Immobilization of Heparin and Highly-Sulphated Hyaluronic Acid onto Plasma-Treated Polyethylene

Heparin and highly-sulphated hyaluronic acid have been successfully immobilized onto plasma-processed polyethylene via a diamine polyethyleneglycol (PEG) spacer molecule. Two different plasma-processes have been utilized, i.e. a treatment and a deposition process, for providing polyethylene surface with the COOH groups necessary for the immobilization reactions. XPS integrated with derivatization procedures, ATR-FTIR and Water Contact Angle measurements have been carried out for characterizing each modification step: 1) the plasma-process, 2) the immobilization of the spacer molecule and 3) the immobilization of the biomolecules. The thrombin time of the modified surfaces has been measured, and their platelet activation characteristics evaluated. The results indicate a certain nonthrombogenic character of the biomolecule-immobilized polyethylene samples.     

Photo‐Induced Ruthenium‐Catalyzed C−H Arylations at Ambient Temperature

Ambient temperature ruthenium‐catalyzed C?H arylations were accomplished by visible light without additional photocatalysts. The robustness of the ruthenium‐catalyzed C?H functionalization protocol was reflected by a broad range of sensitive functional groups and synthetically useful pyrazoles, triazoles and sensitive nucleosides and nucleotides, as well as multifold C?H functionalizations. Biscyclometalated ruthenium complexes were identified as the key intermediates in the photoredox ruthenium catalysis by detailed computational and experimental mechanistic analysis. Calculations suggested that the in situ formed photoactive ruthenium species preferably underwent an inner‐sphere electron transfer.     

The role of chemometrics in single and sequential extraction assays: a review: part I. Extraction procedures, uni- and bivariate techniques and multivariate variable reduction techniques for pattern recognition

Element mobility and availability in natural solid matrices can be studied with single and sequential extraction procedures; such procedures provide reliable and useful information only if the experiments are correctly planned and executed and the results are properly interpreted. Chemometrics can be a valuable tool for these aims, especially taking into account the large amounts of data generated with extraction essays and the complexity of the processes under investigation. This review deals with the application of chemometrics in research studies involving single and sequential extractions on soils or sediments, for several purposes: the development and optimization of the extraction conditions, the calculation of element fractionation, the visual illustration of the experimental results, the acquisition of different areas of information, including relationships among variables, similarities and differences among samples, causes of the observed behaviour (e.g. source identification), risk assessment, models and predictions of future events. In Part I of the review, following an overview on extraction procedures, the applications of univariate and bivariate chemometric methods are reported; then the principles of multivariate techniques for pattern recognition based on variable reduction, their applications and the main findings obtained are addressed.     

Fitted finite element discretization of two‐phase Stokes flow

We propose a novel fitted finite element method for two‐phase Stokes flow problems that uses piecewise linear finite elements to approximate the moving interface. The method can be shown to be unconditionally stable. Moreover, spherical stationary solutions are captured exactly by the numerical approximation. In addition, the meshes describing the discrete interface in general do not deteriorate in time, which means that in numerical simulations, a smoothing or a remeshing of the interface mesh is not necessary. We present several numerical experiments for our numerical method, which demonstrate the accuracy and robustness of the proposed algorithm. Copyright © 2016 John Wiley & Sons, Ltd.     

In Situ Liquid SAXS Studies on the Early Stage of Calcium Carbonate Formation

Calcium carbonate is a model system to investigate the mechanism of solid formation by precipitation from solutions, and it is often considered in the debated classical and nonclassical nucleation mechanism. Despite the great scientific relevance of calcium carbonate in different scientific areas, little is known about the early stage of its formation. Therefore, contactless devices are designed that are capable of providing informative investigations on the early stages of the precipitation pathway of calcium carbonate in supersaturated solutions using classical scattering methods such as wide‐angle X‐ray scattering (WAXS) and small‐angle X‐ray scattering (SAXS) techniques. In particular, SAXS is exploited for investigating the size of entities formed from supersaturated solutions before the critical conditions for amorphous calcium carbonate (ACC) nucleation are attained. The saturation level is controlled and kept constant by mixing four diluted solutions (i.e., NaOH, CaCl₂, NaHCO₃, H₂O) at constant T and pH. The scattering data are collected on a liquid jet generated about 75 s after the mixing point. The data are modeled using parametric statistical models providing insight about the size distribution of denser matter in the liquid jet. Theoretical implications on the early stage of solid formation pathway are inferred.     

