Emersonkjellerup3373

Copper(i) catalyzes the borylative cyclization of γ-alkenyl aldehydes through chemo- and regioselective addition of Cu-B to C[double bond, length as m-dash]C and concomitant intramolecular 1,2-addition of Cu-C on C[double bond, length as m-dash]O. The products are formed in an exclusive diastereoselective manner and computational analysis identifies the key points for the observed chemo- and diastereoselectivity.Reported herein is the first catalytic oxidative [4+2] cycloaddition of 2-aminophenols with cyclic enamines. This biomimetic catalytic oxidative strategy expediently accommodates the very labile structurally unbiased ortho-quinone monoimine intermediate for cycloaddition by controlling its formation rate, thus refraining from otherwise prerequisite steric or electronic stabilization and allowing efficient assembly of various tricyclic 1,4-benzoxazines in a step and atom economic fashion.Partial metathesis between two weakly-coordinating anions in the archetypical dysprosium metallocene results in the first example of [BPh4]- as a bridging ligand in 4f metals, with a unique η2,η2η2,η2-bridge. Magnetic susceptibility and relaxation dynamics studies along with ab initio calculations reveal improved slow relaxation of the magnetization in over its mononuclear congener, resulting in an energy barrier of 490 K/340 cm-1 and waist-restricted hysteresis up to 6.5 K.The reaction mechanism leading to the formation of cross-coupling palladium pre-catalysts of the PEPPSI family was investigated. Two intermediates were isolated and proved to be both suitable synthons to the pre-catalysts, with one permitting the design of a novel and greener user-friendly synthetic route. In light of this mechanistic understanding, the traditional one-pot method was shown to be possible using stoichiometric amounts of throw-away ligand, which represents a considerable synthetic improvement over the wasteful "in pyridine" approach.Polycrystalline bulk of TiS2 with a remarkable enhancement of the texture degree was obtained by densifying powders refined by a liquid-based mechanical exfoliation process. As compared to the pristine TiS2, the in-(a-b)-plane mobility in the exfoliation sample increased from 5.9 to 9.8 cm2 V-1 s-1 with an almost unaffected carrier concentration, in spite of the increased scattering due to grain boundaries. As a result, a tremendously high power factor of up to 16 μW cm-1 K-2 at 673 K was achieved, which is 60% higher than that of the pristine TiS2 and is the highest for bulk TiS2 at high temperatures.A supramolecular assembly was constructed by the nonconvalent interaction of pillar[5]arene (WP5) with a pyridinium modified tetraphenylethene (Py-TPE) derivative, in which Py-TPE/WP5 acted as a donor, and sulforhodamine 101 and sulfonated aluminum phthalocyanine acted as acceptors to realize a highly efficient light-harvesting system with two-step sequential energy transfer.A terbium(iii) complex can recognize soluble Aβ in plasma through human serum albumin (HSA)-mediated co-assembly, which can not only circumvent the interference of HSA, but also benefit Aβ enrichment with amplified time-resolved luminescence enhancement.We present a time-resolved broadband cavity-enhanced UV-absorption spectrometer apparatus that we have constructed and utilized for temperature- and pressure-dependent kinetic measurements of formaldehyde oxide (CH2OO) reactions. We also introduce and utilize a new photolytic precursor, bromoiodomethane (CH2IBr), which photolysis at 213 nm in presence of O2 produces CH2OO. Importantly, this precursor appears to be free from secondary reactions that may regenerate CH2OO in kinetic experiments. The unimolecular decomposition rate coefficient of CH2OO has been measured over wide pressure (5-400 Torr) and temperature (296-600 K) ranges and master equation simulations of the decomposition kinetics have been performed using MESMER program. The MESMER simulations of the experimental data with the calculated zero-point energy corrected transition state energy 85.9 kJ mol-1 for decomposition required no adjustment and returned ΔEdown = 123.2 × (T/298 K)0.74 cm-1 for temperature-dependent exponential-down model of the e coefficients is about ±20%. Current bimolecular rate coefficient at room temperature agrees with the previously reported rate coefficients from the direct kinetic experiments. The reaction is found to be pressure independent over the range between 5 and 150 Torr at 296 K in He.Two new families of lanthanide antennas are described. 8-Methoxy-4,5-dihydrocyclopenta[de]quinolin-2(1H)-one phosphonates or carboxylates behave as selective antennas exhibiting Eu3+ luminescence in organic solvents, while quinolin-2(1H)-one analogues selectively sensitize the Tb3+ emission. These emissions are quenched by H2O addition. Based on this behaviour, the new lanthanide antennas can be used as highly sensitive water sensors.Methyl jasmonate (MeJA) and its free-acid form, jasmonic acid (JA), collectively referred to as jasmonates (JAs), are natural plant growth regulators that are widely present in higher plants. Simultaneous detection of JA and MeJA in plant samples is of significance and is a great challenging issue. In this study, coupling with two extraction methods, a sensitive monoclonal antibody (mAb) based enzyme-linked immunosorbent assay (ELISA) for simultaneous detection of JA and MeJA in plant samples was developed. The JA-bovine serum albumin (BSA) conjugate was used as an immunogen for the production of mAb. As the produced mAb exhibited higher recognition ability towards MeJA than towards JA, ELISA was established using MeJA as the standard. Under optimal experimental conditions, the IC50 and LOD values of ELISA for MeJA were 2.02 ng mL-1 and 0.20 ng mL-1, respectively. In the first extraction method, MeJA in plant samples was evaporated and only JA was extracted. In the second extraction method, both JA and MeJA were extracted. After methylation, JA in the extracts was converted into MeJA, and the whole MeJA in the extracts was