specialized sensing demands in a wide range of applications. However, until quite recently, semiconductor-based SERS materials have generally exhibited low activity compared to conventional noble metal substrates, with enhancement factors (EF) typically reaching 103, confining the study of semiconductor-based SERS to purely academic settings. In recent years, defect engineering has been proposed to effectively improve the SERS activity of semiconductor materials. Defective semiconductors can now achieve noble-metal-comparable SERS enhancement and exceedingly low, nano-molar detection concentrations towards certain molecules. The reason for such success is that defect engineering effectively harnesses the complex enhancement mechanisms behind the SERS phenomenon by purposefully tailoring many physicochemical parameters of semiconductors. In this perspective, we introduce the main defect engineering approaches used in SERS-activation, and discuss in depth the electromagnetic and chemical enhancement mechanisms (EM and CM, respectively) that are influenced by these defect engineering methods. We also introduce the applications that have been reported for defective semiconductor-based SERS platforms. With this perspective we aim to meet the imperative demand for a summary on the recent developments of SERS material design based on defect engineering of semiconductors, and highlight the attractive research and application prospects for semiconductor-based SERS.Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these ylides have also been used in a surprising plethora of novel and intrinsic chemical reactions, especially in recent years. Bench stability and handling are also an advantage of this class of organosulfur molecules. Despite this, efficient asymmetric transformations, specifically catalytic enantioselective versions, have only recently been reported, and there are specific reasons for this. This perspective article covers this topic from the first studies up to the latest advances, giving personal perspectives and showing the main challenges in this area in the coming years.
The development of an integral and global treatment to improve the quality of life in those with fibromyalgia syndrome (FMS) is challenging. The aim of this study is to investigate the impact of whole-body photobiomodulation (PBM) on pain perception, functionality, quality of soft tissue, central sensitisation and psychological factors in patients suffering with FMS.
This study is a randomised, placebo-controlled clinical trial. A total of 44 participants will be recruited in a private care practice and randomised to receive either a whole-body PBM therapy programme or placebo in the same care centre. The parameters of the PBM programme are as follows wavelengths of red and near-infrared LEDs 5050 ratio with 660-850 nanometers; fluence of 25.2 J/cm
; treatment time of 1200 s and a total power emitted of 967 W. Treatment sessions will be 3 times weekly for a period of 4 weeks, totalling 12 treatment sessions. Primary outcome will be pain (Numeric Pain Rating Scale; Widespread Pain Index; Symptom Severity ered on January 29, 2020, https//clinicaltrials.gov/ct2/show/NCT04248972?term=navarro-ledesma+santiago&draw=2&rank=2.
NCT04248972. Registered on January 29, 2020, https//clinicaltrials.gov/ct2/show/NCT04248972?term=navarro-ledesma+santiago&draw=2&rank=2.
Mounting evidence has demonstrated that various chronic inflammatory diseases are associated with incident heart failure (HF). However, there is scarce evidence about the association between primary Sjögren's syndrome (pSS) and HF. We aimed to explore this association using a nationwide database in Taiwan.
We selected patients with incident pSS and no history of HF. Using propensity score matching based on age, sex, cohort entry time, comorbidities, and concomitant medications, cohorts of patients with and without pSS (as controls) were created in a 11 ratio and the groups were compared. The cumulative incidence of HF was calculated using Kaplan-Meier estimation. Cox proportional hazard regression analysis was used to measure the hazard ratio (HR) of HF-related hospitalization for the pSS cohort compared with the comparison group.
A total of 16,466 pairs of patients with pSS and those without pSS were identified. The cumulative incidence of HF-related hospitalization at 3, 5, and 10 years in patients with pSS was 1.
