Nido‐Carboranes: Donors for Thermally Activated Delayed Fluorescence

An approach to the design of nido‐carborane‐based luminescent compounds that can exhibit thermally activated delayed fluorescence (TADF) is proposed. 7,8‐Dicarba‐nido‐undecaboranes (nido‐carboranes) having various 8‐R groups (R=H, Me, i‐Pr, Ph) are appended to the meta or para position of the phenyl ring of the dimesitylphenylborane (PhBMes₂) acceptor, forming donor–acceptor compounds (nido‐ m1 – m4 and nido‐ p1 – p4 ). The bulky 8‐R group and meta substitution of the nido‐carborane are essential to attain a highly twisted arrangement between the donor and acceptor moieties, leading to a very small energy splitting between the singlet and triplet excited states (ΔE_ST <0.05 eV for nido‐ m2 , ‐ m3 , and ‐ p3 ). These compounds exhibit efficient TADF with microsecond‐range lifetimes. In particular, nido‐ m2 and ‐ m3 display aggregation‐induced emission (AIE) with TADF properties.     

Glycosyl‐Substituted Dicarboxylates as Detergents for the Extraction,Overstabilization, and Crystallization of Membrane Proteins

To tackle the problems associated with membrane protein (MP) instability in detergent solutions, we designed a series of glycosyl‐substituted dicarboxylate detergents (DCODs) in which we optimized the polar head to clamp the membrane domain by including, on one side, two carboxyl groups that form salt bridges with basic residues abundant at the membrane–cytoplasm interface of MPs and, on the other side, a sugar to form hydrogen bonds. Upon extraction, the DCODs 8 b , 8 c , and 9 b preserved the ATPase function of BmrA, an ATP‐binding cassette pump, much more efficiently than reference or recently designed detergents. The DCODs 8 a , 8 b , 8 f , 9 a , and 9 b induced thermal shifts of 20 to 29 °C for BmrA and of 13 to 21 °C for the native version of the G‐protein‐coupled adenosine receptor A_2AR. Compounds 8 f and 8 g improved the diffraction resolution of BmrA crystals from 6 to 4 Å. DCODs are therefore considered to be promising and powerful tools for the structural biology of MPs.     

Plasmonic Hotspots in Air: An Omnidirectional Three‐Dimensional Platform for Stand‐Off In‐Air SERS Sensing of Airborne Species

Molecular‐level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface‐enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS‐active depth. “Aerosolized plasmonic colloidosomes” (APCs) are introduced as airborne plasmonic hotspots for direct in‐air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100‐fold higher tolerance to laser misalignment along the z‐axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in‐air SERS detection is demonstrated in stand‐off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas.     

DNA Origami Scaffolds as Templates for Functional Tetrameric Kir3 K+ Channels

In native systems, scaffolding proteins play important roles in assembling proteins into complexes to transduce signals. This concept is yet to be applied to the assembly of functional transmembrane protein complexes in artificial systems. To address this issue, DNA origami has the potential to serve as scaffolds that arrange proteins at specific positions in complexes. Herein, we report that Kir3 K⁺ channel proteins are assembled through zinc‐finger protein (ZFP)‐adaptors at specific locations on DNA origami scaffolds. Specific binding of the ZFP‐fused Kir3 channels and ZFP‐based adaptors on DNA origami were confirmed by atomic force microscopy and gel electrophoresis. Furthermore, the DNA origami with ZFP binding sites nearly tripled the K⁺ channel current activity elicited by heterotetrameric Kir3 channels in HEK293T cells. Thus, our method provides a useful template to control the oligomerization states of membrane protein complexes in vitro and in living cells.     

Synthesis,conformational preferences in gas and solution,and molecular gear rotation in 1-(dimethylamino)-1-phenyl-1-silacyclohexane by gas phase electron diffraction (GED), LT NMR and theoretical calculations

1-(Dimethylamino)-1-phenyl-1-silacyclohexane 1, was synthesized, and its molecular structure and conformational properties studied by gas-phase electron diffraction (GED), low temperature ¹³C NMR spectroscopy and quantum-chemical calculations. The predominance of the 1-Ph_ax conformer (1-Ph_eq:1-Ph_ax ratio of 20:80%, ΔG°(317?K)?=??0.87?kcal/mol) in the gas phase is close to the theoretically estimated conformational equilibrium. In solution, low temperature NMR spectroscopy showed analyzable decoalescence of C_ipso and C(1,5) carbon signals in ¹³C NMR spectra at 103?K. Opposite to the gas state in the freon solution employed (CD₂Cl₂/CHFCl₂/CHFCl₂?=?1:1:3), which is still liquid at 100?K, the 1-Ph_eq conformer was found to be the preferred one [(1-Ph_eq: 1-Ph_ax?=?77%: 23%, K?=?77/23?=?2.8; ?ΔG°?=??RT ln K (at 103?K)?=?0.44?±?0.1?kcal/mol]. When comparing 1 with 1-phenyl-1-(X)silacylohexanes (X?=?H, Me, OMe, F, Cl), studied so far, the trend of predominance of the Ph_ax conformer in the gas phase and of the Ph_eq conformer in solution is confirmed.     