measured by ELISA. Plant samples including the leaves of Salvia splendens, the flowers of Salvia splendens and the fruit of grapes were collected. JA and MeJA in these samples were detected by the proposed ELISA. It was found that the concentrations of JA in these three plant samples were about 3-5 times higher than those of MeJA in those samples. ELISA was also confirmed by HPLC. There was a good correlation between ELISA and HPLC.Glyoxal (C2H2O2) is a highly reactive molecule present at trace levels in specific gaseous environments. For analyses by chemical ionization mass spectrometry, it is important to understand the gas-phase chemistry initiated by reactions of H3O+ ions with C2H2O2 molecules in the presence of water vapour. This chemistry was studied at variable humidity using a selected ion flow tube, SIFT. The initial step is a proton transfer reaction forming protonated glyoxal C2H3O2+. The second step, in the presence of water vapour, is the association forming C2H3O2+(H2O) and interestingly also protonated formaldehyde CH2OH+. Hydrated protonated formaldehyde CH2OH+(H2O) was also observed. Relative signals of these four ionic products were studied at the end of the flow tube where the reactions took place during 0.3 ms in helium carrier gas (1.5 mbar, 300 K) as the water vapour number density varied up to 1014 cm-3. The data were interpreted using numerical kinetics modelling of the reaction sequences and the mechanisms and kinetics of the reaction steps were characterised. The results thus facilitate SIFT-MS analyses of glyoxal in humid air whilst drawing attention to ion overlaps with formaldehyde products.The application and understanding of dendritic cell (DC) based immune cancer therapy are largely hindered by insufficient or improper presentation of antigens and the inability to track the homing of reprogrammed DCs to draining lymph nodes in real-time. To tackle these challenges, multi-functional and hierarchically structured silica nanospheres are rationally designed and fabricated, which encapsulate quantum dots to permit near infrared deep tissue imaging and are loaded with carcinoembryonic antigen messenger RNA (CEAmRNA) to enable stable and abundant antigen expression in DCs. After being injected into animals and inducing an antigen-specific immune response, the homing process of reprogrammed labelled DCs from peripheral tissues to draining lymph nodes can be simultaneously and precisely tracked. Significant inhibition of tumor growth is achieved via strong antigen-specific immune responses including induced DC maturation, enhanced T cell proliferation and cytotoxic T lymphocyte (CTL)-mediated responses. Both in vitro and in vivo experiments demonstrate the high effectiveness of this new strategy of imaging-guided cancer immunotherapy by using reprogrammed DCs as immunotherapeutic and tracking agents.The gold-catalyzed hydration reaction of haloalkynes is highly regioselective producing 2-halomethylketones as the sole products. Herein, we document a drastic fluorine effect where the reaction of 1-halo-3,3-difluoroalkynes as substrates leads to a complete reversal of selectivity and produces 3,3-difluoroesters as the unique products.Two triphenylamine or 4,4'-di(tert-butyl)triphenylamine groups are introduced at the 1,8-positions of 3,6-di(tert-butyl)-9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)carbazole to yield two emitters containing a cofacial donor-acceptor-donor chromophore, which exhibit strong TADF characteristics dominated by through-space charge-transfer. The solution-processed OLEDs achieve maximum external quantum efficiencies of up to 17.4% and 24.3% with small efficiency roll-off rates.Targeted epitope-based mass spectrometry imaging (MSI) utilizes laser cleavable mass-tags bound to targeting moieties for detecting proteins in tissue sections. Our work constitutes the first proof-of-concept of a novel laser desorption ionization (LDI)-MSI strategy using photocleavable Ru(ii) polypyridine complexes as mass-tags for imaging of integrins αvβ3 in human cancer tissues.This paper reports in-air monitoring of in vitro monolayer cells under air-exposure utilizing electrochemical impedance spectroscopy (EIS). In-air impedance measurement was performed by placing integrated electrodes laterally, instead of vertically, to a cell membrane, avoiding electrical disconnection, unlike conventional transepithelial-electrical-resistance (TEER). The in-air EIS sensor platform mainly consisted of two chambers, separated by a porous membrane where cells were cultured, that enabled cell exposure to both air (apical side) and liquid (basal side) for long-term measurement. On top of the membrane, EIS interdigitated electrodes were patterned and lung epithelial cells (A549 type II) were cultured with air exposure on one side. The fabricated in-air EIS sensor successfully demonstrated in situ real-time measurement of cell populations in confluency in the range of 7.8 × 104 and 9.6 × 105 cells per cm2 at a sensitivity of 3.0 × 10-2 Ω per cell in impedance and in the range of 1.0 × 104 and 9.6 × 105 cells per cm2 at a sensitivity of 0.17 × 10-15 F per cell in capacitance under AC frequencies of 100 kHz and 1 MHz, respectively. It also successfully monitored transient modulation of tight-junctions that collectively began to open in 30 minutes after the injection of 100 ng ml-1 TNF-α (a relaxation agent), reached maximum relaxation with a 12.6% increase in impedance value and a 12% decrease in capacitance in 60 minutes, and recovered back to its original junction status after 720 minutes, which confirmed the observation in animal models in the literature. Note that the opposite trends in impedance and capacitance allowed the in-air EIS sensor to distinguish cell population changes from tight junction modulation. It was concluded that the developed in-air EIS sensor in an in vitro platform can enable in situ and real-time monitoring of the population of the 'air-exposed' cells as well as the modulation of tight-junctions, which has not been demonstrated yet.