Sterngunn9458

This study documents the first-time detection of hexadecafluorosebacic acid and perfluoro-3,6,9-trioxaundecane-1,11-dioic acid within environmental samples.Challenges in the selective manipulation of functional groups (chemoselectivity) in organic synthesis have historically been overcome either by using reagents/catalysts that tunably interact with a substrate or through modification to shield undesired sites of reactivity (protecting groups). Although electrochemistry offers precise redox control to achieve unique chemoselectivity, this approach often becomes challenging in the presence of multiple redox-active functionalities. Historically, electrosynthesis has been performed almost solely by using direct current (DC). In contrast, applying alternating current (AC) has been known to change reaction outcomes considerably on an analytical scale but has rarely been strategically exploited for use in complex preparative organic synthesis. Here we show how a square waveform employed to deliver electric current-rapid alternating polarity (rAP)-enables control over reaction outcomes in the chemoselective reduction of carbonyl compounds, one of the most widely used reaction manifolds. The reactivity observed cannot be recapitulated using DC electrolysis or chemical reagents. The synthetic value brought by this new method for controlling chemoselectivity is vividly demonstrated in the context of classical reactivity problems such as chiral auxiliary removal and cutting-edge medicinal chemistry topics such as the synthesis of PROTACs.In an effort to probe the impacts of speciation on spin-state switching, the synthesis and unique solution-phase magnetic properties of [((TIPSC≡C)3tren)Fe(OTf)2] (1) are described. Analysis of the single-crystal X-ray diffraction data shows that the tris(iminoalkyne) ligand coordinates to the iron(II) center through all four nitrogen atoms, while the other two coordination sites are filled by the oxygen atoms from triflate anions. Solid-state variable-temperature (VT) magnetic studies show that 1 remains high-spin (HS) at all temperatures. In the presence of moderately strong coordinating solvents, solvent replaces the two bound triflate counteranions, as observed by 19F NMR spectroscopy and supported by conductivity measurements. CDK and cancer VT solution measurements show 1 to be in the HS state when this solvent is oxygen-donating but low-spin (LS) with a nitrogen-donating solvent. In the noncoordinating solvent dichloromethane, both triflates are bound to the iron(II) center at room temperature, but upon cooling, 1 undergoes a coordination change, resulting in the loss of one triflate, as shown by 19F NMR. With the moderately coordinating solvent acetone, triflate dissociation upon cooling results in a spin-switching species with a T1/2 value of 171 K, characterized via 19F NMR, Evans' method, and solution magnetometry measurements. Solution magnetic measurements collected in structurally similar cyclopentanone suggest that the spin-state switching event is exclusive to the acetone environment, suggesting the influence of both the local coordination environment and aggregation. Additionally, a comparison of the solvodoynamic diameters via dynamic light scattering suggests that aggregation of 1 is significantly different in (CH3)2CO and (CD3)2CO, leading to the observation of spin-switching behavior in the former and fully HS behavior in the latter. This study highlights the sensitivity of solution magnetic properties to solvent choice.The continued success of pest control using insecticidal crystal (Cry) proteins from Bacillus thuringiensis (Bt) in transgenic plants was threatened by the evolution of resistance. Previous studies suggested that polycalin from Plutella xylostella could bind to Cry1Ac toxin as a potential receptor. In this study, a fragment of P. xylostella polycalin (Pxpolycalinf, G2209-A2942) containing a carboxyl-terminal GPI-anchored signal peptide was cloned and expressed. Purified Pxpolycalinf retained the binding ability to Cry1Ac and synergized Cry1Ac toxicity to the third larvae of P. xylostella in bioassays. Moreover, the polyclonal antibody of Pxpolycalinf decreased the Cry1Ac activity after being fed together with normal food. Further, the ELISA results showed the concentration-dependent binding of Pxpolycalinf to P. xylostella brush border membrane vesicles (BBMV). Spodoptera frugiperda 9 (Sf9) cells expressing Pxpolycalinf were not susceptive to Cry1Ac, whereas Pxpolycalinf increased Cry1Ac cytotoxicity to Sf9 cells expressing P. xylostella ATP-dependent binding cassette transporter C2 (PxABCC2). Immunolocalization presented the binding of Pxpolycalinf to the Sf9 cell membrane, and ELISA showed the concentration-dependent binding of Pxpolycalinf to Sf9 cell extraction. These results here provide the first evidence that a fragment of P. xylostella polycalin, a potential receptor of Cry1Ac, synergizes Cry1Ac toxicity to P. xylostella larvae and Sf9 cells expressing PxABCC2.Surgical masks have been worn by the public worldwide during the COVID-19 pandemic, yet hazardous chemicals in the petroleum-derived polymer layer of masks are currently ignored and unregulated. These organic compounds pose potential health risks to the mask wearer through dermal contact or inhalation. Here, we show that surgical masks from around the world are loaded with semivolatile and volatile organic compounds (VOCs), including alkanes, polycyclic aromatic hydrocarbons (PAHs), phthalate esters, and reactive carbonyls at ng to