Carbon-coated LiFePO4–carbon nanotube electrodes for high-rate Li-ion battery

Journal of Solid State Electrochemistry - Olivine LiFePO4 (LFP) is a promising cathode material for high-rated lithium-ion batteries. However, olivine faced a severe disadvantage of low...     

Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product

A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21?C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically.     

Quantum‐Tunneling Metal‐Insulator‐Metal Diodes Made by Rapid Atmospheric Pressure Chemical Vapor Deposition

A quantum‐tunneling metal‐insulator‐metal (MIM) diode is fabricated by atmospheric pressure chemical vapor deposition (AP‐CVD) for the first time. This scalable method is used to produce MIM diodes with high‐quality, pinhole‐free Al₂O₃ films more rapidly than by conventional vacuum‐based approaches. This work demonstrates that clean room fabrication is not a prerequisite for quantum‐enabled devices. In fact, the MIM diodes fabricated by AP‐CVD show a lower effective barrier height (2.20 eV) at the electrode–insulator interface than those fabricated by conventional plasma‐enhanced atomic layer deposition (2.80 eV), resulting in a lower turn on voltage of 1.4 V, lower zero‐bias resistance, and better asymmetry of 107.     

Biomimetic Natural Killer Membrane Camouflaged Polymeric Nanoparticle for Targeted Bioimaging

In the present study, a biomimetic nanoconstruct (BNc) with a multimodal imaging system is engineered using tumor homing natural killer cell membrane (NKM), near‐infrared (NIR) fluorescent dye, and gadolinium (Gd) conjugate‐based magnetic resonance imaging contrast agent onto the surface of a polymeric nanoparticle. The engineered BNc is 110 ± 20 nm in size and showed successful retention of NKM proteins. The magnetic properties of the BNc are found to be tunable from 2.1 ± 0.17 to 5.3 ± 0.5 mm ^?1 s^?1 under 14.1 T, by adjusting the concentration of Gd‐lipid conjugate onto the surface of the BNc. Confocal imaging and cell sorting analysis reveal a distinguishable cellular interaction of the BNc with MCF‐7 cells in comparison to that of bare polymeric nanoparticles suggesting the tumor homing properties of NKM camouflage system. The in vitro cellular interaction results are further confirmed by in vivo NIR fluorescent tumor imaging and ex vivo MR imaging, respectively. Pharmacokinetics and biodistribution analysis of the BNc show longer circulation half‐life (≈9.5 h) and higher tumor accumulation (10% of injected dose) in MCF‐7 induced tumor‐bearing immunodeficient NU/NU nude mice. Owing to the proven immunosurveillance potential of NK‐cell in the field of immunotherapy, the BNc engineered herein would hold promises in the design consideration of nanomedicine engineering.     

Ultrasonication‐Induced Self‐Assembled Fixed Nanogap Arrays of Monomeric Plasmonic Nanoparticles inside Nanopores

Monomeric gold (Au) and silver (Ag) nanoparticle (NP) arrays are self‐assembled uniformly into anodized aluminium oxide (AAO) nanopores with a high homogeneity of greater than 95%, using ultrasonication. The monomeric metal NP array exhibits asymmetric plasmonic absorption due to Fano‐like resonance as interpreted by finite‐difference time‐domain (FDTD) simulation for the numbers up to 127 AuNPs. To examine gap distance‐dependent collective‐plasmonic resonance, the different dimensions of S, M, and L arrays of the AuNP diameters/the gap distances of ≈36 nm/≈66 nm, ≈45 nm/≈56 nm, and ≈77 nm/≈12 nm, respectively, are prepared. Metal NP arrays with an invariable nanogap of ≈50 nm can provide consistent surface‐enhanced Raman scattering (SERS) intensities for Rhodamine 6G (Rh6G) with a relative standard deviation (RSD) of 3.8–5.4%. Monomeric arrays can provide an effective platform for 2D hot‐electron excitation, as evidenced by the SERS peak‐changes of 4‐nitrobenzenethiol (4‐NBT) adsorbed on AgNP arrays with a power density of ≈0.25 mW µm^‐2 at 514 and 633 nm. For practical purposes, the bacteria captured by 4‐mercaptophenylboronic acid are found to be easily destroyed under visible laser excitation at 514 nm with a power density of ≈14 mW µm^‐2 for 60 min using Ag due to efficient plasmonic‐electron transfer.