Harnessing Selectivity and Sensitivity in Ion Sensing via Supramolecular Recognition: A 3D Hybrid Gold Nanoparticle Network Chemiresistor

The monitoring of K+ in saliva, blood, urine, or sweat represents a future powerful alternative diagnostic tool to prevent various diseases. However, several K+ sensors are unable to meet the requirements for the development of point‐of‐care (POC) sensors. To tackle this grand‐challenge, the fabrication of chemiresistors (CRs) based on 3D networks of Au nanoparticles covalently bridged by ad‐hoc supramolecular receptors for K+, namely dithiomethylene dibenzo‐18‐crown‐6 ether is reported here. A multi‐technique characterization allows optimizing a new protocol for fabricating high‐performing CRs for real‐time monitoring of K+ in complex aqueous environments. The sensor shows exceptional figures of merit: i) linear sensitivity in the 10^–3 to 10^–6 m concentration range; ii) high selectivity to K+ in presence of interfering cations (Na+, Ca2+, and Mg2+); iii) high shelf‐life stability (>45 days); iv) reversibility of K+ binding and release; v) successful device integration into microfluidic systems for real‐time monitoring; vi) fast response and recovery times (<18 s), and v) K+ detection in artificial saliva. All these characteristics make the supramolecular CRs a potential tool for future applications as POC devices, especially for health monitoring where the determination of K+ in saliva is pivotal for the early diagnosis of diseases

Immune Response to Mycobacterium tuberculosis Infection in the Parietal Pleura of Patients with Tuberculous Pleurisy

The T lymphocyte-mediated immune response to Mycobacterium tuberculosis infection in the parietal pleura of patients with tuberculous pleurisy is unknown. The aim of this study was to investigate the immune response in the parietal pleura of tuberculous pleurisy compared with nonspecific pleuritis. We have measured the numbers of inflammatory cells particularly T-cell subsets (Th1/Th2/Th17/Treg cells) in biopsies of parietal pleura obtained from 14 subjects with proven tuberculous pleurisy compared with a control group of 12 subjects with nonspecific pleuritis. The number of CD3+, CD4+ and CCR4+ cells and the expression of RORC2 mRNA were significantly increased in the tuberculous pleurisy patients compared with the nonspecific pleuritis subjects. The number of toluidine blue+ cells, tryptase+ cells and GATA-3+ cells was significantly decreased in the parietal pleura of patients with tuberculous pleurisy compared with the control group of nonspecific pleuritis subjects. Logistic regression with receiver operator characteristic (ROC) analysis for the three single markers was performed and showed a better performance for GATA-3 with a sensitivity of 75%, a specificity of 100% and an AUC of 0.88. There was no significant difference between the two groups of subjects in the number of CD8, CD68, neutrophil elastase, interferon (IFN)-γ, STAT4, T-bet, CCR5, CXCR3, CRTH2, STAT6 and FOXP3 positive cells. Elevated CD3, CD4, CCR4 and Th17 cells and decreased mast cells and GATA-3+ cells in the parietal pleura distinguish patients with untreated tuberculous pleurisy from those with nonspecific pleuritis