μg/mask levels. Naphthalene was the most abundant mask-borne PAH, accounting for over 80% of total PAH levels; acrolein, a mutagenic carbonyl, was detected in most of the mask samples, and di(2-ethylhexyl) phthalate, an androgen antagonist, was detected in one-third of the samples. Furthermore, there is large mask-to-mask variability of the residue VOCs, revealing the uneven quality of masks. We confirm that masks containing more residue VOCs lead to significantly higher exposure levels and associated disease risks to the wearer, which should warrant the attention of the general public and regulatory agencies. We find that heating the masks at 50 °C for as short as 60 min lowers the total VOC content by up to 80%, providing a simple method to limit our exposure to mask-borne VOCs.Bacterial infectious diseases seriously threaten public health and life. The specific interaction between an antibody and its multivalent antigen is an attractive way to defeat infectious disease. However, due to the high expense and strict storage and applied conditions for antibodies, it is highly desirable but remains an urgent challenge for disease diagnosis and treatment to construct artificial antibodies with strong stability and binding ability and excellent selectivity. Herein, we designed and synthesized antibody-like bio-orthogonal catalysts with the ability to recognize specific bacteria and accomplish in situ drug synthesis in captured bacteria by using improved bacterial imprinting technology. On one hand, the artificial antibody possesses a matching morphology for binding pathogens, and on the other hand, it acts as a bio-orthogonal catalyst for in situ synthesis of antibacterial drugs in live bacteria. Both in vitro and in vivo experiments have demonstrated that our designed antibody can distinguish and selectively bind to specific pathogens and eliminate them on site with the activated drugs. Therefore, our work provides a strategy for designing artificial antibodies with bio-orthogonal catalytic activity and may broaden the application of bio-orthogonal chemistry.CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous ligands are in contrast with the typical behavior that may be expected for gas sorption in metal-organic frameworks (MOFs), which generally follows similar periodic trends for a given set of systematic changes to the host MOF structure. A combination of computational and spectroscopic data reveals that the divergent behavior, especially between CO and ethylene, stems from a predominantly σ-donor interaction between the former and Ni2+ and a π-acceptor interaction for the latter. These findings will facilitate further deliberate postsynthetic modifications of MOFs with open metal sites to control the equilibrium selectivity of gas sorption.Dermal exposure to semivolatile organic compounds (SVOCs) has recently attracted widespread attention; understanding these exposures is particularly important for people whose skin is frequently exposed to different pollution surfaces. In this study, handwipes were collected from exposed occupational workers and local residents near a typical electronic waste (e-waste) dismantling area; urine samples were also sampled. The wipes were analyzed for three typical SVOCs polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and organophosphate flame retardants (OPFRs). The median levels of PAHs, OPFRs, and PBDEs in handwipes from e-waste dismantlers were 96.0, 183, and 238 ng, respectively. The analytes were higher in the handwipes collected from workers than those from residents, indicating that they were subjected to greater dermal exposure during primitive e-waste dismantling activities. Among the three SVOCs, the strongest correlation was found between triphenyl phosphate (TPhP) in handwipes and diphenyl phosphate (DPhP) in paired urine; the next strongest correlations were between PAHs and PBDEs and their corresponding urinary metabolites. The results showed that TPhP contributed the highest exposure to e-waste dismantlers via dermal exposure. Our research highlights the importance of dermal exposure to TPhP, which should be considered in future exposure risk assessments.The continuously developing lithium battery market makes seeking a reliable lithium supply a top priority for technology companies. Although metal-organic frameworks have been extensively researched as adsorbents owing to their exceptional properties, lithium adsorption has been scarcely investigated. Herein, we prepared a novel cuboid rod-shaped three-dimensional framework termed TJU-21 composed of fluorine-pillared coordination layers of Fe-O inorganic chains and benzene-1,3,5-tricarboxylate (BTC) linkages. Besides thermal and chemical robustness, a remarkably high lithium uptake of about 41 mg·g-1 was observed on TJU-21 as a fast-spontaneous endothermic process. Single-crystal X-ray diffraction demonstrated that the adsorbed lithium was located in the cavity symmetrically assembled by iron sites and organic ligands between adjacent layers, while another kind of cavity in the framework circled by Fe-O-Fe-O-Fe-O-Fe chains and shared BTC linkages was occupied by hydrogen-bonded water molecules. Lithium adsorption resulted in decreased curviness of the coordination layers, and the binding energy change at O 1s as well as the increased Fe 2p peak, suggested potential interaction with iron sites. The practicability of TJU-21 as a lithium adsorbent was further proved by the considerable capacity and selectivity in simulated salt brines with excellent reusability.