Search for: All records

The use of 18-crown-6 (18-c-6) in place of 2.2.2-cryptand (crypt) in rare earth amide reduction reactions involving potassium has proven to be crucial in the synthesis of Ln( ii ) complexes and isolation of their CO reduction products. The faster speed of crystallization with 18-c-6 appears to be important. Previous studies have shown that reduction of the trivalent amide complexes Ln(NR 2 ) 3 (R = SiMe 3 ) with potassium in the presence of 2.2.2-cryptand (crypt) forms the divalent [K(crypt)][Ln II (NR 2 ) 3 ] complexes for Ln = Gd, Tb, Dy, and Tm. However, for Ho and Er, the [Ln(NR 2 ) 3 ] 1− anions were only isolable with [Rb(crypt)] 1+ counter-cations and isolation of the [Y II (NR 2 ) 3 ] 1− anion was not possible under any of these conditions. We now report that by changing the potassium chelator from crypt to 18-crown-6 (18-c-6), the [Ln(NR 2 ) 3 ] 1− anions can be isolated not only for Ln = Gd, Tb, Dy, and Tm, but also for Ho, Er, and Y. Specifically, these anions are isolated as salts of a 1 : 2 potassium : crown sandwich cation, [K(18-c-6) 2 ] 1+ , i.e. [K(18-c-6) 2 ][Ln(NR 2 ) 3 ]. The [K(18-c-6) 2 ] 1+ counter-cation was superior not only in the synthesis, but it also allowed the isolation of crystallographically-characterizable products from reactions of CO with the [Ln(NR 2 ) 3 ] 1− anions that were not obtainable from the [K(crypt)] 1+ analogs. Reaction of CO with [K(18-c-6) 2 ][Ln(NR 2 ) 3 ], generated in situ , yielded crystals of the ynediolate products, {[(R 2 N) 3 Ln] 2 (μ-OCCO)} 2− , which crystallized with counter-cations possessing 2 : 3 potassium : crown ratios, i.e. {[K 2 (18-c-6) 3 ]} 2+ , for Gd, Dy, Ho. In contrast, reaction of CO with a solution of isolated [K(18-c-6) 2 ][Gd(NR 2 ) 3 ], produced crystals of an enediolate complex isolated with a counter-cation with a 2 : 2 potassium : crown ratio namely [K(18-c-6)] 2 2+ in the complex [K(18-c-6)] 2 {[(R 2 N) 2 Gd 2 (μ-OCHCHO) 2 ]}. 

This chapter describes a personal journey through the periodic table in which an undergraduate starting research in boron hydride chemistry developed into a professorial researcher in rare earth chemistry. The chapter details how the periodic table became a career guide through connections and developments that led the boron chemist into the rare earth field. Also presented is the evolution of reductive rare-earth chemistry which started with just a few +2 lanthanide ions, Eu(II), Yb(II), and Sm(II), and now extends to +2 ions for all the rare earth metals, i.e. Sc, Y, and the lanthanides, La-Lu. The special reactivity of Sm(II), which led to the first lanthanide-based dinitrogen reduction is described, as well as the rare earth dinitrogen reduction that led to the new Ln(II) ions. Periodic trends in these developments are discussed and speculation on the future of the rare-earth elements in terms of periodic properties is also presented. 

Herein, this work reports the first synthetic vaccine adjuvants that attenuate potency in response to small, 1–2 °C changes in temperature about their lower critical solution temperature (LCST). Adjuvant additives significantly increase vaccine efficacy. However, adjuvants also cause inflammatory side effects, such as pyrexia, which currently limits their use. To address this, a thermophobic vaccine adjuvant engineered to attenuate potency at temperatures correlating to pyrexia is created. Thermophobic adjuvants are synthesized by combining a rationally designed trehalose glycolipid vaccine adjuvant with thermoresponsive poly‐N‐isoporpylacrylamide (NIPAM) via reversible addition fragmentation chain transfer (RAFT) polymerization. The resulting thermophobic adjuvants exhibit LCSTs near 37 °C, and self‐assembled into nanoparticles with temperature‐dependent sizes (90–270 nm). Thermophobic adjuvants activate HEK‐mMINCLE and other innate immune cell lines as well as primary mouse bone marrow derived dendritic cells (BMDCs) and bone marrow derived macrophages (BMDMs). Inflammatory cytokine production is attenuated under conditions mimicking pyrexia (above the LCST) relative to homeostasis (37 °C) or below the LCST. This thermophobic behavior correlated with decreased adjuvantR_gis observed by DLS, as well as glycolipid‐NIPAM shielding interactions are observed by NOESY‐NMR. In vivo, thermophobic adjuvants enhance efficacy of a whole inactivated influenza A/California/04/2009 virus vaccine, by increasing neutralizing antibody titers and CD4⁺/44⁺/62L⁺lung and lymph node central memory T cells, as well as providing better protection from morbidity after viral challenge relative to unadjuvanted control vaccine. Together, these results demonstrate the first adjuvants with potency regulated by temperature. This work envisions that with further investigation, this approach can enhance vaccine efficacy while maintaining safety.

 

The citizen Continental-America Telescopic Eclipse (CATE) Experiment was a new type of citizen science experiment designed to capture a time sequence of white-light coronal observations during totality from 17:16 to 18:48 UT on 2017 August 21. Using identical instruments the CATE group imaged the inner corona from 1 to 2.1 RSun with 1.″43 pixels at a cadence of 2.1 s. A slow coronal mass ejection (CME) started on the SW limb of the Sun before the total eclipse began. An analysis of CATE data from 17:22 to 17:39 UT maps the spatial distribution of coronal flow velocities from about 1.2 to 2.1 RSun, and shows the CME material accelerates from about 0 to 200 km s⁻¹across this part of the corona. This CME is observed by LASCO C2 at 3.1–13 RSun with a constant speed of 254 km s⁻¹. The CATE and LASCO observations are not fit by either constant acceleration nor spatially uniform velocity change, and so the CME acceleration mechanism must produce variable acceleration in this region of the corona.