Self-Assembly of Mono- And Bidentate Oligoarylene Thiols onto Polycrystalline Au

Four thiolated oligoarylene molecules (i) 4-methoxy-terphenyl-4″-methanethiol (MTM), (ii) 4-methoxy-terphenyl-3″,5″-dimethanethiol (MTD), (iii) 4-nitro-terphenyl-4″-methanethiol (NTM), and (iv) 4-nitro-terphenyl-3″,5″-dimethanethiol (NTD) were synthesized and self-assembled as monolayers (SAMs) on polycrystalline Au electrodes of organic field-effect transistors (OFETs). SAMs were characterized by contact angle and AC/DC electrochemical measurements, whereas atomic force microscopy was used for imaging the pentacene films grown on the coated electrodes. The electrical properties of functionalized OFETs, the electrochemical SAMs features and the morphology of pentacene films were correlated to the molecular organization of the thiolated oligoarylenes on Au, as calculated by means of the density functional theory. This multi-methodological approach allows us to associate the systematic replacement of the SAM anchoring head group (viz. methanethiol and dimethanethiol) and/or terminal tail group (viz. nitro-, -NO2, and methoxy, -OCH3) with the change of the electrical features. The dimethanethiol head group endows SAMs with higher resistive features along with higher surface tensions compared with methanethiol. Furthermore, the different number of thiolated heads affects the kinetics of Au passivation as well as the pentacene morphology. On the other hand, the nitro group confers further distinctive properties, such as the positive shift of both threshold and critical voltages of OFETs with respect to the methoxy one. The latter experimental evidence arise from its electron-withdrawing capability, which has been verified by both DFT calculations and DC electrochemical measurements

Tetrapodal Diazatriptycene Enforces Orthogonal Orientation in Self-Assembled Monolayers

none17Conformationally rigid multipodal molecules should control the orientation and packing density of functional head groups upon self-assembly on solid supports. Common tripods frequently fail in this regard because of inhomogeneous bonding configuration and stochastic orientation. These issues are circumvented by a suitable tetrapodal diazatriptycene moiety, bearing four thiol-anchoring groups, as demonstrated in the present study. Such molecules form well-defined self-assembled monolayers (SAMs) on Au(111) substrates, whereby the tetrapodal scaffold enforces a nearly upright orientation of the terminal head group with respect to the substrate, with at least three of the four anchoring groups providing thiolate-like covalent attachment to the surface. Functionalization by condensation chemistry allows a large variety of functional head groups to be introduced to the tetrapod, paving the path toward advanced surface engineering and sensor fabrication.NEXUSnoneBenneckendorf, Frank S; Rohnacher, Valentina; Sauter, Eric; Hillebrandt, Sabina; Münch, Maybritt; Wang, Can; Casalini, Stefano; Ihrig, Katharina; Beck, Sebastian; Jänsch, Daniel; Freudenberg, Jan; Jaegermann, Wolfram; Samorì, Paolo; Pucci, Annemarie; Bunz, Uwe H F; Zharnikov, Michael; Müllen, KlausBenneckendorf, Frank S; Rohnacher, Valentina; Sauter, Eric; Hillebrandt, Sabina; Münch, Maybritt; Wang, Can; Casalini, Stefano; Ihrig, Katharina; Beck, Sebastian; Jänsch, Daniel; Freudenberg, Jan; Jaegermann, Wolfram; Samorì, Paolo; Pucci, Annemarie; Bunz, Uwe H F; Zharnikov, Michael; Müllen, Klau

Prosafe: a european endeavor to improve quality of critical care medicine in seven countries

BACKGROUND: long-lasting shared research databases are an important source of epidemiological information and can promote comparison between different healthcare services. Here we present ProsaFe, an advanced international research network in intensive care medicine, with the focus on assessing and improving the quality of care. the project involved 343 icUs in seven countries. all patients admitted to the icU were eligible for data collection. MetHoDs: the ProsaFe network collected data using the same electronic case report form translated into the corresponding languages. a complex, multidimensional validation system was implemented to ensure maximum data quality. individual and aggregate reports by country, region, and icU type were prepared annually. a web-based data-sharing system allowed participants to autonomously perform different analyses on both own data and the entire database. RESULTS: The final analysis was restricted to 262 general ICUs and 432,223 adult patients, mostly admitted to Italian units, where a research network had been active since 1991. organization of critical care medicine in the seven countries was relatively similar, in terms of staffing, case mix and procedures, suggesting a common understanding of the role of critical care medicine. conversely, icU equipment differed, and patient outcomes showed wide variations among countries. coNclUsioNs: ProsaFe is a permanent, stable, open access, multilingual database for clinical benchmarking, icU self-evaluation and research within and across countries, which offers a unique opportunity to improve the quality of critical care. its entry into routine clinical practice on a voluntary basis is testimony to the success and viability of the endeavor