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The cytosolic delivery of hydrophilic, anionic molecular probes and therapeutics is a major challenge in chemical biology and medicine. Herein, we describe the design and synthesis of peptide-cage hybrids that allow an efficient supramolecular binding, cell membrane translocation and cytosolic delivery of a number of anionic dyes, including pyranine, carboxyfluorescein and several sulfonate-containing Alexa dyes. This supramolecular caging strategy is successful in different cell lines, and the dynamic carrier mechanism has been validated by U-tube experiments. The high efficiency of the reported approach allowed intracellular pH tracking by exploiting the ratiometric excitation of the pyranine fluorescent probe. This journal is © The Royal Society of Chemistry 2019.The first examples of stable metal complexes with coordinated ethylene and carbon dioxide ligands are reported. Reaction of tris(ethylene) complexes mer-M(C2H4)3(PNP) (M = Mo and W; PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) with CO2 yields the corresponding, mixed cis-M(C2H4)2(CO2)(PNP) derivatives. X-ray studies reveal six-coordinate structures exhibiting η2-ethylene and κ2-C,O carbon dioxide coordination. Remarkably, the formation of the molybdenum CO2 adduct occurs also in the solid state at room temperature, under 4 bar of CO2, in a nearly quantitative manner. This journal is © The Royal Society of Chemistry 2019.Prediction of aqueous solubilities or hydration free energies is an extensively studied area in machine learning applications in chemistry since water is the sole solvent in the living system. However, for non-aqueous solutions, few machine learning studies have been undertaken so far despite the fact that the solvation mechanism plays an important role in various chemical reactions. Here, we introduce Delfos (deep learning model for solvation free energies in generic organic solvents), which is a novel, machine-learning-based QSPR method which predicts solvation free energies for various organic solute and solvent systems. A novelty of Delfos involves two separate solvent and solute encoder networks that can quantify structural features of given compounds via word embedding and recurrent layers, augmented with the attention mechanism which extracts important substructures from outputs of recurrent neural networks. As a result, the predictor network calculates the solvation free energy of a given solvent-solute pair using features from encoders. With the results obtained from extensive calculations using 2495 solute-solvent pairs, we demonstrate that Delfos not only has great potential in showing accuracy comparable to that of the state-of-the-art computational chemistry methods, but also offers information about which substructures play a dominant role in the solvation process. This journal is © The Royal Society of Chemistry 2019.A series of Cu-Pd alloy nanoparticles supported on Al2O3 were prepared and tested as catalysts for deNO x reactions. https://www.selleckchem.com/products/ew-7197.html XRD, HAADF-STEM, XAFS, and FT-IR analyses revealed that a single-atom alloy structure was formed when the Cu/Pd ratio was 5, where Pd atoms were well isolated by Cu atoms. Compared with Pd/Al2O3, Cu5Pd/Al2O3 exhibited outstanding catalytic activity and N2 selectivity in the reduction of NO by CO for the first time, the complete conversion of NO to N2 was achieved even at 175 °C, with long-term stability for at least 30 h. High catalytic performance was also obtained in the presence of O2 and C3H6 (model exhaust gas), where a 90% decrease in Pd use was achieved with minimum evolution of N2O. Kinetic and DFT studies demonstrated that N-O bond breaking of the (NO)2 dimer was the rate-determining step and was kinetically promoted by the isolated Pd. This journal is © The Royal Society of Chemistry 2019.Background Our objective was to provide consensus recommendations on the optimal management of the immune-mediated inflammatory diseases (IMIDs) seen in patients with spondyloarthritis (SpA) using a multidisciplinary approach, and to develop a simple tool to help earlier recognition and referral of coexisting IMIDs in patients who already have one type of IMID. Methods A total of 28 experts in the multidisciplinary management of the SpA-associated IMIDs assessed two questionnaires one with statements focused on the multidisciplinary management of IMIDs, and a second questionnaire focused on questions useful for early recognition and referral. Panelists assessed the statements with a 9-point ordinal scale (1 = strongly disagree, 9 = strongly agree) using a modified Delphi methodology. Results Consensus was reached on 72 out of the 82 statements (87.8%). Panelists agreed that the multidisciplinary approach to IMIDs is not sufficiently developed. The creation of multidisciplinary IMID units might be necessary. These units might focus primarily on patients with two or more coexisting IMIDs, or on IMIDs that are especially complex from a diagnostic or therapeutic point of view. Specialists who attend to patients with IMIDs should perform a screening for other coexisting IMIDs. A simple tool to help earlier recognition and referral of coexisting IMIDs is proposed. Conclusions There is a need to improve care for patients with SpA-associated IMIDs. We provide expert recommendations to guide the adoption of a multidisciplinary approach for these cases, and a simple tool that may be useful for earlier recognition of coexisting IMIDs. © The Author(s), 2020.Myelofibrosis is one of the Philadelphia chromosome (Ph)-negative myeloproliferative neoplasms with heterogeneous clinical course. Though many treatment options, including Janus kinase (JAK) inhibitors, have provided clinical benefits and improved survival, allogeneic hematopoietic stem-cell transplantation (AHSCT) remains the only potentially curative therapy. Considering the significant transplant-related morbidity and mortality, it is crucial to decide who to proceed to AHSCT, and when. In this review, we discuss recent updates in patient selection, prior splenectomy, conditioning regimen, donor type, molecular mutation, and other factors affecting AHSCT outcomes. Relapse is a major cause of treatment failure; we also describe recent data on minimal residual disease monitoring and management of relapse. In addition, emerging studies have reported pretransplant therapy with ruxolitinib for myelofibrosis showing favorable results, and further research is needed to explore its use in the post-transplant setting.
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