Photoinduced Electron vs. Concerted Proton Electron Transfer Pathways in SnIV (l-Tryptophanato)2 Porphyrin Conjugates

Aromatic amino acids such as l -tyrosine and l -tryptophan are deployed in natural systems to mediate electron transfer (ET) reactions. While tyrosine oxidation is always coupled to deprotonation (proton-coupled electron-transfer, PCET), both ET-only and PCET pathways can occur in the case of the tryptophan residue. In the present work, two novel conjugates 1 and 2 , based on a Sn^IV tetraphenylporphyrin and Sn^IV octaethylporphyrin, respectively, as the chromophore/electron acceptor and l -tryptophan as electron/proton donor, have been prepared and thoroughly characterized by a combination of different techniques including single crystal X-ray analysis. The photophysical investigation of 1 and 2 in CH₂Cl₂ in the presence of pyrrolidine as a base shows that different quenching mechanisms are operating upon visible-light excitation of the porphyrin component, namely photoinduced electron transfer and concerted proton electron transfer (CPET), depending on the chromophore identity and spin multiplicity of the excited state. The results are compared with those previously described for metal-mediated analogues featuring Sn^IV porphyrin chromophores and l -tyrosine as the redox active amino acid and well illustrate the peculiar role of l -tryptophan with respect to PCET.     

Self-assembled organic radicals on Au(111) surfaces: a combined ToF-SIMS, STM, and ESR study

Electron spin resonance (ESR), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and scanning tunneling microscopy (STM) have been used in parallel to characterize the deposition on gold surface of a series of nitronyl nitroxide radicals. These compounds have been specifically synthesized with methyl-thio linking groups suitable to interact with the gold surface to form self-assembled monolayers (SAMs), which can be considered relevant in the research for molecular-based spintronics devices, as suggested in recent papers. The degree of the expected ordering on the surface of these SAMs has been tuned by varying the chemical structure of synthesized radicals. ToF-SIMS has been used to support the evidence of the occurrence of the deposition process. STM has shown the different qualities of the obtained SAMs, with the degree of local order increasing as the degree of freedom of the molecules on the surface is decreased. Finally, ESR has confirmed that the deposition process does not affect the paramagnetic characteristics of radicals and that it affords a complete single-layered coverage of the surface. Further, the absence of angular dependence in the spectra indicates that the small regions of local ordering do not give rise to a long-range order and suggests a quite large mobility of the radical on the surface, probably due to the weak interaction with gold provided by the methyl-thio linking group.     

Association of Systemic Steroid Treatment and Outcome in Patients Treated with Immune Checkpoint Inhibitors: A Real-World Analysis

Background: Immune-related adverse events (irAEs) are inflammatory side effects, which can occur during immune-checkpoint(s) inhibitors (ICIs) therapy. Steroids are the first-line agents to manage irAEs because of their immunosuppressive properties. However, it is still debated whether or when steroids can be administered without abrogating the therapeutic efforts of immunotherapy. Methods: We retrospectively evaluated 146 patients with metastatic non-small cell lung cancer (NSCLC), melanoma and renal cell carcinoma (RCC) treated with ICIs. We assessed the progression-free survival (PFS) of patients treated with steroids due to an irAE compared to a no-steroid group. Results: The early treatment with steroid (within the first 30 days from the beginning of immunotherapy) was not related to a shorter PFS (p = 0.077). Interestingly, patients who were treated with steroids after 30 days from the start of immunotherapy had significantly longer PFS (p = 0.017). In a multivariate analysis, treatment with steroids after 30 days was an independent prognostic factor for PFS (HR: 0.59 [95% CI 0.36–0.97], p = 0.037). Conclusions: This retrospective study points out that early systemic steroids administration to manage irAEs might not have a detrimental effect on patient clinical outcome in NSCLC, melanoma and RCC patients.     

Photo-Induced Ruthenium-Catalyzed C−H Benzylations and Allylations at Room Temperature

The ruthenium-catalyzed synthesis of diarylmethane compounds was realized under exceedingly mild photoredox conditions without the use of exogenous photocatalysts. The versatility and robustness of the ruthenium-catalyzed C−H benzylation was reflected by an ample scope, including multifold C−H functionalizations, as well as transformable pyrazoles, imidates and sensitive nucleosides. Mechanistic studies were indicative of a photoactive cyclometalated ruthenium complex, which also enabled versatile C−H allylations.