A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

The efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two‐step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β‐alanine betaine G5 , which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea‐based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen‐bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self‐associate. Remarkably, host 6 is able to perform solid–liquid as well as liquid–liquid extraction of G5 . Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.     

Synthesis of (diarylmethyl)amines using Ni-catalyzed arylation of C(sp3)–H bonds

The first nickel catalyzed deprotonative cross coupling between C(sp³)–H bonds and aryl chlorides is reported, allowing the challenging arylation of benzylimines in the absence of directing group or stoichiometric metal activation. This methodology represents a convenient access to the (diarylmethyl)amine moiety, which is widespread in pharmaceutically relevant compounds.     

A radioxenon detection system using CdZnTe,an array of SiPMs,and a plastic scintillator

This paper presents the design and characterization of a prototype compact beta–gamma radioxenon detection system that utilizes a coplanar CdZnTe crystal, an array of SiPMs, and a plastic scintillator. The detector is directly mounted on a custom PCB. The system provides the advantage of room-temperature operation, while being compact, low noise, and with simple readout electronics. Preliminary measurements using ¹³⁷Cs, ¹³⁵Xe, and ^133/133mXe were conducted to optimize various system parameters to achieve optimal resolution of key photopeaks. The purpose of this research was to explore the potential of these radiation detection elements for use in beta–gamma coincidence applications.     

Effective transformation of cellulose to 5-hydroxymethylfurfural catalyzed by fluorine anion-containing ionic liquid modified biochar sulfonic acids in water

This article first discloses that the fluorine anion-containing ionic liquids-functionalized biochar sulfonic acids (BCSA-IL-F_1–3s), which were simply synthesized by an ionic exchange of 1-trimethoxysilylpropyl-3-methylimidazolium chloride (IL-Cl) grafted on the BCSA with CF₃SO₃H (HF₁), HBF₄ (HF₂), HPF₆ (HF₃), respectively, can efficiently catalyze cellulose hydrolysis into reducing sugars (RSs) and 5-hydroxymethyl furfural (HMF) in water under microwave irradiation. This process provides a very high catalysis efficiency (turnover numbers, 4.03–4.89) at mild temperature (80 °C) for 3 h, but also possesses an excellent repeatability. More outstandingly, they can achieve much higher HMF yields (12.70–27.94%) compared to the IL-Cl-functionalized BCSA catalyst (HMF yields are lower than 0.1%) under the same reaction conditions. This is likely because the introduction of IL-F_1–3s groups can significantly improve the accessibility, acidity and thermal stability of BCSA’s SO₃H sites, as supported by evidence from a solid ³¹P NMR spectrum and thermogravimetric analysis. It is proposed that the good selectivity for HMF perhaps originates from a co-catalysis action of the IL-F_1–3s and SO₃H groups on BCSA-IL-F_1–3s in the further conversion of RSs to HMF.     

Two formulas for the BR multiplicity

We prove a projection formula, expressing a relative Buchsbaum–Rim multiplicity in terms of corresponding ones over a module-finite algebra of pure degree, generalizing an old formula for the ordinary (Samuel) multiplicity. Our proof is simple in spirit: after the multiplicities are expressed as sums of intersection numbers, the desired formula results from two projection formulas, one for cycles and another for Chern classes. Similarly, but without using any projection formula, we prove an expansion formula, generalizing the additivity formula for the ordinary multiplicity, a case of the associativity formula.     

ISSUE INFORMATION

Modeling social‐ecological systems is difficult due to the complexity of ecosystems and of individual and collective human behavior. Key components of the social‐ecological system are often over‐simplified or omitted. Generalized modeling is a dynamical systems approach that can overcome some of these challenges. It can rigorously analyze qualitative system dynamics such as regime shifts despite incomplete knowledge of the model's constituent processes. Here, we review generalized modeling and use a recent study on the Baltic Sea cod fishery's boom and collapse to demonstrate its application to modeling the dynamics of empirical social‐ecological systems. These empirical applications demand new methods of analysis suited to larger, more complicated generalized models. Generalized modeling is a promising tool for rapidly developing mathematically rigorous, process‐based understanding of a social‐ecological system's dynamics despite limited knowledge of the system.     

Quantification of Polycyclic Aromatic Hydrocarbons in Avian Dried Blood Spots by Ultra-performance Liquid Chromatography with Simple Liquid Extraction and Phospholipid Solid-phase Extraction Preparation

Here, a simple, reliable method for the quantification of the 16 EPA priority polycyclic aromatic hydrocarbons in dried blood spots is outlined using liquid extraction and phospholipid solid-phase sample cleanup coupled with analysis by ultra-performance liquid chromatography with ultraviolet–visible detection. Whole blood spotted on Whatman FTA cards was efficiently quantified by extraction into acidified methanol and passed through a phospholipid solid-phase extraction well plate before injection into a liquid chromatography under reverse-phase conditions. The analyte recoveries in quality control samples ranged from 63.4 to 104.1%, with relative standard deviations from 0.48 to 2.04%. These figures of merit are comparable with measurements in whole blood or serum using similar techniques. The method detection limits were from 45.0?ng·g^?1 for benzo[g,h,i]perylene to 118.7?ng·g^?1 for chrysene, with matrix spike recoveries from 64.3 to 99.4%, demonstrating acceptable sensitivity and low matrix interference. With a simple liquid extraction approach and short 16-min liquid chromatography, the dried blood spots were effectively and rapidly analyzed.     

Combined OX40 Agonist and PD-1 Inhibitor Immunotherapy Improves the Efficacy of Vascular Targeted Photodynamic Therapy in a Urothelial Tumor Model

Purpose: Vascular targeted photodynamic therapy (VTP) is a nonsurgical tumor ablation approach used to treat early-stage prostate cancer and may also be effective for upper tract urothelial cancer (UTUC) based on preclinical data. Toward increasing response rates to VTP, we evaluated its efficacy in combination with concurrent PD-1 inhibitor/OX40 agonist immunotherapy in a urothelial tumor-bearing model. Experimental design: In mice allografted with MB-49 UTUC cells, we compared the effects of combined VTP with PD-1 inhibitor/OX40 agonist with those of the component treatments on tumor growth, survival, lung metastasis, and antitumor immune responses. Results: The combination of VTP with both PD-1 inhibitor and OX40 agonist inhibited tumor growth and prolonged survival to a greater degree than VTP with either immunotherapeutic individually. These effects result from increased tumor infiltration and intratumoral proliferation of cytotoxic and helper T cells, depletion of Treg cells, and suppression of myeloid-derived suppressor cells. Conclusions: Our findings suggest that VTP synergizes with PD-1 blockade and OX40 agonist to promote strong antitumor immune responses, yielding therapeutic efficacy in an animal model of urothelial cancer.     

Time-resolved particle image velocimetry analysis and computational modeling of transient optically induced electrothermal micro vortex

Trapping, sorting, transportation, and manipulation of synthetic microparticles and biological cells enable investigations in their behavior and properties. Microfluidic techniques like rapid electrokinetic patterning (REP) provide a non-invasive means to probe into the nature of these micro and nanoparticles. The opto-electrically induced nature of a REP micro vortex allows tuning of the trap characteristics in real-time. In this work, we studied the effects of transient optical heating on the induced electrothermal vortex using micro-particle image velocimetry (μ-PIV) and computational modeling. A near infra-red (980 nm) laser beam was focused on a colloidal suspension of 1 μm polystyrene beads sandwiched between two parallel-plate electrodes. The electrodes were subjected to an AC current. The laser spot was scanned back-and-forth in a line, at different frequencies, to create the transient vortex. This phenomenon was also studied with a computational model made using COMSOL Multiphysics. We visualize fluid flow in custom-shaped REP traps by superposing multiple axisymmetric (spot) vortices and discuss the limitations of using superposition in dynamically changing traps.